Frühjahrssymposium 2013 in Berlin - JungChemikerForum Berlin
Frühjahrssymposium 2013 in Berlin - JungChemikerForum Berlin
Frühjahrssymposium 2013 in Berlin - JungChemikerForum Berlin
Create successful ePaper yourself
Turn your PDF publications into a flip-book with our unique Google optimized e-Paper software.
1 5 th<br />
JCF-<strong>Frühjahrssymposium</strong><br />
March 6 th -9 th , 201 3<br />
Berl<strong>in</strong>
Sponsors
Impr<strong>in</strong>t<br />
<strong>JungChemikerForum</strong> Berl<strong>in</strong><br />
<strong>2013</strong><br />
LATEX realization by courtesy of the JCF Erlangen-Nürnberg<br />
We are grateful to Hans-Jörg Drescher for his help with the LATEX code.
Contents<br />
Greet<strong>in</strong>gs 1<br />
Program 7<br />
Information 15<br />
Plenary Lectures 23<br />
Prof. Hashmi (Thursday 9:30 - 10:30) 24<br />
Dr. Loth (Thursday 14:50 - 15:50) 26<br />
Dr. habil. Becker (Friday 9:10 - 10:10) 28<br />
Prof. Schre<strong>in</strong>er (Friday 14:50 - 15:50) 30<br />
Prof. Roth (Saturday 11:30 - 12:30) 32<br />
Oral Presentations 35<br />
Session 1 (Thursday 10:50 - 12:00) 36<br />
Session 2 (Thursday 13:30 - 14:30) 39<br />
Session 3 (Thursday 16:10 - 17:40) 42<br />
Session 4 (Friday 10:30 - 12:00) 46<br />
Session 5 (Friday 13:30 - 14:30) 50<br />
Session 6 (Friday 16:10 - 17:40) 53<br />
Posters 57<br />
Poster Session 1 (Thursday 17:40 - 20:10) 58<br />
Poster Session 2 (Saturday 9:00 - 11:30) 188<br />
Index 315<br />
Sudoku 329
Greet<strong>in</strong>gs<br />
1
Liebe Jungchemiker<strong>in</strong>nen und Jungchemiker,<br />
<strong>in</strong> diesem Jahr treffen Sie sich zu Ihrem Forum <strong>in</strong> Berl<strong>in</strong>, e<strong>in</strong>er Stadt, die dank ihrer<br />
zahlreichen Hochschulen und weiterer Forschungse<strong>in</strong>richtungen <strong>in</strong> besonderer Weise<br />
dazu geeignet ist, sich über Wissenschaft auszutauschen. Sie ist zugleich aber auch<br />
besonderes Symbol für Deutschland, für Vere<strong>in</strong>igung von Ost und West und für <strong>in</strong>ternationale<br />
Sichtbarkeit. Das s<strong>in</strong>d wichtige Charakteristika, wenn Sie mite<strong>in</strong>ander<br />
reden wollen über unsere Wissenschaft, die Chemie - ihre Inhalte, ihre Bedeutung<br />
und ihre Relevanz für die Zukunft unserer Gesellschaft!<br />
Bereits im letzten Jahr schrieb ich Ihnen, wie wichtig und gut ich es f<strong>in</strong>de, dass<br />
Sie mit der aufwändigen Organisation und Durchführung der jährlich stattf<strong>in</strong>denden<br />
Konferenz des Jungchemikerforums das persönliche Treffen und das Gespräch über<br />
elektronische Kommunikationswege setzen. Täglich erlebe ich <strong>in</strong> me<strong>in</strong>em Beruf als<br />
Professor<strong>in</strong> an e<strong>in</strong>er Universität, dass Ideen und E<strong>in</strong>sichten, gedankliche Fortschritte<br />
und neue wissenschaftliche Ergebnisse durch persönliche, barrierelose Gespräche und<br />
Diskussionen geboren werden oder zur Reife gelangen. Nur so ersetzen wir <strong>in</strong> me<strong>in</strong>er<br />
Überzeugung Rout<strong>in</strong>e und Mittelmass durch Inspiration und Exzellenz. Sie wissen es<br />
alle: E<strong>in</strong>e Gruppe von Menschen ist mehr als die Summe e<strong>in</strong>zelner Personen.<br />
In diesem S<strong>in</strong>ne wünsche ich Ihnen auch für <strong>2013</strong>, dass sie <strong>in</strong> Berl<strong>in</strong> die Fasz<strong>in</strong>ation<br />
von Wissenschaft und menschlicher Begegnung spüren, <strong>in</strong> überdurchschnittlichen,<br />
anspruchsvollen und kurzweiligen Vorträgen, an Postern, <strong>in</strong> Diskussionsrunden und<br />
bei geselligen Treffen.<br />
Prof. Dr. Barbara Albert<br />
(Präsident<strong>in</strong> der Gesellschaft Deutscher Chemiker e.V.)<br />
2
Dear “Jungchemiker“,<br />
it provides me with great pleasure to welcome all of you to the 15 th JCF Spr<strong>in</strong>g<br />
Symposium here at Berl<strong>in</strong>’s Humboldt-Universität. Based on the great tradition of<br />
this unique event, I am absolutely conv<strong>in</strong>ced that you will enjoy the next few days<br />
with lots of excit<strong>in</strong>g new chemistry, <strong>in</strong>spir<strong>in</strong>g discussions, and joyful moments.<br />
Right from the beg<strong>in</strong>n<strong>in</strong>g, I wish to thank all of the people, who were <strong>in</strong>volved <strong>in</strong> the<br />
excellent organization. After all it is an event for young chemists by young chemists<br />
and you did a marvelous job.<br />
I am particularly grateful that this event has developed <strong>in</strong> such a success story as it<br />
br<strong>in</strong>gs together the people, who actually DO the science. While academic supervisors<br />
are concerned with arguably too much management, adm<strong>in</strong>istration, and politics, it is<br />
mostly doctoral students such as YOU, who are carry<strong>in</strong>g out experiments on a daily<br />
basis thereby pav<strong>in</strong>g the way to new scientific discoveries. The JCF Spr<strong>in</strong>g Symposia<br />
are a great platform to meet and get to know the person beh<strong>in</strong>d a specific type of<br />
research. After all, science is be<strong>in</strong>g carried out by <strong>in</strong>dividuals and it’s communication<br />
among them that makes science a unique social endeavor as well.<br />
In this spirit, I wish you a great and successful symposium – enjoy the chemistry <strong>in</strong><br />
all dimensions!<br />
Prof. Stefan Hecht, Ph.D.<br />
(Dean of the Faculty of Mathematics and Natural Sciences I of the Humboldt-Universität<br />
zu Berl<strong>in</strong>)<br />
3
Dear Participants,<br />
it is my great pleasure to welcome you to this conference on behalf of the whole<br />
organiz<strong>in</strong>g team! We are the Berl<strong>in</strong> division of the Young Chemists Forum. Our<br />
members are either study<strong>in</strong>g chemistry or do<strong>in</strong>g their PhD work here <strong>in</strong> the capital<br />
of Germany.<br />
Berl<strong>in</strong> has got three universities with chemistry study<strong>in</strong>g courses as well as a few other<br />
colleges that pursue related topics. The local Young Chemists Forum meets once a<br />
month to exchange experiences, share ideas and also organize events.<br />
In the past two years, we have respectively hosted a one-day scientific symposium on<br />
the natural science campus of the Humboldt-Universität. This year, we have worked<br />
hard <strong>in</strong> order to <strong>in</strong>corporate our experiences <strong>in</strong>to this year’s <strong>Frühjahrssymposium</strong> to<br />
make it truly enjoyable for all of you. But a symposium like this would not be feasible<br />
without a long list of supporters. We are extremely grateful for the big number of<br />
<strong>in</strong>stitutes, companies and organizations that helped us <strong>in</strong> various ways to make this<br />
conference happen. We are also very thankful for all the helpers that lend us a hand<br />
and serve your coffee.<br />
Once aga<strong>in</strong>, welcome to Berl<strong>in</strong> and enjoy the conference!<br />
Christ<strong>in</strong> Büchner<br />
(Chair of the Young Chemists Forum Berl<strong>in</strong>)<br />
4
Dear participants of the 15 th <strong>Frühjahrssymposium</strong>,<br />
I am very pleased to welcome you on behalf of the <strong>JungChemikerForum</strong> to the <strong>Frühjahrssymposium</strong><br />
at the Humboldt-Universität zu Berl<strong>in</strong> this year.<br />
The cont<strong>in</strong>uous ris<strong>in</strong>g number of participants shows the obvious success of the <strong>Frühjahrssymposium</strong><br />
and the <strong>in</strong>creas<strong>in</strong>g need for communication between young scientists.<br />
But especially the great number of the <strong>in</strong>ternational students allows an <strong>in</strong>terest<strong>in</strong>g<br />
and wide-rang<strong>in</strong>g exchange of knowledge. In consideration of present scientific challenges,<br />
like <strong>in</strong>creas<strong>in</strong>g lack of raw materials, grow<strong>in</strong>g and age<strong>in</strong>g world population<br />
and related food supply and medical care, the motivated young scientists all over the<br />
world can contribute to solutions of problems of our everyday life by meet<strong>in</strong>g and<br />
exchang<strong>in</strong>g at a conference like the <strong>Frühjahrssymposium</strong>.<br />
The plann<strong>in</strong>g and carry<strong>in</strong>g out of such a big event would not be possible without<br />
a great team. For that reason I want to thank on behalf of all participants of the<br />
<strong>Frühjahrssymposium</strong> the organization team and the assistants for the great job. Furthermore<br />
I want to express my gratitude to all the companies for the f<strong>in</strong>ancial support.<br />
I wish all participants a pleasant time <strong>in</strong> Berl<strong>in</strong>, fruitful discussions, creative ideas<br />
and many new friends.<br />
Anna Hofmann<br />
(Chair of the Young Chemists Forum of the German Chemical Society)<br />
5
Program<br />
7
Wednesday (March 6 th )<br />
12:00 – 20:00 Registration<br />
Unter den L<strong>in</strong>den 6 - Foyer<br />
12:00 – 19:00 Strukturwettbewerb - Organized by JCF Jena<br />
Dorothenstr. 24 - Room 1.406<br />
16:00 – 20:00 JCF Sprechertreffen<br />
Dorothenstr. 24 - Room 1.103<br />
16:00 – 19:00 City Tour<br />
Unter den L<strong>in</strong>den 6<br />
16:00 – 17:00 Boat Trip<br />
Unter den L<strong>in</strong>den 6<br />
20:00 – 23:00 Welcome Reception - Sponsored by Lanxess<br />
Dorothenstr. 24 - Foyer<br />
8
Thursday (March 7 th )<br />
8:50 – 9:30 Open<strong>in</strong>g Ceremony<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Christ<strong>in</strong> Büchner<br />
Chair of the 15 th JCF <strong>Frühjahrssymposium</strong><br />
Prof. Dr. Peter Frensch<br />
Vice President for Research of the Humboldt-Universität zu Berl<strong>in</strong><br />
Prof. Dr. Stefan Hecht<br />
Dean of the Faculty of Mathematics and Natural Sciences I<br />
Prof. Dr. Eckhard Ottow<br />
Vice President of the German Chemical Society (GDCh)<br />
Anna Hofmann<br />
Chair of the Young Chemists Forum (JCF)<br />
9:30 – 10:30 Plenary Lecture<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Prof. Dr. S. Hashmi - Ruprecht-Karls-Universität Heidelberg<br />
"Gold Catalysis 2.0"<br />
10:50 – 12:00 Session 1<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Anne-Kathr<strong>in</strong> Baum - Universität Hamburg<br />
"Sugar Complexes and the Asymmetric Transfer Hydrogenation"<br />
Laith Almazahreh - Friedrich-Schiller-Universität Jena<br />
"Novel [FeFe] Hydrogenase Models with (SCH2)2P=O L<strong>in</strong>ker"<br />
Burkhard Butschke - The Weizmann Institute of Science, Rehovot<br />
"From ’Rollover’ Cyclometalation towards the Catalytic<br />
Dehydrogenation of Alkanes"<br />
12:00 – 12:20 Conference Photo<br />
Unter den L<strong>in</strong>den 6<br />
9
13:30 – 14:30 Session 2<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Björn Raimer - Technische Universität Braunschweig<br />
"New Insights <strong>in</strong>to the Chemistry of Photoaff<strong>in</strong>ity Label<strong>in</strong>g with<br />
Diazir<strong>in</strong>es"<br />
Chiara Palumbo - Sapienza University of Rome<br />
"Asymmetric synthesis of Natural-product-<strong>in</strong>spired Spiro<br />
epoxyox<strong>in</strong>doles via Hydrogen-Bond Organocatalysis"<br />
Guillaume Povie - Universität Bern<br />
"Polar Effects <strong>in</strong> Hydrogen Atom Transfers from Catechols<br />
to Alkyl Radicals"<br />
14:50 – 15:50 Plenary Lecture<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Dr. S. Loth - Center for Free-Electron Laser Science, Hamburg<br />
"Atom-by-atom assembly of stable nanomagnets"<br />
16:10 – 17:40 Session 3<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Maria Wuithschick - Humboldt-Universität zu Berl<strong>in</strong><br />
"Understand<strong>in</strong>g the Growth Mechanism: Key to Size Control<br />
of Colloidal Nanoparticles"<br />
Lydia Liebscher - Technische Universität Dresden<br />
"PbS-mesocrystals - Coherence between atomistic arrangement<br />
and <strong>in</strong>ternal nanocrystal superstructure order<strong>in</strong>g"<br />
Jonathan De Roo - Ghent University<br />
"Synthesis of BaZrO3, Ta2O5 and HfO2 nanoparticles as artificial<br />
p<strong>in</strong>n<strong>in</strong>g centers <strong>in</strong> High Temperature Superconductors"<br />
Krzysztof Sozanski - Polish Academy of Sciences, Warsaw<br />
"Viscosity at the Nanoscale"<br />
17:40 – 20:10 Poster Session 1 and Champagne Reception<br />
Unter den L<strong>in</strong>den 6 - Senatssaal<br />
10
Friday (March 8 th )<br />
9:10 – 10:10 Plenary Lecture<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Dr. habil. J. S. Becker - Forschungszentrum Jülich<br />
"Mass Spectrometry Imag<strong>in</strong>g (MSI) of Elements <strong>in</strong> Biological Tissue"<br />
10:30 – 12:00 Session 4<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Gerrit Hermann - BOKU Wien<br />
"Study<strong>in</strong>g arsenic <strong>in</strong> cancer cells by elemental speciation analysis"<br />
Inga Pfeffer - University of Oxford<br />
"2-Oxoglutarate Oxygenases as Therapeutic Targets"<br />
Fernando Gomollon-Bel - Universidad de Zaragoza<br />
"Design and synthesis of fungical transglycosidase <strong>in</strong>hibitors"<br />
Aleksandra Kubica - Jagiellonian University, Krakow<br />
" 2 H NMR spectroscopy <strong>in</strong> application to selected am<strong>in</strong>o-acids"<br />
13:30 – 14:30 Session 5<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
P. Skup<strong>in</strong>-Mrugalska - Poznan University of Medical Sciences<br />
"Synthesis and development of the novel phthalocyan<strong>in</strong>e derivatives<br />
possess<strong>in</strong>g 2-(morphol<strong>in</strong>-4-yl)ethyloxy groups of potential applications<br />
<strong>in</strong> photodynamic therapy"<br />
Sören Gehne - University of Potsdam<br />
"Novel drug carrier systems - Spectroscopic characterization<br />
of cell-penetrat<strong>in</strong>g peptide analogous"<br />
Torsten Rossow - Freie Universität Berl<strong>in</strong><br />
"Controlled Synthesis of Cell-Laden Degradable Microgels by<br />
Radical-Free and Supramolecular Gelation <strong>in</strong> Droplet Microfluidics"<br />
14:50 – 15:50 Plenary Lecture<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Prof. Dr. P. R. Schre<strong>in</strong>er - Justus-Liebig Universität Giessen<br />
"Tunnel<strong>in</strong>g Control of Chemical Reactions"<br />
11
16:10 – 17:40 Session 6<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Ismael Gracia - Universidad de Zaragoza<br />
"Liquid Crystal and Electro-Optic Block Codendrimers:<br />
Synthesis and Characterization"<br />
Nicolas Dietl - Technische Universität Berl<strong>in</strong><br />
"Great Insights from a Small System: Structure and reactivity<br />
of [VPO4] + <strong>in</strong> comparison with [V2O4] + "<br />
Gregor Koch - Technische Universität Berl<strong>in</strong><br />
"Comparison of different Cu particles supported on SBA-15 as<br />
methanol steam reform<strong>in</strong>g catalysts"<br />
Maria Fritz - Lomonosov Moscow State University<br />
"New Trifluoromethyl Derivatives of 5 IPR Isomers the<br />
Fullerene C84"<br />
19:00 – 21:30 Conference D<strong>in</strong>ner<br />
Unter den L<strong>in</strong>den 6 - Zeltmensa<br />
22:00 Conference Party<br />
Revaler Straße 99 - Cassiopeia<br />
12
Saturday (March 9 th )<br />
9:00 – 11:30 Poster Session 2 and "Frühschoppen"<br />
Unter den L<strong>in</strong>den 6 - Senatssaal<br />
11:30 – 12:30 Clos<strong>in</strong>g Lecture<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
Prof. Dr. K. Roth - Freie Universität Berl<strong>in</strong><br />
"’Berl<strong>in</strong>er Currywurst’ - Some like it hot"<br />
12:30 – 13:30 Clos<strong>in</strong>g Ceremony<br />
Unter den L<strong>in</strong>den 6 - K<strong>in</strong>osaal<br />
14:00 – 17:00 Paper Chase<br />
Unter den L<strong>in</strong>den 6<br />
14:20 – 17:30 Memorial Hohenschönhausen<br />
Unter den L<strong>in</strong>den 6<br />
17:00 – 18:30 Berl<strong>in</strong> Underworld<br />
Badstraße/Böttgerstraße<br />
13
Information<br />
15
Poster Sessions<br />
There will be two poster sessions. To f<strong>in</strong>d out <strong>in</strong> which session your poster is, go to<br />
the <strong>in</strong>dex of this book and look up your name. Go to the page which is <strong>in</strong>dicated<br />
there. Beneath your abstract you’ll f<strong>in</strong>d the session you are <strong>in</strong>. The poster number<br />
right next to the session you’ll need to f<strong>in</strong>d your poster wall.<br />
If your poster is part of the first session: You may put up your poster dur<strong>in</strong>g Thursday<br />
afternoon. S<strong>in</strong>ce the room is used for a different event dur<strong>in</strong>g Friday, please remove<br />
your poster directly after the poster session. Posters that rema<strong>in</strong> after the end of the<br />
poster session will be removed.<br />
If your poster is part of the second session: You may put up your poster on Saturday<br />
morn<strong>in</strong>g right before your poster session. Please remove your poster before the start<br />
of the social activities. Posters that rema<strong>in</strong> after 2 pm will be removed.<br />
Poster Prize<br />
The prizes for the best posters will be awarded by all participants. All posters with<br />
highlight<strong>in</strong>g talks will be awarded <strong>in</strong> their separate category. Each participant can<br />
cast TWO votes for EACH poster session. Both on Thursday and on Saturday each<br />
participant can vote for one highlighted poster and one other poster.<br />
For the Thursday session, please drop your ballot <strong>in</strong>to the box (located <strong>in</strong> foyer of<br />
poster session) by the end of the Thursday session. For the Saturday session, please<br />
drop your ballot <strong>in</strong>to the box (located <strong>in</strong> foyer of poster session) by the end of the<br />
Saturday session.<br />
All prizes for best posters and best talks will be handed over <strong>in</strong> the Clos<strong>in</strong>g Ceremony<br />
on Saturday morn<strong>in</strong>g.<br />
Information regard<strong>in</strong>g Social Activities<br />
At the registration desk you will receive vouchers for the social events that you booked.<br />
Please have your vouchers ready for the respective social events.<br />
On Wednesday<br />
City Tour:<br />
Meet at the Humboldt-Universität ma<strong>in</strong> build<strong>in</strong>g near the registration desk at 15:50.<br />
Tour will take approximately 3 hours.<br />
Boat Trip:<br />
Meet at the Humboldt-Universität ma<strong>in</strong> build<strong>in</strong>g near the registration desk at 15:40.<br />
On Saturday<br />
Paper Chase:<br />
Meet near the <strong>in</strong>fo desk on Saturday at 14:00. Tour will take approximately 3 hours.<br />
Underworld Tours:<br />
Tour <strong>in</strong> English: Meet near the <strong>in</strong>fo desk on Saturday at 16:15 or come directly to the<br />
Bad- / corner Böttgerstraße, 13357 Berl<strong>in</strong> at 17:00. Tour <strong>in</strong> German: Meet near the<br />
<strong>in</strong>fo desk on Saturday at 17:15 or come directly to the Bad- / corner Böttgerstraße,<br />
13357 Berl<strong>in</strong> at 18:00. Tours will take approximately 1.5 hours.<br />
16
Memorial Hohenschönhausen:<br />
Meet near the <strong>in</strong>fo desk on Saturday at 14:20 or come directly to the Genslerstr. 13<br />
A, 13055 Berl<strong>in</strong> at 15:30. Tour will take approximately 2 hours.<br />
Lunch Options<br />
Around the ma<strong>in</strong> build<strong>in</strong>g of the Humboldt-Universität you will f<strong>in</strong>d various lunch<br />
options. In the yard of the ma<strong>in</strong> build<strong>in</strong>g, the student canteen of the Humboldt-<br />
Universität is located <strong>in</strong> the large white tent. If you want to have your lunch there,<br />
please come to the conference desk and buy a meal voucher worth 9 e (per day), as the<br />
canteen discourages payment with cash. Around the university, you can f<strong>in</strong>d various<br />
restaurants. The closer you get to either S-Bahnhof Friedrichstraße or S-Bahnhof<br />
Alexanderplatz, the larger will be the selection of <strong>in</strong>expensive food alternatives.<br />
Public Transport<br />
Dur<strong>in</strong>g the conference (Wednesday to Saturday) every participant may use the public<br />
transport <strong>in</strong> the zones A, B, C (Berl<strong>in</strong>, Potsdam and surround<strong>in</strong>gs) for free. You<br />
need your conference nametag and an ID card or passport. All <strong>in</strong>formation (routes,<br />
timetables etc.) on public transport may be found here: www.bvg.de<br />
WLAN Access<br />
If your home <strong>in</strong>stitute takes part <strong>in</strong> the eduroam project, you may use the WLAN<br />
<strong>in</strong>frastructure of the Humboldt-Universität by just logg<strong>in</strong>g <strong>in</strong> with your account from<br />
your home university. If you are not sure what eduroam is, please visit www.eduroam.org<br />
and ask your local IT adm<strong>in</strong>istrator for it.<br />
In case you can not use eduroam you may ask for a guest account at the registration<br />
desk. Unfortunatly this has several disadvantages: The connection is much slower and<br />
less stable and you have to accept the IT regulations of the Humboldt-Universität.<br />
Thus, please consider to use eduroam!<br />
Science Location Berl<strong>in</strong><br />
With its large number of scientific <strong>in</strong>stitutions, Berl<strong>in</strong> provides excellent opportunities<br />
for researchers from all over the world. Berl<strong>in</strong> is home to four universities (Freie Universität,<br />
Humboldt-Universität, Technische Unversität and Universität der Künste),<br />
several universities of the applied sciences and 70 non-university research <strong>in</strong>stitutions.<br />
The Charité hospital is the largest medic<strong>in</strong>e faculty <strong>in</strong> Europe. It is a perfect example<br />
of how basic and applied research are <strong>in</strong> symbiosis here <strong>in</strong> Berl<strong>in</strong>. You f<strong>in</strong>d unique<br />
research facilities like the synchrotron radiation source BESSY, the research reactor<br />
BER-II (both parts of the Helmholtz-Zentrum Berl<strong>in</strong> for Materials and Energy) and<br />
the free electron laser <strong>in</strong> the Fritz-Haber-Institute of the Max-Planck-Society. As<br />
an example for other research <strong>in</strong>stitutions the Max Delbrück Center for Molecular<br />
Medic<strong>in</strong>e, three additional Max-Planck-Institutes or the Federal Institute for Materials<br />
Research and Test<strong>in</strong>g should be mentioned.<br />
In so-called clusters of excellence, funded by the German government, different <strong>in</strong>stitutes<br />
collaborate on larger topics that are relevant from a social and economic<br />
17
standpo<strong>in</strong>t. UniCat is one of these clusters <strong>in</strong> Berl<strong>in</strong>. It deals with unify<strong>in</strong>g different<br />
concepts <strong>in</strong> heterogeneous, homogeneous and biological catalysis.<br />
Berl<strong>in</strong> was one of the first cities to host a "long night of the sciences". In this annual<br />
event, research <strong>in</strong>stitutes open their doors to the public to give people <strong>in</strong>sights <strong>in</strong>to<br />
the projects they research and the methods they use. Last year over 34,000 people<br />
came to the 73 participat<strong>in</strong>g academic <strong>in</strong>stitutions.<br />
Berl<strong>in</strong> at a Glance<br />
If you have a bit more time <strong>in</strong> Berl<strong>in</strong>, there is a large number of different places to go<br />
and th<strong>in</strong>gs to see. A few of our recommendations:<br />
Museums<strong>in</strong>sel<br />
It is the name for the northern part of an island <strong>in</strong> the center of Berl<strong>in</strong>, with five<br />
<strong>in</strong>ternationally significant museums. Last year this museum complex was visted by<br />
2,75 million people. It consists of the Altes Museum (antique collection), the Neues<br />
Museum (Prehistorical, Egyptian and Early History collections), the Alte Nationalgallerie<br />
(collection of Neoclassical, Romantic, Biedermeier, Impressionist and early<br />
Modernist artwork), the Bode-Museum (collection of sculptures, Byzant<strong>in</strong>e art, and<br />
co<strong>in</strong>s and medals) and the Pergamonmuseum (antiquity collection, the Middle East<br />
Museum, and the Museum of Islamic art).<br />
Naturkundemuseum<br />
It is the largest museum of natural history <strong>in</strong> Germany with 30 million zoological,<br />
paleontological, m<strong>in</strong>eralogical, and geological objects. The m<strong>in</strong>eral collection <strong>in</strong>cludes<br />
75 % of all m<strong>in</strong>erals <strong>in</strong> the world. Two spectacular exhibits are the largest mounted<br />
d<strong>in</strong>osaur <strong>in</strong> the world which is 23 m long and 12 m high and an exemplar of the<br />
earliest known bird, Archaeopteryx.<br />
Deutsches Technikmuseum Berl<strong>in</strong><br />
This museum exhibits a large collection of historical technical exhibition pieces, it<br />
is focused on the waterways and rail transport <strong>in</strong> / to Berl<strong>in</strong> and <strong>in</strong> Germany, the<br />
beer, jewelry production and energy. Also a reproduction of the Z1, the first freely<br />
programmable computer <strong>in</strong> the world, is shown.<br />
Old Airport Tempelhof<br />
Built <strong>in</strong> the 1920ies, this was the first airport <strong>in</strong> Berl<strong>in</strong>. The Nazis added a monumental<br />
airport build<strong>in</strong>g, the US Army used it as their air base after WWII. Dur<strong>in</strong>g<br />
the Berl<strong>in</strong> blockade <strong>in</strong> 1948/49, the airport was a major hub for the historic airlift<br />
that provided supplies for two million citizens. The airport was closed <strong>in</strong> 2008 and<br />
the area converted <strong>in</strong>to a recreational territory. A huge plane stretches <strong>in</strong> the middle<br />
of the city, allow<strong>in</strong>g runn<strong>in</strong>g, skat<strong>in</strong>g, bik<strong>in</strong>g, kit<strong>in</strong>g, areas for barbecues, lacrosse,<br />
baseball, urban garden<strong>in</strong>g and many more activities. You can visit for free daily from<br />
6 AM to 7 PM. Just get off the S-Bahn at station Tempelhof and walk for 5 m<strong>in</strong>utes.<br />
Views Above the City<br />
On Alexanderplatz, you f<strong>in</strong>d one of Berl<strong>in</strong>s landmarks: the 356 metres high TV tower.<br />
The visitors platform provides spectacular views <strong>in</strong> all directions. Just opposite to<br />
the TV Tower, also on Alexanderplatz, you can visit the 37th floor of the Park Inn<br />
Hotel and view the city centre. On Potsdamer Platz, you can use the fastest elevator<br />
<strong>in</strong> Europe to get to a platform with a view over all the important landmarks of Berl<strong>in</strong>.<br />
TV tower: 12 e pp http://www.tv-turm.de Park Inn: 3 e pp Just walk <strong>in</strong> and take<br />
18
the elevator to the top (only open <strong>in</strong> good weather) Panorama (Potsdamer Platz):<br />
5.50 e p.P. http://www.panoramapunkt.de<br />
Not a lot of time? Hop on public bus l<strong>in</strong>e 100!<br />
Operat<strong>in</strong>g from S Alexanderplatz to S Zoologischer Garten, this bus l<strong>in</strong>e takes you<br />
past a big number of the important sites <strong>in</strong> Berl<strong>in</strong>. There is Alexanderplatz, home to<br />
the Rotes Rathaus, the town hall of Berl<strong>in</strong> and the most famous landmark of Berl<strong>in</strong>,<br />
the TV tower which is the tallest structure <strong>in</strong> Germany. St. Marys Church is one of<br />
the oldest churches <strong>in</strong> Berl<strong>in</strong>, the exact age is unknown. The Nikolaiviertel is the reconstructed<br />
historical heart of the city with the oldest church <strong>in</strong> Berl<strong>in</strong> Nikolaikirche,<br />
build between 1220 and 1230. The Staatsoper Berl<strong>in</strong> unfortunately is under reconstruction<br />
at the moment, but you can try to get a glance across Bebelplatz at the very<br />
beautiful Alte Bibliothek. On the other site of the street you can f<strong>in</strong>d the ma<strong>in</strong> build<strong>in</strong>g<br />
of Humboldt-Universität. The Brandenburger Tor is a build<strong>in</strong>g that is attached<br />
to a lot of German history. When the copper statue of the victory goddess was first<br />
put on top, the citizens compla<strong>in</strong>ed that the lady was wear<strong>in</strong>g too reveal<strong>in</strong>g clothes,<br />
so the copper robe was added. Mark<strong>in</strong>g the border between Warsaw Pact and NATO,<br />
it was a symbol of the cold war. From 1990, it became a symbol for the reunification<br />
of Germany. The Reichstag build<strong>in</strong>g accommodates the German Parliament, called<br />
the Bundestag. After the abdication of the Kaiser <strong>in</strong> 1918, the first German republic<br />
was proclaimed to the public from one of the Reichstags balconies. The Haus der<br />
Kulturen der Welt (Berl<strong>in</strong>ers call it the pregnant oyster because of its shape) was a<br />
gift from the United States of America and is the national centre for contemporary<br />
non-European art. Schloss Bellevue is the official residence of the German president.<br />
Due to many reconstruction periods and the representative rooms tak<strong>in</strong>g up a lot of<br />
space, there is only one German president who has actually lived <strong>in</strong> the castle (Roman<br />
Herzog). At the Großer Stern <strong>in</strong>tersection, <strong>in</strong> the center of the Großer Tiergarten,<br />
the Siegessäule watches over the west part of Berl<strong>in</strong>. It was built after a series of wars<br />
that lead to the unification of the many small states to the Kaiserreich. In the late<br />
90s, the Siegessäule was the focal po<strong>in</strong>t for the annual Loveparade, one of the largest<br />
Techno festivals at that time. Beh<strong>in</strong>d the park lies the Potsdamer Platz, an example<br />
for the ’new Berl<strong>in</strong>’ and the urban renewal after the cold war. On the place stands<br />
a replica of the first traffic light <strong>in</strong> Berl<strong>in</strong> from the year 1924. The Breitscheidplatz<br />
lies at one end of the most prestigious shopp<strong>in</strong>g street of the city, the Kurfürstendamm.<br />
Its most strik<strong>in</strong>g build<strong>in</strong>g is the Kaiser-Wilhelm-Gedächtnis-Kirche, which<br />
was heavily damaged <strong>in</strong> World War II, and is kept <strong>in</strong> its state as a war memorial.<br />
The remarkably large church bells, which were made out of cannon balls captured <strong>in</strong><br />
the German-French war (1871) were repurposed for weaponry <strong>in</strong> 1943. The Zoologischer<br />
Garten is a zoo that also consists of a very large aquarium where mar<strong>in</strong>e animals<br />
as well as reptiles, amphibians and <strong>in</strong>sects can be found.<br />
Personal Recommodation of the Organizers<br />
District Friedrichsha<strong>in</strong>:<br />
In the triangle between S Warschauer Straße, S Ostkreuz and U Samariterstraße you<br />
will f<strong>in</strong>d a large selection of bars, restaurants and pubs. Just start at one corner and<br />
f<strong>in</strong>d someth<strong>in</strong>g you like.<br />
Near the conference venue:<br />
Along the Oranienburger Straße you will f<strong>in</strong>d many <strong>in</strong>ternational bars and restaurants.<br />
Start at S Oranienburger Straße and walk through the Oranienburger Straße<br />
19
or the small byroads. Or take a small walk start<strong>in</strong>g at the conference hall along the<br />
Friedrichstraße.<br />
Burger Restaurant Rosenburger – Brunnenstr. 196, 10119 Berl<strong>in</strong>-Prenzl. Berg<br />
At U Rosenthaler Platz, <strong>in</strong> Brunnenstr. 196, you get served some of the nicest burgers<br />
<strong>in</strong> Berl<strong>in</strong>. You can choose from a range of topp<strong>in</strong>gs and organic meat patties are<br />
available as well. Homemade curly fries are my personal favourite.<br />
Que Pasa – Skalitzer Str. 107, 10997 Berl<strong>in</strong>-Kreuzberg or Oranienburger Str. 27,<br />
10117 Berl<strong>in</strong>-Mitte Here you can eat mexican food or dr<strong>in</strong>k tasty cocktails. My<br />
personal favourite is Chilli con Carne. If you are with a bigger group, you should try<br />
this bar, as they have a bit more space.<br />
Hops & Barley – Wühlischstr. 22/23, 10245 Berl<strong>in</strong>-Friedrichsha<strong>in</strong> This pub has<br />
its own brewery and serves several homebrewed beers and cider.<br />
Aspendos – Hauptstraße 11, 10827 Berl<strong>in</strong>-Schöneberg This little restaurant has<br />
Turkish specialities (<strong>in</strong>clud<strong>in</strong>g the Berl<strong>in</strong> default fast food - the Döner) <strong>in</strong> great quality.<br />
Varadero – Vorbergstraße 11, 10823 Berl<strong>in</strong> This Cuban restaurant serves great<br />
typical food. The music and overall atmosphere are perfect, and they make good<br />
cocktails.<br />
Paules Metal Eck – Krossener Straße 15, 10245 Berl<strong>in</strong>-Friedrichsha<strong>in</strong> For friends<br />
of metal musik, Paules Metal Eck can be recommended.<br />
Vapiano – Mittelstraße 51, 10117 Berl<strong>in</strong> This self service restaurant offers you delicious<br />
low budget mediterranean food.<br />
Villa Rixdorf – Richardplatz, 12055 Berl<strong>in</strong> There you can eat good traditional fare<br />
<strong>in</strong> a characteristic german atmosphere.<br />
Important Telephone Numbers<br />
20<br />
Police 110<br />
Ambulance & Fire Department 112<br />
Taxi (english speak<strong>in</strong>g) (+49) 30 20 20 21 22 0<br />
Poison hotl<strong>in</strong>e (+49) 30 19 2 40<br />
Emergency dental service (<strong>in</strong>formation) (+49) 30 89 00 43 33<br />
National enquiries (+49) 11 8 33<br />
International enquiries (+49) 11 8 34<br />
BVG (public transport) customer services (+49) 30 19 4 49<br />
Central (public) lost property office (+49) 30 902 77 31 01
Map of the Conference Venue – Unter den L<strong>in</strong>den 6<br />
21
Plenary Lectures<br />
23
Curriculum Vitae<br />
Prof. Dr. A. Stephen K. Hashmi<br />
Professor for Chemistry<br />
Organisch-Chemisches Institut<br />
Ruprecht-Karls-Universität Heidelberg<br />
Im Neuenheimer Feld 270<br />
69120 Heidelberg<br />
Germany<br />
hashmi@hashmi.de<br />
www.hashmi.de<br />
2007 – Chair for Organic Chemistry at the Institute of Organic Chemistry of the<br />
Ruprecht-Karls-University Heidelberg, Germany<br />
2001 – 2007 Appo<strong>in</strong>ted to professor for Organic Chemistry at the Institute of Organic<br />
Chemistry of Stuttgart University, Germany<br />
1999 – 2000 Temporary professorship for organic chemistry at the Department of<br />
Chemistryof Philipps-University Marburg, Germany<br />
1998 End of the Habilitation with the <strong>in</strong>itiation-lecture as Privatdozent at the<br />
Institute of Organic Chemistry of Johann Wolfgang Goethe-Universität<br />
Frankfurt, Germany<br />
1995 Move with Prof. Dr. J. Mulzer to the Institute of Organic Chemistry of<br />
Johann Wolfgang Goethe-University Frankfurt, Germany<br />
1993 Beg<strong>in</strong>n<strong>in</strong>g of the Habilitation <strong>in</strong> the group of Prof. Dr. J. Mulzer at the<br />
Institute of Organic Chemistry of Free University Berl<strong>in</strong>, Germany<br />
1991 – 1993 Postdoctoral studies <strong>in</strong> the group of Prof. B. M. Trost at Stanford University,<br />
California, USA<br />
1983 – 1991 Chemistry studies at Ludwig-Maximilians-University Munich, Germany;<br />
Diploma thesis <strong>in</strong> the group of Prof. Dr. G. Szeimies; Doctoral thesis <strong>in</strong><br />
the group of Prof. Dr. G. Szeimies<br />
Awards<br />
2010 Hector Research Award<br />
2007 Prize awarded by the students for the best lecture 2007 <strong>in</strong> Chemistry at<br />
Ruprecht-Karls-University Heidelberg<br />
2002 ORCHEM Prize for natural sciences of the German Chemical Society<br />
2001 Karl-Ziegler Memorial Fellowship<br />
1999 Heisenberg Fellowship of the Deutsche Forschungsgeme<strong>in</strong>schaft<br />
1998 Dr. Otto Röhm Memorial Fellowship<br />
1995 Habilitanden-fellowship of the Deutsche Forschungsgeme<strong>in</strong>schaft<br />
1993 Justus von Liebig Fellowship of the Fonds der Chemischen Industrie for<br />
the Habilitation<br />
1991 Postdoctoral fellowship of the Deutsche Forschungsgeme<strong>in</strong>schaft<br />
24 Thursday 9:30 - 10:30 Plenary: Prof. Hashmi
Gold Catalysis 2.0<br />
Stephen Hashmi<br />
The first decade of homogeneous gold catalysis has been dom<strong>in</strong>ated by simple nucleophilic<br />
addition reactions. [1] The field has experienced an exponential growth dur<strong>in</strong>g<br />
that time. With<strong>in</strong> the last 12 months new results <strong>in</strong>dicate very <strong>in</strong>terest<strong>in</strong>g new options,<br />
which are based on entirley new reactivity patterns and complex catalytic<br />
cycles. [2]<br />
[1] a) A. S. K. Hashmi, G. J. Hutch<strong>in</strong>gs, Angew. Chem. 2006, 118, 8064-8105; Angew. Chem.<br />
Int. Ed. 2006, 45, 7896-7936; b) M. Rudolph, A. S. K. Hashmi, Chem. Soc. Rev. 2012, 41,<br />
2448-2462.<br />
[2] a) R. Döpp, C. Lothschütz, T. Wurm, M. Pernpo<strong>in</strong>tner, S. Keller, F. Rom<strong>in</strong>ger, A. S. K. Hashmi,<br />
Organometallics 2011, 30, 5894-5903; b) A. S. K. Hashmi, I. Braun, P. Nösel, J. Schädlich, M.<br />
Wieteck, M. Rudolph, F. Rom<strong>in</strong>ger, Angew. Chem. 2012, 124, 4532-4536; Angew. Chem. Int.<br />
Ed. 2012, 51, 4456-4460; c) A. S. K. Hashmi, M. Wieteck, I. Braun, M. Rudolph, F. Rom<strong>in</strong>ger,<br />
Angew. Chem. 2012, 124, 10785-10789; Angew. Chem. Int. Ed. 2012, 51, 10633-10637.<br />
Plenary: Prof. Hashmi Thursday 9:30 - 10:30 25
Curriculum Vitae<br />
Dr. Sebastian Loth<br />
Group Leader<br />
Max Planck Research Department for Structural Dynamics<br />
Center for Free-Electron Laser Science<br />
Notkestrasse 85<br />
22607 Hamburg<br />
Germany<br />
sebastian.loth@mpsd.cfel.de<br />
www.fastatoms.de<br />
2011 – Max-Planck Research Group - Dynamics of Nanoelectronic Systems –<br />
Group Leader hosted at the Center for Free-Electron Laser Science, Hamburg,<br />
Germany and the Max-Planck Institute for Solid State Research,<br />
Stuttgart, Germany<br />
2008 – 2011 IBM Almaden Research Center, San Jose CA, USA – Postdoctoral Researcher<br />
exploration of atomically assembled nanostructures for novel<br />
schemes <strong>in</strong> data-storage and quantum <strong>in</strong>formation process<strong>in</strong>g<br />
2007 Ph.D. degree <strong>in</strong> Physics, IV. Physikalisches Institut (Semiconductor<br />
Physics) studies of nanoscale phenomena <strong>in</strong> operat<strong>in</strong>g semiconductor elements<br />
us<strong>in</strong>g low-temperature scann<strong>in</strong>g tunnell<strong>in</strong>g microscopy, Georg-<br />
August-University of Gött<strong>in</strong>gen, Germany<br />
2004 Diploma degree <strong>in</strong> Physics, Georg-August-University of Gött<strong>in</strong>gen, Germany<br />
2001 – 2002 General Manager – Olesno Konstrukcje + Montaz Sp. z o. o., Zabrze,<br />
Poland adm<strong>in</strong>istration and time schedul<strong>in</strong>g for assembly of <strong>in</strong>dustrial<br />
wood process<strong>in</strong>g plants<br />
2001 Intermediate diploma, University of Bielefeld, Germany<br />
Awards<br />
2008 – 2010 Feodor-Lynen research scholarship of the Alexander von Humboldt foundation<br />
2007 Dissertation award of the Berl<strong>in</strong>er-Ungewitter foundation<br />
2005 – 2007 Doctorate scholarship of the German National Academic Foundation<br />
26 Thursday 14:50 - 15:50 Plenary: Dr. Loth
Atom-by-atom assembly of stable nanomagnets<br />
Sebastian Loth<br />
The scann<strong>in</strong>g tunnel<strong>in</strong>g microscope has changed our view of the nanoworld. Atoms are<br />
no longer <strong>in</strong>tangible objects. They can be imaged <strong>in</strong>dividually and even manipulated<br />
<strong>in</strong>to structures that do not exist naturally.<br />
We focus on magnetic nanostructures and test how classical concepts of magnetism<br />
emerge from the quantum mechanical behavior of <strong>in</strong>dividual atoms. We use a lowtemperature<br />
scann<strong>in</strong>g tunnel<strong>in</strong>g microscope (STM) and assemble the nanostructures<br />
from different transition metal elements. Inelastic tunnel<strong>in</strong>g spectroscopy serves as<br />
a highly sensitive tool to achieve chemical identification of the atoms and to resolve<br />
their magnetic properties.<br />
With this technique we can quantify magnetic exchange <strong>in</strong>teraction and follow the<br />
evolution of magnetic states as we build the nanostructure one atom at a time. This<br />
makes it possible to optimize arrangements of atoms that either enhance or reduce<br />
magnetic stability. We identified a new route to create stable magnetic states us<strong>in</strong>g<br />
antiferromagnetic sp<strong>in</strong>-sp<strong>in</strong> <strong>in</strong>teraction enabl<strong>in</strong>g a model demonstration of dense<br />
magnetic memory with only 12 atoms per bit. [1]<br />
[1] Sebastian Loth, Susanne Baumann, Christopher P. Lutz, D. M. Eigler, Andreas J. He<strong>in</strong>rich,<br />
Science 2012, 335, 196.<br />
Plenary: Dr. Loth Thursday 14:50 - 15:50 27
Curriculum Vitae<br />
2009 – Head of Bra<strong>in</strong>Met<br />
Dr. habil. J. Sab<strong>in</strong>e Becker<br />
Leader of trace and ultratrace analysis<br />
Forschungszentrum Jülich<br />
Analytik (ZEA-3)<br />
Wilhelm-Johnen-Str.<br />
52428 Jülich<br />
Germany<br />
s.becker@fz-juelich.de<br />
www.bra<strong>in</strong>met.de<br />
1997 – 2003 Deputy head of the Central Division of Analytical Chemistry<br />
1992 – Head of mass spectrometry, Central Division of Analytical Chemistry,<br />
Forschungszentrum Jülich<br />
1988 Habilitation on "Ultrasensitive Mass Spectrometric Techniques", University<br />
Leipzig<br />
1974 – 1991 Central Institute for Isotope and Radiation Research, Leipzig<br />
1974 Promotion <strong>in</strong> Quantum Chemistry, University Leipzig<br />
1967 – 1974 Studies of Chemistry, University Leipzig<br />
Awards<br />
2012 W<strong>in</strong>ter Conference Award on Plasma Spectrochemistry sponsored by<br />
Thermo Fisher Scientific, Tucson, Arizona<br />
2010 IUPAC Fellow (International Union of Pure and Applied Chemistry)<br />
2009 DGMS-Award "Massenspektrometrie <strong>in</strong> den Biowissenschaften" (Mass<br />
Spectrometry <strong>in</strong> the Bioscience)<br />
2001 – 2012 Different Guest Professorships at Universities and Research Centres<br />
<strong>in</strong>clud<strong>in</strong>g Bulgaria, Rumania, France, Czech Republic, Israel, Ch<strong>in</strong>a,<br />
Poland, Brazil, Thailand, Canada, Taiwan and the USA<br />
1999 – 2004 Guest professor: Nuclear Research Centre, Atomic Energy Authority,<br />
Cairo<br />
28 Friday 9:10 - 10:10 Plenary: Dr. habil. Becker
Mass Spectrometry Imag<strong>in</strong>g (MSI) of Elements <strong>in</strong> Biological<br />
Tissue<br />
J. Sab<strong>in</strong>e Becker<br />
The application of mass spectrometry with soft ionization techniques (ESI, electrospray<br />
ionization, and MALDI, matrix-assisted laser desorption ionization) <strong>in</strong> the life<br />
sciences for the detection and identification of biomolecules is already well established.<br />
The application of elemental mass spectrometry us<strong>in</strong>g laser ablation <strong>in</strong>ductively coupled<br />
plasma mass spectrometry (LA-ICP-MS) for the determ<strong>in</strong>ation of metals, metalloids<br />
and non-metals biological tissue is rather new and there is some hesitation <strong>in</strong><br />
accept<strong>in</strong>g this analytical method, although it offers many advantages. Elemental and<br />
biomolecular mass spectrometric methods are highly complementary. LA-ICP-MS, as<br />
a solid state mass spectrometric technique, allows the direct determ<strong>in</strong>ation of trace<br />
elements <strong>in</strong> biological and environmental samples and is applied for microlocal and<br />
imag<strong>in</strong>g technique of elements with spatial resolution <strong>in</strong> the µm range. [1-5] Based<br />
on the established rout<strong>in</strong>e Bra<strong>in</strong>Met technique (Bra<strong>in</strong>Met - Bioimag<strong>in</strong>g of Metals <strong>in</strong><br />
Bra<strong>in</strong> and Metallomics) <strong>in</strong> quantitative elemental imag<strong>in</strong>g us<strong>in</strong>g LA-ICP-MS with a<br />
spatial resolution between 200 to ∼ 10 µm, we developed the comb<strong>in</strong>ation of a laser<br />
microdissection apparatus to ICP-MS (LMD-ICP-MS) to imag<strong>in</strong>g of metals at higher<br />
spatial resolution (10 to < 1 µm) and develop a method comb<strong>in</strong><strong>in</strong>g elemental imag<strong>in</strong>g<br />
by LA/LMD-ICP-MS with molecular imag<strong>in</strong>g by MALDI-MS.<br />
Fig. 1: Mass spectrum of a l<strong>in</strong>e scan (top left) and images of selected metals and<br />
non-metals measured by LA-ICP-MS <strong>in</strong> rout<strong>in</strong>e mode. [4]<br />
On the basis of selected examples, it will be shown that the comb<strong>in</strong>ation of different elemental<br />
and biomolecular mass spectrometric techniques can solve analytical problems <strong>in</strong><br />
the life sciences. Future developments and trends will be discussed concern<strong>in</strong>g <strong>in</strong>strumental<br />
developments of new mass spectrometric techniques provid<strong>in</strong>g improvement of spatial<br />
resolution and high sensitivity with lower detection limits for different application areas <strong>in</strong><br />
life sciences.<br />
[1] J. S. Becker, Inorganic Mass Spectrometry: Pr<strong>in</strong>ciples and Application, J. Wiley and Sons:<br />
Chichester, 2007, 520 pages.<br />
[2] J. S. Becker et al., Mass Spectrom. Rev. 2010, 29, 156.<br />
[3] J. S. Becker, N. Jakubowski, Chem. Soc. Rev. 2009, 38 (7),1969-1983.<br />
[4] J. S. Becker, Int. J. Mass Spectrom. 2010, 289, 65-75.<br />
[5] J. S. Becker et al., Int. J. Mass Spectrom. 2011, 307, 3-15.<br />
Plenary: Dr. habil. Becker Friday 9:10 - 10:10 29
Curriculum Vitae<br />
Prof. Dr. Peter R. Schre<strong>in</strong>er<br />
Profssor for Organic Chemistry<br />
Institute of Organic Chemistry<br />
Justus-Liebig Universität Giessen<br />
He<strong>in</strong>rich-Buff-R<strong>in</strong>g 58<br />
35392 Giessen<br />
Germany<br />
Peter.R.Schre<strong>in</strong>er@org.chemie.uni-giessen.de<br />
www.chemie.uni-giessen.de/schre<strong>in</strong>er<br />
2002 – Full professor of Organic Chemistry, Justus-Liebig-University Giessen<br />
1999 – 2002 Associate Professor of Organic Chemistry, Univ. of Georgia, Athens, USA<br />
1996 – 1999 Habilitand, Georg-August-Universität Gött<strong>in</strong>gen<br />
1995 – 1996 Project Coord<strong>in</strong>ator, The Encyclopedia of Computational Chemistry<br />
1995 Ph.D. (Computational Chem., Prof. H. F. Schaefer III), UGA, Athens,<br />
USA<br />
1994 Dr. rer.nat. (Organic Chem., Prof. P. v. R. Schleyer), Univ. Erlangen<br />
1992 Dipl.Chem. (Organic Chem., Prof. P. v. R. Schleyer), Univ. Erlangen<br />
1991 M.Sc. (Organic Chem., Prof. R. K. Hill), UGA, Athens, USA<br />
Awards<br />
2012 Schulich Visit<strong>in</strong>g Professorship, Technion-Israel Institute of Technology<br />
2010 P. v. R. Schleyer Lectureship Award (University of Georgia, USA)<br />
2010 Lifetime Honorary Member, Israel Chemical Society<br />
2009 Török Lectureship Award (Eötvös University, Budapest, Hungary)<br />
2009 Chair, Gordon Research Conference on Physical-Organic Chemistry -<br />
Molecular Design and Synthesis (New Hampshire, USA)<br />
2003 Dirac Medal of the World Association of Theoretical and Computational<br />
Chemists<br />
2000 Research Innovation Award of the Research Corporation<br />
2000 Chemical Research Publicity Award , The University of Georgia<br />
1999 Chair, Gordon Research Conference on Physical-Organic Chemistry -<br />
Molecular Design and Synthesis (New Hampshire, USA)<br />
1999 Dirac Medal of the World Association of Theoretical and Computational<br />
Chemists<br />
1999 Research Innovation Award of the Research Corporation<br />
1997 – 1999 Chemical Research Publicity Award , The University of Georgia<br />
1996 Robert C. Anderson Memorial Award<br />
1995 Mart<strong>in</strong>-Reynolds-Smith-Award, American Chemical Society (ACS)<br />
1993 Karl-Giehrl-Prize, Best Promotion 1994, University of Erlangen-Nürnberg<br />
30 Friday 14:50 - 15:50 Plenary: Prof. Schre<strong>in</strong>er
Tunnel<strong>in</strong>g Control of Chemical Reactions [1,2]<br />
David Ley, Dennis Gerbig, Hans Peter Reisenauer, Jan Philipp Wagner, Peter R.<br />
Schre<strong>in</strong>er*<br />
Chemical reactivity is traditionally understood [3,4] <strong>in</strong> terms of k<strong>in</strong>etic versus thermodynamic<br />
control, [5,6] where<strong>in</strong> the driv<strong>in</strong>g force is the lowest activation barrier among<br />
the possible reaction paths or the lowest free energy of the f<strong>in</strong>al products, respectively.<br />
Here we expose quantum mechanical tunnel<strong>in</strong>g as a third driv<strong>in</strong>g force that<br />
can overwrite traditional k<strong>in</strong>etic control and govern reactivity based on nonclassical<br />
penetration of the potential energy barriers connect<strong>in</strong>g the reactants and products.<br />
These f<strong>in</strong>d<strong>in</strong>gs are exemplified with the first experimental isolation and full spectroscopic<br />
and theoretical characterization of the elusive hydroxycarbenes (R-C-OH,<br />
1) [7-10] that undergo facile [1,2]hydrogen tunnel<strong>in</strong>g to the correspond<strong>in</strong>g aldehydes<br />
under barriers of nearly 30.0 kcal mol −1 with half-lives of around 1-2 h even at<br />
experimental temperatures as low as 10 K, despite of the presence of paths with substantially<br />
lower barriers (e.g., CH-tunnel<strong>in</strong>g <strong>in</strong> 1b to 3 or rearrangement of 1c to 4).<br />
We will demonstrate that this is a general phenomenon, [11-13] as exemplified by other<br />
OH-tunnel<strong>in</strong>g examples such as the rotational isomerization of monomeric benzoic<br />
acid. [14] Such tunnel<strong>in</strong>g processes do not merely represent corrections to the reaction<br />
rate, they are the reaction rate, i.e., the completely control the reaction outcome. [1]<br />
[1]<br />
P. R. Schre<strong>in</strong>er, H. P. Reisenauer, D. Ley, D. Gerbig, C.-H. Wu, W. D. Allen, Science 2011,<br />
332, 1300.<br />
[2]<br />
D. Ley, D. Gerbig, P. R. Schre<strong>in</strong>er, Org. Biomol. Chem. 2012, 19, 3769.<br />
[3]<br />
H. Eyr<strong>in</strong>g, J. Chem. Phys. 1935, 3, 107.<br />
[4]<br />
M. G. Evans, M. Polanyi, Trans. Faraday Soc. 1935, 31, 875.<br />
[5]<br />
R. B. Woodward, H. Baer, J. Am. Chem. Soc. 1944, 66, 645.<br />
[6]<br />
A. G. Catchpole, E. D. Hughes, C. K. Ingold, J. Chem. Soc. 1944, 11, 8.<br />
[7]<br />
D. Gerbig, H. P. Reisenauer, C.-H. Wu, D. Ley, W. D. Allen, P. R. Schre<strong>in</strong>er, J. Am. Chem.<br />
Soc. 2010, 132, 7273.<br />
[8]<br />
D. Gerbig, D. Ley, H. P. Reisenauer, P. R. Schre<strong>in</strong>er, Beilste<strong>in</strong> J. Org. Chem. 2010, 6, 1061.<br />
[9]<br />
P. R. Schre<strong>in</strong>er, H. P. Reisenauer, F. C. Pickard IV, A. C. Simmonett, W. D. Allen, E. Mátyus,<br />
A. G. Császár, Nature 2008, 453, 906.<br />
[10]<br />
P. R. Schre<strong>in</strong>er, H. P. Reisenauer, Angew. Chem. Int. Ed. 2008, 47, 7071.<br />
[11]<br />
D. Gerbig, D. Ley, P. R. Schre<strong>in</strong>er, Org. Lett. 2011, 13, 3526.<br />
[12]<br />
D. Ley, D. Gerbig, J. P. Wagner, H. P. Reisenauer, P. R. Schre<strong>in</strong>er, J. Am. Chem. Soc.<br />
2011, 133, 13614.<br />
[13]<br />
D. Ley, D. Gerbig, P. R. Schre<strong>in</strong>er, Chem. Sci. <strong>2013</strong>, 2, <strong>in</strong> press.<br />
[14]<br />
S. Amiri, H. P. Reisenauer, P. R. Schre<strong>in</strong>er, J. Am. Chem. Soc. 2010, 132, 15902.<br />
Plenary: Prof. Schre<strong>in</strong>er Friday 14:50 - 15:50 31
Prof. Dr. Klaus Roth<br />
Professor Emeritus<br />
Institute of Chemistry and Biochemistry<br />
Freie Universität Berl<strong>in</strong><br />
Takustr. 3<br />
14195 Berl<strong>in</strong><br />
Germany<br />
klaus.roth@chemie.fu-berl<strong>in</strong>.de<br />
www.klausroth.de<br />
2000 – Professor at the Institute of Chemistry, Freie Universität Berl<strong>in</strong><br />
1991 – 2000 Director of Dahlem Conferences, Freie Universität Berl<strong>in</strong><br />
1990 Supernumerary professor, Freie Universität Berl<strong>in</strong><br />
1986 – 1988 Visit<strong>in</strong>g Professor, University of California San Francisco<br />
1981 Habilitation, Freie Universität Berl<strong>in</strong><br />
1979 – 1980 Postdoctoral research, Institute for Medical Research <strong>in</strong> Mill Hill, London<br />
1973 Promotion, Freie Universität Berl<strong>in</strong><br />
1964 – 1969 Studies of Chemistry, Freie Universität Berl<strong>in</strong><br />
Awards<br />
2008 Author award of the Gesellschaft Deutscher Chemiker for the book<br />
"Chemische Delikatessen"<br />
1986 – 1988 Max-Kade-Fellowship for a research stay as a Visit<strong>in</strong>g Associate Professor<br />
<strong>in</strong> the group of M.W. We<strong>in</strong>er, Department of Radiology, University of<br />
California, San Francisco<br />
1979 – 1980 DFG-fellowship for a research stay <strong>in</strong> the group of J. Feeney, Institute for<br />
Medical Research, London<br />
32 Saturday 11:30 - 12:30 Plenary: Prof. Roth
“Berl<strong>in</strong>er Currywurst” - Some like it hot<br />
Klaus Roth<br />
A typical local specialty <strong>in</strong> Berl<strong>in</strong> is the “Currywurst”, a fried sausage covered with a<br />
sauce based ma<strong>in</strong>ly on tomato ketchup and a mixture of more or less hot spices. It’s<br />
not a gourmet but fast food, and with an additional help<strong>in</strong>g of French fries it conta<strong>in</strong>s<br />
a four-digit number of kilocalories and keeps your stomach busy for a couple of hours.<br />
When you order a “Currywurst”, the person beh<strong>in</strong>d the counter may ask you how hot<br />
the sausage should be. You should answer quickly and exactly, because if you hesitate<br />
too long, people <strong>in</strong> the queue beh<strong>in</strong>d you will start to get nervous. In that critical<br />
moment solid chemical knowledge can be of great help.<br />
Indeed the biochemistry of Bell Pepper and Chili has many surprises to offer. The<br />
brilliant red color is based on the “paprika ketones”, compounds that only capsicum<br />
can synthesize. The extraord<strong>in</strong>ary pungency, which many humans all over the world<br />
enjoy so much, is due to capsaic<strong>in</strong> and dihydrocapsaic<strong>in</strong>, which are also compounds<br />
that only capsicum can produce. With all that knowledge about capsicums’s unique<br />
and outstand<strong>in</strong>g chemical achievements, you can order your “Currywurst”, more precisely,<br />
qualified, and relaxed, which can make a “Currywurst”, a delicious experience<br />
you shouldn’t miss. This is just another proof that chemistry not only can be excit<strong>in</strong>g<br />
but also taste good.<br />
Guten Appetit!<br />
Plenary: Prof. Roth Saturday 11:30 - 12:30 33
Oral Presentations<br />
35
Sugar Complexes and the Asymmetric Transfer<br />
Hydrogenation<br />
Anne-Kathr<strong>in</strong> Baum, Jürgen Heck<br />
Institut für Anorganische und Angewandte Chemie –<br />
Fachbereich Chemie, Universität Hamburg – Mart<strong>in</strong>-Luther-K<strong>in</strong>g-Platz 6 –<br />
20146 Hamburg – GER<br />
baum@chemie.uni-hamburg.de<br />
The use of carbohydrates as ligands offers the chance of transferr<strong>in</strong>g the natural<br />
chirality from the ligand not only to the complex but, us<strong>in</strong>g the derived complex <strong>in</strong><br />
asymmetric reactions, also to a prochiral substrate.<br />
Various carbohydrate ligands have been synthesised and applied <strong>in</strong> organometal complexes<br />
<strong>in</strong> our group. [1] Glucopyranosidato and allopyranosidato ligands with their<br />
oxygen donor atoms were applied <strong>in</strong> zirconium and titanium complexes present<strong>in</strong>g different<br />
structural motifs and a possible application <strong>in</strong> the hydroam<strong>in</strong>ation reaction. [2-5]<br />
The successful change of donor atoms from oxygen to nitrogen by synthesis of a diam<strong>in</strong>oglucoside<br />
ligand afforded the opportunity for synthesis of group 6 sugar carbonyl<br />
complexes. [6]<br />
To enable the use of sugar ligands <strong>in</strong> late transition metal complexes a N,O-motif was<br />
chosen for coord<strong>in</strong>ation. Three ligand precursors, am<strong>in</strong>oglucopyranoside 1, am<strong>in</strong>oallopyranoside<br />
2 and am<strong>in</strong>omannopyranoside 3, have been prepared and their coord<strong>in</strong>ation<br />
chemistry on ruthenium complexes of the type [Ru(η 6 − arene)Cl2]2 is be<strong>in</strong>g<br />
<strong>in</strong>vestigated. [7] The first promis<strong>in</strong>g results apply<strong>in</strong>g the derived complexes <strong>in</strong> the<br />
Asymmetric Transfer Hydrogenation have been achieved and are subject to further<br />
studies. [7]<br />
Just recently, the molecular structure of dichlorido(η 6 -p-cymene)(methyl-2am<strong>in</strong>o-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside-κN<br />
2 )ruthenium(II) 4 could be<br />
determ<strong>in</strong>ed. [7]<br />
Molecular Structure and Structural Formula of Complex 4<br />
[1]<br />
S. Tschersich, M. Böge, D. Schwidom, J. Heck, Rev. Inorg. Chem. 2011, 31(1), 27-55.<br />
[2]<br />
L. Jessen, E. T. K. Haupt, J. Heck, Chem. Eur. J. 2001, 7, 3791-3797.<br />
[3]<br />
D. Küntzer, L. Jessen, J. Heck, Chem. Commun. 2005, 5653-5655.<br />
[4]<br />
D. Küntzer, S. Tschersich, J. Heck, Z. Anorg. Allg. Chem. 2007, 633, 43-45.<br />
[5]<br />
D. Schwidom, D. Zeys<strong>in</strong>g, M. Schmidt, J. Heck, Eur. J. Inorg. Chem. 2009, 5295-5298.<br />
[6]<br />
C. Fowel<strong>in</strong>, A.Matyja, M. Schmidt, J.Heck, Z. Anorg. Allg. Chem. 2007, 633, 2395-2399.<br />
[7] A.-K. H. Baum, J. Heck manuscript <strong>in</strong> preparation.<br />
36 Thursday 11:00 - 11:20 Talk 01
Novel [FeFe] Hydrogenase Models with (SCH2)2P=O L<strong>in</strong>ker<br />
Laith Almazahreh ∗ , Wolfgang Weigand ∗ , Ulf Peter Apfel † , Wolfgang Imhof ∗ ,<br />
Helmar Görls ∗ , Manfred Rudolph ∗ , Mohammed El-khateeb ‡<br />
∗ Institut für Anorganische und Analytische Chemie – Friedrich-Schiller-Universität –<br />
Humboldtstraße 8 – Jena – GER<br />
† Department of Chemistry – Massachussetts Institute of Technology –<br />
77 Massachusetts Avenue – Cambridge – USA<br />
‡ Chemistry Department – Jordan University of Science and Technology – 22110 Irbid –<br />
JOR<br />
laithmazahreh@yahoo.com<br />
[FeFe] Hydrogenases are enzymes that have high efficiency to catalyze reduction of<br />
protons to form dihydrogen, which <strong>in</strong> microorganisms occur at potentials of -0.1 to<br />
-0.55 V. [1] These high catalytic efficiency and low energy features were the impetus to<br />
scientists for pav<strong>in</strong>g the way to macroscale hydrogen production, based on design<strong>in</strong>g<br />
of <strong>in</strong>expensive electrocatalyst that resembles the structure of the [FeFe] active site<br />
[Figure a]. [2] Protonation of the Fe-Fe core to form term<strong>in</strong>al or bridg<strong>in</strong>g hydride, as<br />
well as the nitrogen atom of the cofactor (SCH2)2NH is considered as a fundamental<br />
step <strong>in</strong> the function of the active site to catalyze the production of hydrogen. [3] The<br />
biological function of the azathiolate cofactor, (SCH2)2NH, is proposed to relay protons<br />
to and from the diiron core via agostic [Figure b] or hydrido-proton <strong>in</strong>teraction<br />
[Figure c]. [4-6] In our research we <strong>in</strong>troduce the synthesis of novel [FeFe] hydrogenase<br />
models, namely [Fe2(CO)5X][(µ-SCH2)2(Ph)P=O] (X = CO, PPh3, P(OEt)3) [Figure<br />
d] to <strong>in</strong>vestigate the <strong>in</strong>fluence of the P=O functionality and the ligand X toward<br />
the electrochemical and the electrocatalytic properties of the [Fe2S2] cluster <strong>in</strong> the<br />
presence of the weak acid, acetic acid, and moderately strong acids, trifluoro acetic<br />
acid and pyrid<strong>in</strong>ium cation. Here<strong>in</strong> we report a catalytic mechanism for reduction of<br />
protons where the P=O function as protonation site and hence can be <strong>in</strong>volved <strong>in</strong> proton<br />
relay. This protonation of the P=O functionality was proved by monitor<strong>in</strong>g the<br />
reaction of the complexes with HBF4·Et2O by IR and 31 P NMR spectroscopic methods.<br />
High level DFT calculations of the protonation by HBF4·Et2O or pyrid<strong>in</strong>ium<br />
acid have been carried out consider<strong>in</strong>g the P=O functionality and the dithiolato sulfur<br />
atoms as potential sites for protonation.<br />
[1]<br />
P. M. Vignais, B. Billoud, J. Meyer, JFEMS Microbiol. Rev. 2001, J25, 455.<br />
[2]<br />
C. Topf, U. Monkowius, G. Knör, J. Inorganic Chemistry Communications 2012, J21, 147.<br />
[3]<br />
M. G. I. Gal<strong>in</strong>ato, M. W. Whaley, D. Roberts, P. Wang, N. Lehnert, JEur. J. Inorg. Chem.<br />
2011, 1147.<br />
[4]<br />
Y. Nicolet, A. L. de Lacey, X. Vernede, V. M. Fernandez, C. E. Hatchikian, J. C. Fontecilla-<br />
Camps, J. Am. Chem. Soc. 2001, J123, 1596.<br />
[5]<br />
Y. Nicolet, B. J. Lemon, J. C. Fontecilla-Camps, J. W. Peters, JTrends Biochem. Sci. 2000,<br />
J25, 138.<br />
[6]<br />
Y. Nicolet, C. Cavazza, J. C. Fontecilla-Camps, J. Inorg. Biochem. 2002, J91, 1.<br />
Talk 02 Thursday 11:20 - 11:40 37
From “Rollover” Cyclometalation towards the Catalytic<br />
Dehydrogenation of Alkanes<br />
Burkhard Butschke ∗ , Helmut Schwarz †<br />
∗ Department of Organic Chemistry – The Weizmann Institute of Science – P.O.Box 26 –<br />
Rehovot – ISR<br />
† Institut für Chemie – Technische Universität Berl<strong>in</strong> – Straße des 17. Juni 135 –<br />
Berl<strong>in</strong> – GER<br />
burkhard.butschke@weizmann.ac.il<br />
“Rollover” cyclometalation, which constitutes a special case of the well-known cyclometalation<br />
reaction, requires decomplexation and rotation of the ligand as key steps<br />
prior to metal mediated C–H bond activation (1 → 2 + HX <strong>in</strong> Figure 1). [1] While<br />
“rollover”-cyclometalated complexes are well known for a long time, their reactivity<br />
has hardly been studied. In mass-spectrometric experiments, however, which constitute<br />
a powerful tool to probe chemical reactions <strong>in</strong> a highly idealized environment,<br />
this particular k<strong>in</strong>d of cyclometalated species exhibits a rich chemistry. [2] “Rollover”cyclometalated<br />
[Pt(bipy - H)] + (2) (bipy = 2,2’-bipyrid<strong>in</strong>e) is conveniently produced<br />
by electrospray ionization (ESI) of methanolic solutions of dimeric [Pt(CH3)2(µ-<br />
(CH3)2S)]2 and 2,2’-bipyrid<strong>in</strong>e. In ion/molecule reactions of this complex with ethane,<br />
the liberation of neutral ethene is observed concomitant with the formation of the<br />
plat<strong>in</strong>um-hydride complex [Pt(H)(bipy)] + (2 + C2H6 → 3 + C2H4, Figure 1). The<br />
latter species might, based on DFT results, undergo ejection of H2 via “rollover” cyclometalation<br />
to regenerate [Pt(bipy – H)] + (2) as demonstrated earlier for the correspond<strong>in</strong>g<br />
methyl and chloro complexes [Pt(X)(bipy)] + (1, X = CH3, Cl). [3] This<br />
sequence of processes might be regarded as a catalytic cycle for the oxidative dehydrogenation<br />
of ethane by “rollover”-cyclometalated [Pt(bipy - H)] + (2) as summarized<br />
<strong>in</strong> Figure 1. When the classically cyclometalated plat<strong>in</strong>um complexes [Pt(L - H)] +<br />
(L = 2-phenylpyrid<strong>in</strong>e, 7,8-benzoqu<strong>in</strong>ol<strong>in</strong>e) are subjected to reactions with ethane,<br />
similar processes occur as encountered for [Pt(bipy - H)] + (2), while the relative rates<br />
are drastically reduced when compared with the “rollover”-cyclometalated analogue.<br />
This observation is <strong>in</strong>terpreted <strong>in</strong> terms of a pathway that proceeds directly at the<br />
cyclometalated plat<strong>in</strong>um complexes <strong>in</strong>stead of tak<strong>in</strong>g the route via retro-“rollover” cyclometalation.<br />
This process, however, which generates [Pt(L - H)(H2)(C2H4)] + as an<br />
<strong>in</strong>termediate, is more energy demand<strong>in</strong>g, which expla<strong>in</strong>s the decreased relative rates.<br />
Figure 1: Illustration of the gas-phase generation of "rollover"-cyclometalated [Pt(bipy –<br />
H)] + (2) and its potential use for the catalytic dehydrogenation of ethane.<br />
[1] B. Butschke, H. Schwarz, Chem. Sci. 2012, 3, 308-326.<br />
[2] a) B. Butschke, M. Schlangen, D. Schröder, H. Schwarz, Chem. Eur. J. 2008, 14, 11050-<br />
11060; b) B. Butschke, M. Schlangen, D. Schröder, H. Schwarz, Int. J. Mass Spectrom. 2009,<br />
283, 3-8; c) B. Butschke, S. Ghassemi Tabrizi, H. Schwarz, Chem. Eur. J. 2010, 16, 3962-3969;<br />
d) B. Butschke, S. Ghassemi Tabrizi, H. Schwarz, Int. J. Mass Spectrom. 2010, 291, 125-132;<br />
e) B. Butschke, H. Schwarz, Int. J. Mass Spectrom. 2011, 306, 108-113; f) B. Butschke, H.<br />
Schwarz, Chem. Eur. J. 2012, 18, 14055-14062.<br />
[3] B. Butschke, H. Schwarz, Organometallics 2010, 29, 6002-6011.<br />
38 Thursday 11:40 - 12:00 Talk 03
New Insights <strong>in</strong>to the Chemistry of Photoaff<strong>in</strong>ity Label<strong>in</strong>g<br />
with Diazir<strong>in</strong>es<br />
Björn Raimer, Thomas L<strong>in</strong>del<br />
Chemistry – TU Braunschweig – Hagenr<strong>in</strong>g 30 – Braunschweig – GER<br />
b.raimer@tu-bs.de<br />
3-Aryl-3-trifluoromethyl-3H -diazir<strong>in</strong>es (TFD) developed by Brunner et al. [1] have<br />
been used as covalent l<strong>in</strong>kers <strong>in</strong> photoaff<strong>in</strong>ity labell<strong>in</strong>g (PAL), which aims at the<br />
identification an analysis of biological targets. Although a grow<strong>in</strong>g number of natural<br />
products and other biologically active molecules have been functionalized with a<br />
diazir<strong>in</strong>e moiety, relatively little has been improved regard<strong>in</strong>g the chemoselectivity of<br />
diazir<strong>in</strong>es. [2]<br />
Based on extensive quantum mechanical calculations search<strong>in</strong>g for suitable carbenes<br />
with a s<strong>in</strong>glet ground state, we <strong>in</strong>vestigated experimentally the selectivity of a 3-(pmethoxyphenyl)-3-trifluoromethyl-3H<br />
-diazir<strong>in</strong>e towards phenolic motifs. By deuteration<br />
experiments, we were able to show for the first time that electron rich positions<br />
are alkylated via a carbene-protonation mechanism, which becomes dom<strong>in</strong>ant if the<br />
ground state of the carbene is s<strong>in</strong>glet. [3]<br />
We are currently work<strong>in</strong>g on the design of sterically h<strong>in</strong>dered diazir<strong>in</strong>es which should<br />
ideally undergo only one chemoselective reaction with structural motifs present <strong>in</strong><br />
prote<strong>in</strong>s and nucleic acids. This would clearly facilitate the <strong>in</strong>terpretation of mass<br />
spectra of covalent ligand-prote<strong>in</strong> adducts formed by PAL and the <strong>in</strong>vestigation of<br />
b<strong>in</strong>d<strong>in</strong>g modes.<br />
1<br />
[1] J. Brunner, H. Senn, F. M. Richards, J. Biol. Chem. 1980, 255, 3313-3318.<br />
[2] Reviews: a) A. Blencowe, W. Hayes, Soft Matter 2005, 1, 178-205; b) L. Dub<strong>in</strong>sky, B. P.<br />
Krom, M. M. Meijler, Bioorg. Med. Chem. 2012, 20, 554-570.<br />
[3] B. Raimer, T. L<strong>in</strong>del, 2012, submitted.<br />
Talk 04 Thursday 13:30 - 13:50 39
Asymmetric synthesis of Natural-product-<strong>in</strong>spired Spiro<br />
epoxyox<strong>in</strong>doles via Hydrogen-Bond Organocatalysis<br />
Chiara Palumbo ∗ , Tecla Gasperi † , Andrea Mazziotta ∗ , Mart<strong>in</strong>a Miceli ∗ ,<br />
Maria Antonietta Loreto ∗ , Augusto Gambacorta †<br />
∗ Department of Chemistry – Sapienza University of Rome – Piazzale Aldo Moro 5 –<br />
Rome – ITA<br />
† Department of Sciences – University of Studies Roma Tre – Via della Vasca Navale 79 –<br />
Rome – ITA<br />
chiara.palumbo@uniroma1.it<br />
The spiroox<strong>in</strong>dolic core is among the most valuable build<strong>in</strong>g blocks, as it is featured<br />
<strong>in</strong> several natural products which are endowed of biological <strong>in</strong>terest<strong>in</strong>g properties. For<br />
<strong>in</strong>stance convolutamid<strong>in</strong>es, are proved to be anti-leukaemia agents. [1] Furthermore,<br />
epoxides bear<strong>in</strong>g a phosphonate moiety, like phosphonomyc<strong>in</strong>e, display a quite good<br />
antiviral and antibiotic activities. [2]<br />
Over the last decades organocatalysis has proved to be an excellent asymmetric activation<br />
mode, which can also be used to get new, challeng<strong>in</strong>g reactions and to mold<br />
highly complex scaffolds. [3] Hydrogen-bond <strong>in</strong>teractions have recently had a breakthrough<br />
<strong>in</strong> this field and, whereas covalent organocatalysis has broadly been explored,<br />
non covalent catalysis still represents a novelty for organic chemists. [4] For <strong>in</strong>stance<br />
<strong>in</strong>terest<strong>in</strong>g and very efficient examples of this activation mode have recently been<br />
reported by the use of thioureas, or conf<strong>in</strong>ed Brønsted acids, that have proved to be<br />
very efficient and selective <strong>in</strong> many k<strong>in</strong>ds of synthetic transformations. [5]<br />
Our research group has reported about the epoxidation of new 3-alkylidenox<strong>in</strong>doles<br />
bear<strong>in</strong>g a phosphonate group, because of the previously highlighted expected<br />
properties. [6] Moreover we have recently proved how prol<strong>in</strong>ol derivatives could act<br />
as H-bond<strong>in</strong>g catalysts towards this k<strong>in</strong>d of reaction. [7]<br />
Here<strong>in</strong> we report the last results of a H-bond<strong>in</strong>g catalysed, enantioselective, nucleophilic<br />
epoxidation of 3-alkylidenox<strong>in</strong>doles; this reaction, catalysed by prol<strong>in</strong>ol <strong>in</strong> a<br />
fast, mild way, gave us quite good results <strong>in</strong> terms of enantioselectivities (up to 93%<br />
ee), substrate scope (more than 30 spiro epoxyox<strong>in</strong>doles), and yields (up to 98% Y).<br />
We hypothesised a reaction mechanism which <strong>in</strong>volve a H-bond network between the<br />
catalyst/oxidant system and the olef<strong>in</strong>. We checked, as well, the effect on reactivity<br />
and selectivity of different substituents on the nitrogen atom, on the aromatic<br />
r<strong>in</strong>g, and on the exocyclic double bond, such as phosphonates which could result <strong>in</strong><br />
antiviral activity. [2]<br />
[1] S. Peddibhothla, CBC 2009, 5, 20.<br />
[2] M. Jackson, et al., Science 1969, 166, 122.<br />
[3] D. W. C. MacMillan, Nature 2008 455, 304.<br />
[4] E. N. Jacobsen, et al., ACIE, 2006, 45, 1520.<br />
[5] P. R. a) Schre<strong>in</strong>er, et al., CSR 2009, 38, 1187; b) List, B. et al., Nature, 2012, 483, 315; c)<br />
Lattanzi, A. CC 2009, 1452.<br />
[6] T. Gasperi, et al., EJOC 2011, 385.<br />
[7] T. Gasperi, et al., OL 2011, 13, 6248.<br />
40 Thursday 13:50 - 14:10 Talk 05
Polar Effects <strong>in</strong> Hydrogen Atom Transfers from Catechols to<br />
Alkyl Radicals<br />
Guillaume Povie, Giorgio Villa, Davide Pozzi, Leigh Ford, Philippe Renaud<br />
Department für Chemie und Biochemie – Universität Bern – Freiestrasse 3 – Bern – CH<br />
guillaume.povie@ioc.unibe.ch<br />
In comb<strong>in</strong>ation with organoboranes, 4-tert-butylcatechol can be used as an efficient<br />
hydrogen atom donor <strong>in</strong> radical cha<strong>in</strong> reactions. [1] This surpris<strong>in</strong>g behavior of a class<br />
of compounds generally seen as cha<strong>in</strong> break<strong>in</strong>g anti-oxydants allowed the development<br />
of a broad scope method for the reduction of organoboranes. [2] Extend<strong>in</strong>g this concept<br />
to the reduction of alkyl iodides, the hydrogen atom transfer step was found to<br />
be particularly sensitive to the polarity of the attack<strong>in</strong>g radical. While alkyl substituted<br />
radicals are efficiently reduced, electron poor radicals slowly react with catechol<br />
derivatives giv<strong>in</strong>g them sufficient lifetime to undergo addition reactions. This peculiar<br />
feature could be used to trigger <strong>in</strong>ter and <strong>in</strong>tramolecular processes such as the contrathermodynamic<br />
3-exo-trig cyclisation shown here. The Arrhenius parameters for<br />
the hydrogen atom transfer to different alkyl radicals could be determ<strong>in</strong>ed us<strong>in</strong>g substituted<br />
5-hexenyl radical clocks. The variations of the activation energies <strong>in</strong> function<br />
of the exothermicity of the reaction and of the polar effects affect<strong>in</strong>g the transition<br />
state are discussed.<br />
Catechol/triethylborane mediated 3-exo-trig radical cyclisation<br />
[1]<br />
G. Povie, G. Villa, L. Ford, D. Pozzi, C. H. Schiesser, P. Renaud, Chem.<br />
803-805.<br />
[2]<br />
G. Villa, G. Povie, P. Renaud, J. Am. Chem. Soc. 2011, 133, 5913-5920<br />
Commun. 2010,<br />
Talk 06 Thursday 14:10 - 14:30 41
Understand<strong>in</strong>g the Growth Mechanism: Key to Size Control<br />
of Colloidal Nanoparticles<br />
Maria Wuithschick, Klaus Rademann, Jörg Polte<br />
Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 –<br />
12489 Berl<strong>in</strong> – GER<br />
maria.wuithschick@hu-berl<strong>in</strong>.de<br />
Metal nanoparticles have attracted much attention due to their specific catalytic,<br />
optical and magnetic properties. These properties can be adjusted by alter<strong>in</strong>g size,<br />
composition, crystal structure and morphology. [1] Thus, size control provides one<br />
effective key to an accurate adjustment of the colloidal properties but is often challeng<strong>in</strong>g.<br />
The common approach to size control is a simple parameter variation via trial<br />
and error. The actual particle growth mechanisms and <strong>in</strong> particular the parameter<br />
<strong>in</strong>fluences on the growth process rema<strong>in</strong> a black box. [2]<br />
This contribution presents an approach to size control which is based on a profound<br />
mechanistic understand<strong>in</strong>g. It comprises three steps: (A) the <strong>in</strong>vestigation of the<br />
pr<strong>in</strong>ciple growth mechanism for one set of parameters, (B) the <strong>in</strong>vestigation of parameter<br />
<strong>in</strong>fluences on the growth mechanism which leads to the identification of size<br />
determ<strong>in</strong><strong>in</strong>g parameters and (C) the well-directed development of synthetic recipes.<br />
This approach is exemplified for a silver nanoparticle synthesis, namely the reduction<br />
of AgClO4 with an excess of NaBH4 <strong>in</strong> water.<br />
Recently, we deduced the pr<strong>in</strong>ciple growth mechanism from time-resolved <strong>in</strong>-situ<br />
SAXS <strong>in</strong>vestigations (see figure 1). [3] It comprises (1) the rapid reduction of the ionic<br />
silver, (2) the coalescence of these prelim<strong>in</strong>ary formed clusters, (3) an <strong>in</strong>termediate<br />
phase of stability and (4) a second coalescence which is the result of the complete<br />
conversion of residual BH4- to B(OH)4-. The f<strong>in</strong>al particle mean radius ranges from<br />
4 to 9 nm and is poorly reproducible. In the next step of the approach, the <strong>in</strong>fluences<br />
of reaction parameters on the growth mechanisms were elucidated. [4] It was found<br />
that the reproducibility can be improved by controlled ag<strong>in</strong>g of the reduc<strong>in</strong>g agent<br />
solution. In addition, the decisive size determ<strong>in</strong><strong>in</strong>g parameters could be identified.<br />
As a result, synthetic procedures for silver colloids were developed which allow a size<br />
control <strong>in</strong> a wide range without additional steric stabilization.<br />
Figure 1: Pr<strong>in</strong>ciple nanoparticle growth mechanism for the reduction of silver perchlorate<br />
with sodium borohydride<br />
[1] Y. Sun, Y. Xia, Science 2002, 298, 2176-2179.<br />
[2] Xia, Y. et al., Angewandte Chemie International Edition 2009, 48, 60-103.<br />
[3] J. Polte, et al., ACS Nano 2012, 6, 5791-5802.<br />
[4] M. Wuithschick, et al., submitted.<br />
42 Thursday 16:20 - 16:40 Talk 07
PbS-mesocrystals - Coherence between atomistic<br />
arrangement and <strong>in</strong>ternal nanocrystal superstructure<br />
order<strong>in</strong>g<br />
Lydia Liebscher ∗ , Igor A. Babur<strong>in</strong> ∗ , Wilder Carrillo-Cabrera ∗ , Elena Rosseeva † ,<br />
Paul Simon † , Stephen G. Hickey ∗ , Alexander Eychmüller ∗<br />
∗ Physikalische Chemie – TU Dresden – Bergstraße 66b – Dresden – GER<br />
† MPI for Chemical Physics of Solids – Max Planck Institute – Nöthnitzer Straße 40 –<br />
Dresden – GER<br />
L.Liebscher@chemie.tu-dresden.de<br />
Self aggregation and organization of nanoparticulate build<strong>in</strong>g blocks to form mesocrystals<br />
(Quantum dot solids) with special shapes and tunable properties is promis<strong>in</strong>g for<br />
many applications because such 2D and 3D arrangements comb<strong>in</strong>e the size-dependent<br />
properties of the <strong>in</strong>dividual nanoparticles (NPs) with new features that are derived<br />
from the unique collective properties <strong>in</strong>herent with<strong>in</strong> arrays of ordered particles. At<br />
the present time mesocrystals are of <strong>in</strong>creas<strong>in</strong>g <strong>in</strong>terest because these structures have<br />
further promis<strong>in</strong>g applications as light emitt<strong>in</strong>g devices, photodetectors and solar<br />
cells. [1]<br />
In this work we <strong>in</strong>vestigate the <strong>in</strong>ternal order<strong>in</strong>g of PbS mesocrystals at the atomistic<br />
scale with respect to the superlattice formed through the self assembly of the<br />
NPs. [2] The hierarchical structures were synthesized us<strong>in</strong>g a gentle diffusion technique<br />
employ<strong>in</strong>g spherical lead chalcogenide NPs as build<strong>in</strong>g blocks.<br />
The PbS mesocrystals were characterized by SEM. In order to shed some light on the<br />
<strong>in</strong>ner order<strong>in</strong>g of the PbS mesocrystals FIB cuts have been performed and subjected to<br />
detailed TEM <strong>in</strong>vestigations. The results of the HR-TEM studies show that a dist<strong>in</strong>ct<br />
structural relationship between the crystallographic orientation of the PbS (galena)<br />
core of the NPs and their order<strong>in</strong>g with<strong>in</strong> the fcc superstructure of the mesocrystals<br />
exists. Additionally, careful exam<strong>in</strong>ations of the HR-TEM images along the different<br />
projections of the <strong>in</strong>dividual nanocrystals have revealed that the appearance of the<br />
<strong>in</strong>dividual NPs is closely related to that of truncated octahedra. These f<strong>in</strong>d<strong>in</strong>gs are<br />
further supported by means of atomistic simulations undertaken on the NP assemblies<br />
as well as of the constitution of the monomeric build<strong>in</strong>g blocks.<br />
[1] S. M. Rupich, E. V. Shevchenko, M. I. Bodnarchuk, B. Lee, D. V Talap<strong>in</strong>, Journal of the<br />
American Chemical Society 2010, 132, 289-296.<br />
[2] P. Simon, E. Rosseeva, I. a Babur<strong>in</strong>, L. Liebscher, S. G. Hickey, R. Cardoso-Gil, A. Eychmüller,<br />
R. Kniep, W. Carrillo-Cabrera, Angewandte Chemie (International ed. <strong>in</strong> English) 2012, 51,<br />
10776-10781.<br />
Talk 08 Thursday 16:40 - 17:00 43
Synthesis of BaZrO3, Ta2O5 and HfO2 nanoparticles as<br />
artificial p<strong>in</strong>n<strong>in</strong>g centers <strong>in</strong> High Temperature<br />
Superconductors<br />
Jonathan De Roo ∗ , Katrien De Keukeleere ∗ , Jonas Feys ∗ , Petra Lommens ∗ ,<br />
Zeger Hens ∗ , Isabel Van Driessche ∗<br />
† Department of Inorganic and Physical Chemistry – Ghent University –<br />
Krijgslaan 281, build<strong>in</strong>g S3 – Ghent – BEL<br />
jonathan.deroo@ugent.be<br />
The development of Y Ba2Cu3O7−δ (YBCO) high-temperature superconductors has<br />
reached the level of high performance applications such as magnets, generators and<br />
transformers. These materials will contribute to a susta<strong>in</strong>able future by provid<strong>in</strong>g<br />
major energy sav<strong>in</strong>gs. However, the critical current density (Jc) rema<strong>in</strong>s too low<br />
for optimal application <strong>in</strong> high magnetic fields. Moreover, the dependence of Jc<br />
on the orientation of the magnetic field poses problems for practical application. [1]<br />
These problems can be circumvented by the <strong>in</strong>troduction of various structural and<br />
morphological defects (artificial p<strong>in</strong>n<strong>in</strong>g centers).<br />
Recently, BaZrO3 and Y2O3 nanostructures have proven some effectiveness via <strong>in</strong>situ<br />
approaches. [1] However, our <strong>in</strong>novative research focuses on the ex-situ addition<br />
of nanosized BaZrO3, T a2O5 and HfO2 of which the latter have never been used as<br />
artificial p<strong>in</strong>n<strong>in</strong>g centers up to date. This ex-situ approach provides more control over<br />
the size and morphology of the nanostructures and hence their p<strong>in</strong>n<strong>in</strong>g properties.<br />
We explored solvothermal, microwave and hot-<strong>in</strong>jection synthesis methods for the<br />
creation of these nanostructures. We try to restra<strong>in</strong> the use of organics <strong>in</strong> those<br />
synthesis routes and use as much as possible environmental-friendly, even water-based<br />
precursors. The synthesized nanoparticles were <strong>in</strong>corporated <strong>in</strong> YBCO precursor<br />
solutions. In order to do this we needed to carefully assess the surface chemistry of<br />
the different types of nanoparticles, and study the <strong>in</strong>fluence of ligand exchange on the<br />
stability of the nanoparticle/YBCO precursor mixtures. In the end, these mixtures<br />
will be used as <strong>in</strong>ks <strong>in</strong> order to deposit ex-situ p<strong>in</strong>ned YBCO on selected substrates<br />
through <strong>in</strong>k-jet pr<strong>in</strong>t<strong>in</strong>g.<br />
TEM picture of solvothermally prepared HfO2 nanoparticles. Inset (upper left): High<br />
Resolution TEM picture of an isolated particle. Inset (upper right): TEM diffraction<br />
pattern of the HfO2 nanoparticles.<br />
[1] X. Obradors et al., Comprehensive Nanoscience and technology 2011, 1, 303-349.<br />
44 Thursday 17:00 - 17:20 Talk 09
Viscosity at the Nanoscale<br />
Krzysztof Sozanski, Tomasz Kalwarczyk, Robert Holyst<br />
Department of Soft Condensed Matter –<br />
Institute of Physical Chemistry of the Polish Academy of Sciences – Kasprzaka 44/52 –<br />
Warsaw – POL<br />
krzysiek.sozanski@gmail.com<br />
One of the ma<strong>in</strong> factors <strong>in</strong>fluenc<strong>in</strong>g the k<strong>in</strong>etics of biochemical processes <strong>in</strong> liv<strong>in</strong>g cells<br />
is the mobility of prote<strong>in</strong>s and other macromolecules. It is mostly determ<strong>in</strong>ed by the<br />
diffusion coefficient of a given molecule <strong>in</strong> the cytoplasm. However, <strong>in</strong> an environment<br />
as crowded as the cytoplasm, accurate description of the diffusion rates becomes much<br />
more complicated than <strong>in</strong> simple liquids. It has been frequently observed that small<br />
prote<strong>in</strong>s present diffusion coefficients much greater (even by orders of magnitude)<br />
than predicted by the classical Stokes-E<strong>in</strong>ste<strong>in</strong> equation.<br />
The experiment-based explanation we suggest utilizes the notion of the so-called<br />
nanoviscosity. [1] This parameter <strong>in</strong>cludes both the properties of the complex liquid<br />
as well as the length scale of the object whose mobility is <strong>in</strong>vestigated. Thus, two<br />
objects differ<strong>in</strong>g is size may effectively experience different viscosity of the very same<br />
environment. [2]<br />
The scal<strong>in</strong>g we propose may be merged with the reaction rate theory to produce a<br />
simple yet universal and extremely functional physical description of diffusion processes<br />
<strong>in</strong> complex liquids. Most of the experimental work was performed by means<br />
of fluorescence correlation spectroscopy (FCS) – a fairly new and little known technique<br />
of great potential. To provide a straightforward framework of parameters, we<br />
focused on polymer model systems. However, the results are not only a contribution<br />
to the development of polymer theory. A new perspective is opened for model<strong>in</strong>g the<br />
transport processes and predict<strong>in</strong>g the mobility of any nano-scaled objects <strong>in</strong> crowded<br />
environment.<br />
[1] R. Hołyst, A. Bielejewska, J. Szymański, A. Wilk, A. Patkowski, J. Gapiński, A. Żywociński,<br />
T. Kalwarczyk, E. Kalwarczyk, M. Tabaka, N. Ziębacz, S. A. Wieczorek, Physical Chemistry<br />
Chemical Physics 2009, 11 (40), 9025-9032.<br />
[2] T. Kalwarczyk, N. Ziębacz, A. Bielejewska, E. Zaboklicka, K. Koynov, J. Szymański, A. Wilk,<br />
A. Patkowski, J. Gapiński, H.-J. Butt, R. Hołyst, Nano Letters 2011, 11, 2157.<br />
Talk 10 Thursday 17:20 - 17:40 45
Study<strong>in</strong>g arsenic <strong>in</strong> cancer cells by elemental speciation<br />
analysis<br />
Gerrit Hermann ∗ , Petra Heffeter † , Walter Berger † , Stephan Hann ∗ ,<br />
Gunda Koellensperger ∗<br />
∗ Division of Analytical Chemistry –<br />
University of Natural Resources and Life Sciences – BOKU Vienna – Muthgasse 18 –<br />
Vienna – AUT<br />
† Institute of Cancer Research – Medical University of Vienna – Borschkegasse 8a –<br />
Vienna – AUT<br />
Gerrit.Hermann@boku.ac.at<br />
More than 2000 years Arsenic trioxide (ATO) was used as a remedy by mank<strong>in</strong>d.<br />
S<strong>in</strong>ce the 30ies of the 20th century the importance of the compound as drug decl<strong>in</strong>ed<br />
as more effective medication was available for diseases like syphilis and its side effects<br />
were put more <strong>in</strong>to focus. At the end of the 20th century more evidence emerged for<br />
new application of ATO as a cancer therapeutic. Recently ATO was approved by the<br />
FDA for the use <strong>in</strong> the treatment of relapsed/refractory acute promyelotic leukemia<br />
(APL). S<strong>in</strong>ce the <strong>in</strong>troduction of ATO <strong>in</strong> chemotherapy, we keep learn<strong>in</strong>g about the<br />
cytostatic activity of the drug. Still the knowledge on the <strong>in</strong>tracellular chemistry of<br />
ATO with regard to the activity profile of the drug is however fragmentary. The<br />
debate cont<strong>in</strong>ues if ATO can be applied for other blood and solid cancers. [1,2] The<br />
contoversity about scientific results <strong>in</strong> this case and the etablished concepts of mode<br />
of action for ATO was motivation for this work.<br />
The <strong>in</strong>tracellular metabolism of ATO concern<strong>in</strong>g the b<strong>in</strong>d<strong>in</strong>g dynamics between cytosolic<br />
compounds with special emphasis on the <strong>in</strong>teraction with glutathione and the<br />
formation of its oxidized form was extensively studied. Sensitive versus resistance<br />
cancer cell models as well as cell l<strong>in</strong>es derived from different types of cancer were<br />
subject due to this <strong>in</strong>vestigation.<br />
[1] J. Zhu, Z. Chen, V. Lallemand-Breitenbach, H. De Thé, “How acute promyclocytic leukaemia<br />
revived arsenic”, Nature Reviews Cancer 2002, 2 (9), 705-713.<br />
[2] H. De Thé, Z. Chen, “Acute promyelocytic leukaemia: Novel <strong>in</strong>sights <strong>in</strong>to the mechanisms of<br />
cure”, Nature Reviews Cancer 2010, 10 (11), 775-783.<br />
46 Friday 10:40 - 11:00 Talk 11
2-Oxoglutarate Oxygenases as Therapeutic Targets<br />
Inga Pfeffer, Michael McDonough, Mart<strong>in</strong> Münzel, Ben G. Davis,<br />
Christopher J. Schofield<br />
Chemistry Research Laboratory – University of Oxford – 12 Mansfield Road – Oxford –<br />
UK<br />
<strong>in</strong>ga.pfeffer@chem.ox.ac.uk<br />
2-Oxoglutarate oxygenases [1] are non-haeme Fe(II)-dependent oxygenases that require<br />
2-oxoglutarate (2OG) and oxygen as cosubstrates. They catalyse a wide range of<br />
oxidative reactions on unactivated C-H bonds and are <strong>in</strong>volved <strong>in</strong> all steps of gene<br />
expression. 2OG oxygenases are ‘druggable‘ targets; both <strong>in</strong>hibition and activation<br />
of different 2OG oxygenases can be of therapeutic <strong>in</strong>terest. However, selectivity vs.<br />
other ‘key‘ 2OG oxygenases will be important.<br />
Human aspartyl/asparag<strong>in</strong>yl-β-hydroxylase (AspH) [2] is a 2OG oxygenase and catalyses<br />
hydroxylation of a specific aspartate or asparag<strong>in</strong>e residue <strong>in</strong> epidermal growth<br />
factor-like (EGF-like) doma<strong>in</strong>s. The physiological role of hydroxylations catalysed by<br />
AspH is not yet fully determ<strong>in</strong>ed. AspH is strongly expressed <strong>in</strong> various cancers, [3]<br />
and mice knockouts show <strong>in</strong>creased <strong>in</strong>cidence of tumour growth. The role of AspH<br />
for cancer needs to be further <strong>in</strong>vestigated but it is already be<strong>in</strong>g used as a biomarker<br />
for cancerous tissue <strong>in</strong> histopathological studies.<br />
Crystallographic studies revealed a common structural feature of 2OG oxyenases: The<br />
catalytic doma<strong>in</strong> conta<strong>in</strong>s a double-stranded helix core fold (‘jelly roll’) which supports<br />
a highly but not universally conserved Fe(II)-b<strong>in</strong>d<strong>in</strong>g motif <strong>in</strong> form of a triad<br />
of two histid<strong>in</strong>es and one carboxylate, either Asp or less frequently Glu (HXD/E· · ·H<br />
triad motif). AspH lacks the HXD/E· · ·H triad Fe(II)-b<strong>in</strong>d<strong>in</strong>g motif. Instead, it has<br />
a His-Xxx-Gly· · ·His motif, the Asp or Glu residue is not present. AspH therefore<br />
differs from other 2OG oxygenases and conta<strong>in</strong>s two Fe(II)-b<strong>in</strong>d<strong>in</strong>g residues only. Its<br />
unique active site geometry makes AspH an attractive potential drug target. Here we<br />
demonstrate that the hydroxylase doma<strong>in</strong> of the prote<strong>in</strong> alone has no substrate hydroxylation<br />
activity but another doma<strong>in</strong>, the tetratricopeptide repeat (TPR) doma<strong>in</strong>,<br />
is required for substrate recognition. We present new crystal structures for a multidoma<strong>in</strong><br />
construct of AspH <strong>in</strong>clud<strong>in</strong>g enzyme-substrate-complexes with a peptide from<br />
the natural substrate coagulation factor X and designed cyclic peptides which provide<br />
valuable <strong>in</strong>sight for further mechanistic studies and selective <strong>in</strong>hibitor design.<br />
AspH <strong>in</strong> complex with a substrate peptide from factor X.<br />
[1] R. Chowdhury et al., Chem. Soc. Rev. 2008, 37 (7), 1308-1319.<br />
[2] B. A. McMullen, et al., Biochem. Biophys. Res. Comm. 1983, 115 (1), 8-14.<br />
[3] H. Yang, et al., Oncology Reports 2010, 24 (5), 1257-1264.<br />
Talk 12 Friday 11:00 - 11:20 47
Design and synthesis of fungical transglycosidase <strong>in</strong>hibitors<br />
Fernando Gomollon-Bel ∗ , Eduardo Marca ∗ , Ramon Hurtado-Guerrero † , Ignacio Delso ∗ ,<br />
Tomás Tejero ∗ , Pedro Mer<strong>in</strong>o ∗<br />
∗ Departamento de Síntesis y Estructura de Biomoléculas –<br />
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) –<br />
Universidad de Zaragoza - CSIC - C/ Pedro Cerbuna 12 – Zaragoza – ESP<br />
† BIFI – Instituto de Biocomputación y Física de Sistemas Complejos –<br />
Universidad de Zaragoza - C/ Mariano Esquillor s/n – Zaragoza – ESP<br />
gomobel@unizar.es<br />
Transglycosydases are a group of key enzymes <strong>in</strong> preserv<strong>in</strong>g the structure of the<br />
cell-wall <strong>in</strong> most fungi. Therefore, the study of their active site and preparation of<br />
<strong>in</strong>hibitors could lead to the obtention of powerful fungicides which could be active<br />
aga<strong>in</strong>st <strong>in</strong>fectious organisms such as Aspergillus fumigatus or Candida albicans.<br />
We were able to study the x-ray crystall<strong>in</strong>e structure of Gas2 [1] , a membrane bound<br />
enzyme from Saccharomices cerevisae, a fungus that is usually studied <strong>in</strong> Biochemistry<br />
because of its genetical and structural analogies to pathogens like A. fumigatus<br />
and C. albicans. Know<strong>in</strong>g the active site and the optimal substrate for the enzyme,<br />
molecular dock<strong>in</strong>g studies were carried out to design the target molecules to be synthesized.<br />
We have optimized a purification method [2] of β(1,3)-oligosaccharides from commercially<br />
available glucans (Figure 1, A) and we have studied the synthesis of cyclic six<br />
membered nitrones that can be functionalized [3] with hydrophobic substituents (R)<br />
(Figure 1, B) which will be able to fit <strong>in</strong> a lipophilic cavity close to Gas2 active site.<br />
Nowadays, new dock<strong>in</strong>g, molecular dynamics and <strong>in</strong>hibition studies are be<strong>in</strong>g carried<br />
out to determ<strong>in</strong>e the activity as fungicides of the prepared compounds.<br />
Figure 1 - Saccharomyces cerevisae Gas2 transglycosidase and synthetic goals<br />
Acknowledgments: F. G.-B. thanks the Spanish Council for Scientific Research (CSIC) for a<br />
JAE-Predoctoral grant. R. H.-G. thanks the ARAID Foundation for a permanent position.<br />
[1]<br />
R. Hurtado-Guerrero, A. W. Schüttelkopf, I. Mouyna, A. F. M. Ibrahim, S. Shepherd, T.<br />
Fonta<strong>in</strong>e, J.-P. Latgé, D. M. F. van Aalten, J. Biol. Chem. 2009, 284, 8461-8469.<br />
[2]<br />
V. Moreau, J.-L. Viladot, E. Sama<strong>in</strong>, A. Planas, H. Driguez, Bioorg. Med. Chem. 1996, 4,<br />
1849-1855.<br />
[3]<br />
a) P. Mer<strong>in</strong>o, S. Franco, F. Merchán, T. Tejero, Synlett. 2000, 442-454; b) I. Delso, T. Tejero,<br />
A. Goti, P. Mer<strong>in</strong>o, J. Org. Chem. 2011, 76, 4139-4143.<br />
48 Friday 11:20 - 11:40 Talk 13
2 H NMR spectroscopy <strong>in</strong> application to selected am<strong>in</strong>o-acids<br />
Aleksandra Kubica ∗ , Danuta Kruk † , Artur Birczyński ‡<br />
∗ Faculty of Physics, Astronomy and Applied Computer Science –<br />
Jagiellonian University – Reymonta 4 – Krakow – POL<br />
† Faculty of Mathematics and Computer Science – University of Warmia and Mazury –<br />
Sloneczna 54 – Olsztyn – POL<br />
‡ Institute of Nuclear Physics – Polish Academy of Science – Radzikowskiego 152 –<br />
Krakow – POL<br />
aleksandra.kubica@uj.edu.pl<br />
2 H Nuclear Magnetic Resonance (NMR) is one of the key methods provid<strong>in</strong>g <strong>in</strong>formation<br />
on mechanisms of molecular dynamics. [1] 2 H NMR spectral shapes as well<br />
as sp<strong>in</strong> relaxation are dom<strong>in</strong>ated by strong quadrupolar <strong>in</strong>teraction. [1] Comb<strong>in</strong><strong>in</strong>g<br />
these great advantages of 2 H NMR with selective substitution of 1 H by 2 H one gets<br />
powerful tool for study<strong>in</strong>g dynamics of biomolecules. Generally 2 H spectral shapes<br />
analysis of 2 H NMR is based on perturbation theory. For biological systems the description<br />
of time scale outside of the perturbation regime is needed. Unswerv<strong>in</strong>g to<br />
this need <strong>in</strong> this work a theory of 2 H l<strong>in</strong>eshape based on Stochastic Liouville Equation<br />
is presented. [2] . This treatment is an adaptation of “Swedish slow motion theory” [3,4]<br />
applied <strong>in</strong> Electron Sp<strong>in</strong> Resonance (ESR). The presented theory of 2 H l<strong>in</strong>eshapes is<br />
valid for arbitrary motional conditions and allow for consider<strong>in</strong>g various mechanisms<br />
of motion, for <strong>in</strong>stance simple (Brownian), free - or jump rotational dynamics. The<br />
free diffusion model assumes that the molecule reorients freely for a given time and<br />
then jumps to a new orientation and then reorients aga<strong>in</strong>. In the case of jump diffusion<br />
it is assumed that the molecule has a fixed average direction around which it<br />
reorients for a given time and then jumps to a new direction. These models are described<br />
by two times: τ - life time of s<strong>in</strong>gle orientation and τR- rotational correlation<br />
time. Illustrative simulations of 2 H l<strong>in</strong>eshapes for the simple, jump- and free diffusion<br />
models are shown <strong>in</strong> the Fig.1. The theory has been applied to analyze 2 H l<strong>in</strong>eshapes<br />
of am<strong>in</strong>o acids (lizyne, glicyne, alan<strong>in</strong>e) and prote<strong>in</strong>s [5] (concanaval<strong>in</strong>e and leuc<strong>in</strong>e-<br />
69 from chicken vill<strong>in</strong> - spectra were taken from [6] ) for the purpose of extract<strong>in</strong>g<br />
<strong>in</strong>formation on the dynamical mechanisms of the selectively deuterated parts of the<br />
molecules. One can conclude from this attempt that the models capture the essential<br />
features of the dynamical processes and allow for a consistent <strong>in</strong>terpretation of the<br />
2 H NMR spectral shapes.<br />
Left: 2 H NMR spectra, B0=0.1T for quadrupolar coupl<strong>in</strong>g constant aq=220kHz and<br />
different models of diffusion. Right: 2 H NMR spectra for leuc<strong>in</strong>e-69 and simulations.<br />
[1]<br />
D. Kruk, Theory of Evolution and Relaxation of Multi-Sp<strong>in</strong> Systems (Arima, Bury St Edmunds,<br />
2007).<br />
[2]<br />
D.Kruk et al., J.Chem. Phys. 2011, 135, 224511.<br />
[3]<br />
T. Nilsson, J. Kowalewski, J. Magn. Reson. 2000, 146, 345.<br />
[4]<br />
D. Kruk et al., J. chem. Phys. 2011, 135, 224511.<br />
[5]<br />
D. Kruk et al., J. chem. Phys. 2012, 136, 244509.<br />
[6]<br />
Vugmeyster et al., J. Am. Chem. Soc. 2009, 131, 13652.<br />
Talk 14 Friday 11:40 - 12:00 49
Synthesis and development of the novel phthalocyan<strong>in</strong>e<br />
derivatives possess<strong>in</strong>g 2-(morphol<strong>in</strong>-4-yl)ethyloxy groups of<br />
potential applications <strong>in</strong> photodynamic therapy<br />
P. Skup<strong>in</strong>-Mrugalska ∗ , L. Sobotta ∗ , W. Szczolko † , K. Konopka ⋄ , E. Tykarska † ,<br />
M. Wierzchowski † , J. Dlugaszewska ‡ , M. Kuc<strong>in</strong>ska ‡ , M. Murias ‡ , N. Duzgunes ⋄ ,<br />
T. Gosl<strong>in</strong>ski † , J. Mielcarek ∗<br />
∗ Department of Inorganic and Analytical Chemistry –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
† Department of Chemical Technology of Drugs –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
‡ Department of Toxicology – Poznan University of Medical Sciences – Dojazd 30 –<br />
Poznan – POL<br />
⋄ Department of Biomedical Sciences – University of the Pacific – 2155 Webster Street –<br />
San Francisco – USA<br />
p_skup<strong>in</strong>@wp.pl<br />
Phthalocyan<strong>in</strong>es (Pcs) are macrocyclic compounds which possess many applications.<br />
In biomedical field, Pcs have been <strong>in</strong>vestigated as potential photosensitizers (PSs)<br />
for photodynamic therapy (PDT). PDT is a medical modality which exploits oxygen,<br />
visible light and PS to treat various diseases <strong>in</strong>clud<strong>in</strong>g cancer, age-related macular<br />
degeneration, psoriasis, keratosis, etc. [1] Chemical modifications of exist<strong>in</strong>g PSs, design<strong>in</strong>g<br />
novel molecules and pharmaceutical formulations are ongo<strong>in</strong>g approaches aim<strong>in</strong>g<br />
to improve PSs properties. As most Pcs are highly <strong>in</strong>soluble <strong>in</strong> water, they have<br />
been ma<strong>in</strong>ly modified either by chemical reactions lead<strong>in</strong>g to more soluble derivatives<br />
or by <strong>in</strong>corporation <strong>in</strong>to vehicles like liposomes. [2] Here<strong>in</strong>, novel Pcs endowed with<br />
2-(morphol<strong>in</strong>-4-yl)ethyloxy substituents were synthesized (1-4). Moreover, alkylation<br />
reaction of 1 led to water soluble Pc (4). Novel macrocycles were characterized us<strong>in</strong>g<br />
NMR techniques and crystallography. Their purity was assessed by HPLC method. In<br />
addition, absorption, emission and aggregation properties of the novel Pcs were studied.<br />
S<strong>in</strong>glet oxygen quantum yield of compounds 1-4 was measured both <strong>in</strong> DMSO<br />
and <strong>in</strong> DMF. Cytotoxic activity of these compounds was <strong>in</strong>vestigated us<strong>in</strong>g panel of<br />
cancer cell l<strong>in</strong>es. The Pc 3 was found the most active compound which showed light<br />
but not dark cytotoxicity. Pcs 1-3 were then <strong>in</strong>corporated <strong>in</strong>to liposomes follow<strong>in</strong>g<br />
hydration procedure, and extruded to achieve a uniform size distribution. Liposomes<br />
were characterized by dynamic light-scatter<strong>in</strong>g method. F<strong>in</strong>ally, the biological activity<br />
aga<strong>in</strong>st human squamous cell carc<strong>in</strong>oma of novel Pcs, both non-<strong>in</strong>corporated and<br />
<strong>in</strong>corporated <strong>in</strong>to liposomes, was studied.<br />
Studies supported by the National Science Centre - Grant No. N401 067238 and funds from University<br />
of the Pacific, A.A. Dugoni School of Dentistry. P. Skup<strong>in</strong>-Mrugalska, W.Szczolko -scholarship<br />
holders “Scholarship support for Ph.D. students specializ<strong>in</strong>g <strong>in</strong> majors strategic for Wielkopolska’s<br />
development”, Sub-measure 8.2.2 Human Capital Operational Programme, co-f<strong>in</strong>anced by EU under<br />
the ESF.<br />
[1] S. Yano, S. Hirohara, M. Obata, Y. Hagiya, S. Ogura, A. Ikeda, H. Kataoka, M. Tanaka, T.<br />
Joh, J. Photochem. Photobiol. 2011, C 12, 46.<br />
[2] Y.N. Konan, R. Gurny, E. Allemann, J. Photochem. Photobiol. 2002, B 66, 89.<br />
50 Friday 13:30 - 13:50 Talk 15
Novel drug carrier systems - Spectroscopic characterization<br />
of cell-penetrat<strong>in</strong>g peptide analogous<br />
Sören Gehne ∗ , Karl Sydow † , Margitta Dathe † , Michael U. Kumke ∗<br />
∗ Physical Chemistry – University of Potsdam – Karl-Liebknecht-Str. 24-25 – Potsdam –<br />
GER<br />
† Peptide Lipid Interaction/Peptide Transport –<br />
Leibniz Institute for Molecular Pharmacology – Robert-Roessle-Str. 10 – Berl<strong>in</strong> – GER<br />
gehne@uni-potsdam.de<br />
The specific transport of pharmaceutical <strong>in</strong>gredients to the po<strong>in</strong>t of need is a very hot<br />
topic <strong>in</strong> life sciences. Among the molecular transport systems <strong>in</strong>vestigated colloidal<br />
vehicles (e.g. micelles) are of special <strong>in</strong>terest because they are able to transport also<br />
only poorly soluble or rapidly degradable molecules. [1]<br />
We report on the lipopeptide (LP) P2A2, which consists of a cell-penetrat<strong>in</strong>g peptide<br />
part A2 (derived from apoliprote<strong>in</strong> E) and of two palmitoyl cha<strong>in</strong>s P2. [2,3] The unique<br />
comb<strong>in</strong>ation of cell-penetrat<strong>in</strong>g and micelle-form<strong>in</strong>g properties paves the road for the<br />
development of a novel class of powerful drug carrier systems (DCS). Knowledge on<br />
the physico-chemical properties as well as the <strong>in</strong>teraction of the DCS with the target<br />
(e.g. cells, cell membranes) is <strong>in</strong>dispensible for the design of novel highly effective<br />
tailor-made DCS. Fundamental properties such as the critical micelle concentration<br />
(cmc), the aggregation number (Nagg) as well as the exchange rates of drugs between<br />
DCS and environment are needed, which – <strong>in</strong> some cases – are only accessible with<br />
sensitive spectroscopic methods.<br />
For the spectroscopic <strong>in</strong>vestigation A2 and P2A2 were labeled with 5(6)-Carboxyfluoresce<strong>in</strong><br />
(FAM) and used as fluorescent probe. By us<strong>in</strong>g different spectroscopic<br />
methods (e.g. fluorescence anisotropy, fluorescence correlation spectroscopy) the<br />
FAM-labeled biomolecules were characterized regard<strong>in</strong>g their aggregation behavior<br />
(cmc, Nagg). To study the <strong>in</strong>fluence of the chemical composition of the peptide part<br />
on the micelle formation, P2A2 analogous with modified peptide sequences were <strong>in</strong>vestigated.<br />
P2A2 turned out to be a very strong detergent with an outstand<strong>in</strong>g low cmc <strong>in</strong> the<br />
micromolar(!) range. For a powerful drug delivery system also the targeted delivery<br />
to specific cells [4] or the exchange k<strong>in</strong>etics of the pharmaceutical agents is highly<br />
important. Therefore, the exchange k<strong>in</strong>etics of P2A2 micelles were <strong>in</strong>vestigated <strong>in</strong><br />
biomimetic systems us<strong>in</strong>g fluorescent probes as drug analogous.<br />
P2A2-micelle (yellow - palmitoyl cha<strong>in</strong>s).<br />
[1] V. P. Torchil<strong>in</strong>, Pharm Res 2007, 24, 1-16.<br />
[2] S. Keller et al., Angew. Chem. Int. Ed. 2005, 44, 5252-5255.<br />
[3] E. Leupold et al., Biochimica et Biophysica Acta 2009, 1788, 442-449.<br />
[4] I. Sauer et al., Biochimica et Biophysica Acta 2006, 1758, 552-561.<br />
Talk 16 Friday 13:50 - 14:10 51
Controlled Synthesis of Cell-Laden Degradable Microgels by<br />
Radical-Free and Supramolecular Gelation <strong>in</strong> Droplet<br />
Microfluidics<br />
Torsten Rossow, Sebastian Seiffert<br />
Organische Chemie – Freie Universität Berl<strong>in</strong> – Takustraße 3 – Berl<strong>in</strong> – GER<br />
torsten.rossow@onl<strong>in</strong>ehome.de<br />
Hydrogels with micrometer-scale dimensions (microgels) are useful scaffolds for cell<br />
encapsulation, because they mimic the natural extracellular matrix with the possibility<br />
to tailor it. [1] We fabricate microgel particles that conta<strong>in</strong> liv<strong>in</strong>g cells with<br />
exquisite control through droplet-based microfluidics, as shown <strong>in</strong> Figure 1. The microgel<br />
gelation is achieved via the bio-orthogonal thiol-ene click reaction of dithiolated<br />
polyethyleneglycol (PEG) macrocrossl<strong>in</strong>kers and acrylated hyperbranched polyglycerol<br />
(hPG) build<strong>in</strong>g blocks and does not require any <strong>in</strong>itiator. [2] This approach yields<br />
high cell viabilities of about 90%.<br />
To perform efficient cell analysis, fast and stimuli-responsive microgel degradation<br />
must be achievable to release encapsulated cells on demand. For this purpose, reversibly<br />
crossl<strong>in</strong>ked supramolecular polymer gels are an <strong>in</strong>terest<strong>in</strong>g class of materials.<br />
We follow this approach and prepare supramolecularly crossl<strong>in</strong>ked cell-laden<br />
microgels that consist of bipyrid<strong>in</strong>e-term<strong>in</strong>ated PEG, crossl<strong>in</strong>ked by complexation of<br />
non-harmful metal salts such as iron(II)-sulfate. To study the <strong>in</strong>fluence of the microgel<br />
elasticity on mammalian-cell viabilities, we use bpy-PEG-bpy precursors with<br />
different molecular weights and at different concentrations. That way, the microgel<br />
properties can be optimized to obta<strong>in</strong><strong>in</strong>g cell viabilities of up to 96%. These microgels<br />
are stable enough to use them as <strong>in</strong>-vitro 3D-cell cultur<strong>in</strong>g systems, but they are<br />
labile enough to release the cells on demand. This can be achieved by simple dilution<br />
on a timescale of hours or by the addition of decomplex<strong>in</strong>g agents on a timescale of<br />
m<strong>in</strong>utes, with no effect on the viability of the encapsulated and released cells.<br />
Figure 1. Formation of cell-laden microgel particles through the use of droplet-based<br />
microfluidic particle templat<strong>in</strong>g and bio-orthogonal crossl<strong>in</strong>k<strong>in</strong>g of thiol-term<strong>in</strong>ated polyethyleneglycol<br />
(PEG) and ene-term<strong>in</strong>ated hyperbranched polyglycerol (hPG) precursor<br />
polymers.<br />
[1] D. Velasco, E. Tumark<strong>in</strong>, E. Kumacheva, Small 2012, 8, 1633-1642.<br />
[2] T. Rossow, J. A. Heyman, A. J. Ehrlicher, A. Langhoff, D. A. Weitz, R. Haag, S. Seiffert, J.<br />
Am. Chem. Soc. 2012, 134, 4983-4989.<br />
52 Friday 14:10 - 14:30 Talk 17
Liquid Crystal and Electro-Optic Block Codendrimers:<br />
Synthesis and Characterization<br />
Ismael Gracia ∗ , Beatriz Fer<strong>in</strong>gán ∗ , Joaquín Barberá ∗ , Ana Omenat ∗ , Jose Luis Serrano †<br />
∗ Dpto. Química Orgánica –<br />
Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza - CSIC –<br />
C/ Pedro Cerbuna 12 – Zaragoza – ESP<br />
† Dpto. Química Orgánica –<br />
Instituto de Nanociencia de Aragón, Universidad de Zaragoza - CSIC –<br />
C/ Pedro Cerbuna 12 – Zaragoza – ESP<br />
ismaelgg@unizar.es<br />
Dendrimers are polymeric materials that have attracted a lot of attention, <strong>in</strong> many<br />
fields, all over the last decade. One of the ma<strong>in</strong> properties of dendrimers is that<br />
it is possible to achieve a high degree of control over their functionalization, both<br />
<strong>in</strong> the backbone and <strong>in</strong> the periphery. In our group, we have experience <strong>in</strong> the<br />
study of the structure-properties relationship of liquid crystal dendrimers, or the socalled<br />
dendromesogens. [1] In this work, different bifunctional materials have been<br />
synthesized based on block codendrimers. The objective is to obta<strong>in</strong> ordered and<br />
light emitt<strong>in</strong>g materials based on highly controllable dendritic structures.<br />
For the dendrimer backbone, we have used the first and second generation of bis-MPA<br />
dendrons. [2] From this start<strong>in</strong>g material and by means of an orthogonal synthetic<br />
procedure, we obta<strong>in</strong> compounds with two or four peripheral hydroxyl groups for the<br />
first and second generations, respectively. S<strong>in</strong>ce our first goal was to prepare a liquid<br />
crystal material, we have <strong>in</strong>troduced four mesogenic groups, which should favour the<br />
mesophase formation, and a variable amount of chromophores on the other side of the<br />
molecule, <strong>in</strong> order to study the relationship between the mesogenic and the emissive<br />
properties of the codendrimer. Afterwards, we have <strong>in</strong>troduced some modifications<br />
<strong>in</strong> the structure to favour the formation of room temperature stable smectic and<br />
columnar phases that would benefit the ordered fluorescence emission.<br />
WAXD patterns show that dendrons and codendrimers with one term<strong>in</strong>al cha<strong>in</strong><br />
present type A and C smectic mesophases, whereas those with three term<strong>in</strong>al cha<strong>in</strong>s<br />
show columnar mesomorphism <strong>in</strong> some cases. Even though smectic phases are quite<br />
stable <strong>in</strong> the materials under study, the columnar mesomorphism is not always reached<br />
maybe due to the destabilization caused by the photoactive species. Calculations<br />
based on WAXD patterns allow us to propose molecular models for the mesophases.<br />
UV-vis absorption and fluorescence emission experiments show strong signals with<br />
maxima at 264 -268 nm and 351 nm, respectively, while when emission was measured<br />
from multi-doma<strong>in</strong> oriented films maximum emission was found at 370 nm. Optical<br />
properties of these codendrimers show that the <strong>in</strong>troduction of one, two or four<br />
carbazole units does not affect the emission quantum yield.<br />
Fig. 1. Schematic representation of the codendrimers synthesized<br />
[1] M. Marcos, R. Martín-Rapún, A. Omenat, J. L. Serrano, Chem. Soc. Rev. 2007, 36, 1889.<br />
[2] H. Ihre, A. Hult, J. M. Fréchet, I. Gitsov, Macromolecules 1998, 31, 4061.<br />
Talk 18 Friday 16:20 - 16:40 53
Great Insights from a Small System: Structure and<br />
reactivity of [V P O4] + <strong>in</strong> comparison with [V2O4] + .<br />
Nicolas Dietl ∗ , Maria Schlangen ∗ , Knut Asmis † , Helmut Schwarz ∗<br />
∗ Institut für Chemie – Technische Universität Berl<strong>in</strong> – Straße des 17. Juni 135 – Berl<strong>in</strong> –<br />
GER<br />
† Institut für Molekülphysik – Fritz-Haber-Institut der Max-Planck-Gesellschaft –<br />
Faradayweg 4-6 – Berl<strong>in</strong> – GER<br />
nicolas.dietl@mail.chem.tu-berl<strong>in</strong>.de<br />
The selective oxidation of hydrocarbons still constitutes one of the major challenges <strong>in</strong><br />
contemporary chemistry to solve global problems, such as the environmentally benign<br />
and economically feasible conversion of natural gas <strong>in</strong>to value-added products. [1] Today,<br />
there exist numerous effective homogeneous and heterogeneous catalysts which<br />
cover a broad spectrum of oxidation reactivity; however, it is not exaggerated to<br />
note the lack of substantiated knowledge about the <strong>in</strong>tr<strong>in</strong>sic properties of many of<br />
the catalysts which, after all, control the selectivity of the various oxidation processes.<br />
A well-known example for such a poorly understood catalytic process represents<br />
the chemical transformation of n-butane to maleic anhydride by the so-called<br />
VPO-catalysts; this highly complex and selective reaction <strong>in</strong>volves the abstraction of<br />
eight hydrogen atoms from, as well as the transfer of three oxygen atoms to C4H10.<br />
One approach <strong>in</strong> the elucidation of mechanistic aspects at a molecular level employs<br />
reactivity studies which are conducted under near s<strong>in</strong>gle-collision conditions <strong>in</strong> a mass<br />
spectrometer <strong>in</strong> conjunction with computational studies. [2]<br />
Our recent results report on the electrospray-ionization (ESI) generation of the small,<br />
mixed-oxo cluster [V P O4] + , its electronic structure <strong>in</strong> the gas phase as well as its<br />
reactivity towards small hydrocarbons, thus permitt<strong>in</strong>g a comparison to the long-time<br />
known and extensively <strong>in</strong>vestigated vanadium-oxide cation [V2O4] + . [3] As described<br />
<strong>in</strong> previous studies, the latter exhibits no reactivity towards small hydrocarbons, such<br />
as CH4, C2H6, C3H8, C4H10, and C2H4, while the substitution of one vanadium<br />
atom by a phosphorous atom yields the reactive [V P O4] + ion which br<strong>in</strong>gs about<br />
oxidative dehydrogenation from saturated hydrocarbons, i.e. propane and butane, as<br />
well as oxygen-atom transfer to unsaturated hydrocarbons, i.e. ethene, at thermal<br />
conditions. Further, the structure of [V P O4] + was characterized <strong>in</strong> the gas phase<br />
by advanced IR photodissociation spectroscopy, and a comparison is made to the<br />
also structurally characterized gaseous [V2O4] + system, <strong>in</strong>clud<strong>in</strong>g structure-reactivity<br />
relationships. F<strong>in</strong>ally, reaction mechanisms are elucidated by DFT calculations; the<br />
results underl<strong>in</strong>e the key role of phosphorous <strong>in</strong> terms of C-H bond activation of<br />
hydrocarbons by mixed VPO-clusters.<br />
[1] J. R. Webb, T. Bolaño, T. B. Gunnoe, ChemSusChem 2011, 4, 37.<br />
[2] H. Schwarz, Angew. Chem. Int. Ed. 2011, 50, 10096.<br />
[3] a) R. C. Bell, K. A. Zemski, K. P. Kerns, H. T. Deng, A. W. Castleman, J. Phys. Chem. A<br />
1998, 102, 1733; b) K. R. Asmis, J. Sauer, Mass Spectrom. Rev. 2007, 26, 542.<br />
54 Friday 16:40 - 17:00 Talk 19
Comparison of different Cu particles supported on SBA-15<br />
as methanol steam reform<strong>in</strong>g catalysts<br />
Gregor Koch, Thorsten Ressler<br />
Institut für Anorganische und Analytische Chemie – Technische Universität –<br />
Straße des 17. Juni 135, 10623 Berl<strong>in</strong> – Berl<strong>in</strong> – GER<br />
gregor.koch@tu-berl<strong>in</strong>.de<br />
Intensive research has shown the importance of Cu conta<strong>in</strong><strong>in</strong>g catalysts for methanol<br />
steam reform<strong>in</strong>g (MSR) as H2 source. [1] For subsequent fuel cell application CO<br />
formation due to side reactions like water gas shift needs to be avoided. Therefore,<br />
the correlation between catalyst structure and activity has to be understood. From<br />
<strong>in</strong>vestigations of Cu/ZnO/Al2O3 catalyst, Cu was found to be the active phase, while<br />
ZnO and Al2O3 were suggested as both functional and structural promoters. [2] To<br />
further reveal the effect of structural changes of the active Cu phase (e.g. micro stra<strong>in</strong>)<br />
on MSR activity, suitable model systems have to be <strong>in</strong>vestigated. Therefore, b<strong>in</strong>ary<br />
Cu-ZnO catalysts, for <strong>in</strong>stance, have been studied <strong>in</strong> detail [3] . Here, Cu particles were<br />
deposited on nanostructured silica to reveal correlations between the structure of Cu<br />
particles and their catalytic activity. This approach shall allow dist<strong>in</strong>guish<strong>in</strong>g these<br />
effects from any further promot<strong>in</strong>g effect of ZnO.<br />
Cu catalysts were prepared by <strong>in</strong>cipient wetness. Therefore, SBA-15 was treated with<br />
Cu citrate solution. Subsequent decomposition <strong>in</strong> air resulted <strong>in</strong> the oxidic precursor.<br />
XAS at the Cu K edge showed that CuO is the major copper phase <strong>in</strong> the oxidic<br />
precursor of all catalysts. Dur<strong>in</strong>g reduction <strong>in</strong> 5 % H2, formation of an <strong>in</strong>termediate<br />
phase before generation of Cu particles was observed with <strong>in</strong> situ XAS measurements.<br />
After reduction, partially oxidized metallic Cu was found. The average oxidation state<br />
was shifted from ± 0 up to + 0.4. In situ diffraction patterns illustrated enlarged Cu<br />
particles with <strong>in</strong>creas<strong>in</strong>g Cu load<strong>in</strong>g on silica support. XAS measurement of the Cu<br />
K edge also <strong>in</strong>dicated that higher load<strong>in</strong>g of Cu resulted <strong>in</strong> bigger Cu particles after<br />
reduction (Fig. 1). However, these Cu catalysts showed a good catalytic activity<br />
with high selectivity to CO2. Correlation between structure of the Cu phase and the<br />
performance of the catalysts will be discussed.<br />
Fig.1 Comparison of the FT(χ(k)*k 3 ) of three Cu/SBA-15 catalysts with different<br />
load<strong>in</strong>gs after reduction.<br />
[1]<br />
S. Sá, H. Silva, L. Brandão, J. M. Soua, A. Mendes, Appl. Catal., B Environmental 2010,<br />
99, 43.<br />
[2]<br />
M. Behrens, F. Studt, I. Kasatk<strong>in</strong>, S. Kühl, M. Hävecker, F. Abild-Pederson, S. Zander, F.<br />
Girgsdies, P. Kurr, B. L. Kniep, M. Tovar, R. W. Fischer, J. K. Nørskov, R. Schlögl, Science<br />
2012, 366, 893.<br />
[3]<br />
P. Kurr, I. Kasatk<strong>in</strong>, F. Girgsidies, A. Trunschke, R. Schlögl, T. Ressler, Appl. Catal. A<br />
2008, 348, 153.<br />
Talk 20 Friday 17:00 - 17:20 55
New Trifluoromethyl Derivatives of 5 IPR Isomers the<br />
Fullerene C84<br />
Maria Fritz ∗ , Kaich<strong>in</strong> Chang † , Natalia A. Romanova ∗ , Sergey I. Troyanov ∗ ,<br />
Nadezhda B. Tamm ∗<br />
∗ Chemical Department – Lomonosov Moscow State University – Len<strong>in</strong>skie Gori/1-3 –<br />
Moscow – RUS<br />
† Institute of Chemistry – Humboldt University Berl<strong>in</strong> – Brook-Taylor Straße/2 –<br />
Berl<strong>in</strong> – GER<br />
malanskikh@gmail.com<br />
The C84 fullerene corresponds to the higher fullerenes of more than 70 carbon atoms.<br />
As is widely known, the number of possible isomers rapidly grows with the number<br />
of carbon atoms, the isomers which obey the Isolated Pentagon Rule (IPR) [1] be<strong>in</strong>g<br />
the most stable. There are 24 possible IPR-isomers of C84 fullerene. Unambiguous<br />
structural determ<strong>in</strong>ation of the fullerene molecules requires an X-ray study of prist<strong>in</strong>e<br />
isomers or their derivatives. In this regard, the derivatized molecules frequently prove<br />
advantageous as the attached moieties suppress rotational disorder thereby enabl<strong>in</strong>g<br />
reliable determ<strong>in</strong>ation of both cage connectivity and addition patterns.<br />
Here we report synthesis, separation, and structural characterization by means of<br />
s<strong>in</strong>gle crystal X-ray diffraction new trifluoromethyl derivatives of 5 IPR isomers the<br />
fullerene C84. Mixtures of higher fullerenes were reacted with CF3I <strong>in</strong> a sealed<br />
ampoule at 420 ◦ C and 550 ◦ C. The C2m(CF3)2n reaction products were dissolved <strong>in</strong><br />
hexane or toluene and subjected to multistep HPLC separation (Lomonosov Moscow<br />
State University, Moscow, Russia). S<strong>in</strong>gle crystals grown from isolated fractions were<br />
studied by X-ray diffraction with the use of synchrotron radiation (BESSY, Free<br />
University, Berl<strong>in</strong>, Germany). Structural relationship accompanied with theoretical<br />
<strong>in</strong>vestigation (DFT/PRIRODA) allowed determ<strong>in</strong><strong>in</strong>g the ma<strong>in</strong> addition rules and<br />
reveal<strong>in</strong>g the sequential addition pathways.<br />
[1] P. W. Fowler, D. E. Manolopoulos, An Atlas of Fullerenes, Dover Publications, 2006, 392.<br />
56 Friday 17:20 - 17:40 Talk 21
Posters
Nanoporous anodic titanium oxide (ATO) layers as surface<br />
for microbial and cell growth<br />
Magdalena Jarosz ∗ , Katarzyna Malec † , Justyna Sygula-Cholew<strong>in</strong>ska ‡ ,<br />
Tomasz Sawoszczuk ‡ , Iwona Wybranska † , Grzegorz Sulka ∗ , Marian Jaskula ∗<br />
∗ Department of Physical Chemistry & Electrochemistry – Jagiellonian University –<br />
Ingardena 3/30-060 – Krakow – POL<br />
† Department of Cl<strong>in</strong>ical Biochemistry – Collegium Medicum, Jagiellonian University –<br />
Kopernika 15a/31-501 – Krakow – POL<br />
‡ Department of Microbiology, Faculty of Commodity Science –<br />
Cracow University of Economics – Rakowicka 27/31-510 – Krakow – POL<br />
jarosz@chemia.uj.edu.pl<br />
The most commonly considered materials for bone-implants are titanium and its<br />
alloys due to their good biocompatibility, high strength to weight ratio. [1] Titaniumbased<br />
materials are widely used <strong>in</strong> medic<strong>in</strong>e and dentistry, for orthopedic, dental and<br />
other implants, as well as <strong>in</strong> medical devices (e.g. screws and plates). Unfortunately,<br />
there are some drawbacks and limitations to the use of titanium implants, e.g. their<br />
<strong>in</strong>ertness and long-term osseo<strong>in</strong>tegration via the natural oxide (TiO2) exist<strong>in</strong>g on<br />
their surface. Therefore, titanium with nanoporous materials on its surface becomes<br />
a novel solution for bone implant technology. [2]<br />
Anodic titanium oxide (ATO) films on Ti foils were prepared via a three-step anodization<br />
<strong>in</strong> glycol ethylene based solutions conta<strong>in</strong><strong>in</strong>g NH4F (0.38 wt.%) and H2O<br />
(1.79 wt.%) under a constant voltage of 40 V. The duration of first and second anodiz<strong>in</strong>g<br />
step was 3h. The duration of the third step was 10 m<strong>in</strong>. Titanium foils<br />
(99.5 % purity) were used as both work<strong>in</strong>g and counter electrodes. The anodization<br />
was performed <strong>in</strong> two-electrode cells at a constant temperature of 20 ◦ C. After<br />
anodization, some samples were annealed at the temperature of 400 or 1000 ◦ C <strong>in</strong><br />
order to achieve different polymorphic structures of TiO2 (anatase and rutile). Other<br />
samples were modified with silver nanoparticles. Such prepared samples were used<br />
for the cell growth and microbial exam<strong>in</strong>ations. Adipocyte derived stem cells obta<strong>in</strong>ed<br />
from abdom<strong>in</strong>al liposuction were seeded onto TiO2 surfaces. Cell viability,<br />
proliferation and phenotype were assessed by the measurement of redox reactions <strong>in</strong><br />
the cells, cellular DNA, tritiated thymid<strong>in</strong>e ([3H]-TdR) <strong>in</strong>corporation and alkal<strong>in</strong>e<br />
phosphatase (ALP) production. Staphylococcus aureus bacteria were used for exam<strong>in</strong>ation<br />
of antimicrobial character of nanoporous TiO2 on Ti. The evaluations of<br />
the <strong>in</strong>hibition of microorganism growth and biofilm formation on various nanoporous<br />
TiO2 surfaces were performed. Nanoporous TiO2 surfaces were placed either on the<br />
surface of Mueller-H<strong>in</strong>ton agar which was <strong>in</strong>oculated with microorganisms before or<br />
stroked perpendicularly <strong>in</strong>to the <strong>in</strong>oculated selected broth. In both techniques a zone<br />
of <strong>in</strong>hibition on broths was measured. For biofilm formation tests, nanoporous TiO2<br />
surfaces were placed <strong>in</strong> liquid broths with suspension of microorganisms. The occurrence<br />
of biofilm on plates was <strong>in</strong>vestigated with a microscopic and UV radiation<br />
methods.<br />
[1] K.M. Buettner, A.M. Valent<strong>in</strong>e, Chem. Rev. 2012, 112, 1863-1881.<br />
[2] M. Stigter, J. Bezemer, K. de Groot, P. Layrolle, J. Control. Release 2004, 99, 127-137<br />
58 Thursday 17:40 - 20:10 Poster 001
Superparamagnetic Iron Oxide Nanoparticles Coated with<br />
Chitosan - Physicochemical Characterization<br />
Agnieszka Szpak, Szczepan Zapotoczny, Maria Nowakowska<br />
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Kraków – POL<br />
szpak@chemia.uj.edu.pl<br />
Superparamagnetic Iron Oxide Nanoparticles (SPIONs) have attracted attention due<br />
to their great magnetic properties, biodegradablility and nontoxicity, what is crucial<br />
for biomedical applications, especially as tools <strong>in</strong> advanced diagnostic and therapy<br />
(contrast enhancement for magnetic resonance imag<strong>in</strong>g, drug delivery, detoxification,<br />
hyperthermia treatment, cell separation, detoxification of biological fluids). [1,2]<br />
Here we present results of our studies on fabrication and physicochemical characterization<br />
of stable suspensions of SPIONs. Nanoparticles are covered with ultrath<strong>in</strong><br />
layer of polymer prevent<strong>in</strong>g aggregation process.<br />
For <strong>in</strong>vestigat<strong>in</strong>g SPIONs properties we used a wide range of methods such as Dynamic<br />
Light Scatter<strong>in</strong>g (size and charge), Transmission Electron Microscopy (size),<br />
Vibrat<strong>in</strong>g Sample Magnetometer (magnetization of suspension) and High Resolution<br />
Electron Microscope for (crystallographic structure) among others. The possibility of<br />
us<strong>in</strong>g SPIONs towards biological applications will be <strong>in</strong>vestigated <strong>in</strong> the next step.<br />
Acknowledgements: This work was supported by the European Union from the resources<br />
of the European Regional Development Found under the Innovative Economy<br />
Programme (grant coord<strong>in</strong>ated by JCET-UJ, No POIG.01.01.02-00-060/09)<br />
[1] A.K. Gupta, M. Gupta, Biomaterials 2005, 26, 3995-4021.<br />
[2] S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. Vander Elst, R.N. Muller, Chemical<br />
Reviews 2008, 108, 2064-2110.<br />
Poster 002 Thursday 17:40 - 20:10 59
Synthesis of Substituted Pyrid<strong>in</strong>yl Im<strong>in</strong>othiazolid<strong>in</strong>one<br />
Compounds via One-Pot Method<br />
Fatma Tülay Tugcu<br />
Department of Chemistry – Yildiz Technical University, Faculty of Science – İstanbul –<br />
TUR<br />
ttugcu@yahoo.com<br />
Because of their reaction capabilities both as N-nucleophiles and as S-nucleophiles,<br />
thioureas are successfully used <strong>in</strong> the synthesis of biologically active compounds. As a<br />
result of comprehensive researches made <strong>in</strong> recent years, new thiourea compounds hav<strong>in</strong>g<br />
anticancer, antitumor, antiviral, anti-HIV, antimalarial and other various pharmacological<br />
activities have been synthesized. [1]<br />
On the other hand, antimicrobial, antituberculosis and antibacterial activities of<br />
im<strong>in</strong>othiazolid<strong>in</strong>one compounds have been observed <strong>in</strong> their biological and pharmacological<br />
activity studies. [2] In addition, existence of anti-<strong>in</strong>flammatory [3] and antifungal<br />
[4] effects of these compounds are also mentioned.<br />
Therefore, <strong>in</strong> this study, some new substituted pyrid<strong>in</strong>yl im<strong>in</strong>othiazolid<strong>in</strong>one derivatives<br />
which are considered that may possess biological activity have been obta<strong>in</strong>ed via<br />
one-pot multicomponent method by us<strong>in</strong>g thiophene-2-carboxaldehyde, chloroacetic<br />
acid and several hetaryl-thioureas; and the structures of all these synthesized compounds<br />
have been clarified with spectral data: [5]<br />
Thanks for Yıldız Technical University Scientific Research Projects Coord<strong>in</strong>ation’s support<br />
<strong>in</strong> this study.Project No: 2010-01-02-GEP01.<br />
[1] W. Liu, J. Zhou, T. Zhang, H. Zhu, H. Qian, H. Zhang, W. Huang, R. Gust, Bioorganic and<br />
Medic<strong>in</strong>al Chemistry Letters 2012, 22, 2701-2704.<br />
[2] Ş. G. Küçükgüzel, S. Rollas, H. Erdeniz, M. Kiraz, A. C. Ek<strong>in</strong>ci, A. Vid<strong>in</strong>, European Journal<br />
of Medic<strong>in</strong>al Chemistry 2000, 35, 761-771.<br />
[3] R. Ottana, R. Maccari, M.L. Barreca, G. Bruno, A. Rotondo, A. Rossi, G. Chiricosta, R. Di<br />
Paola, L. Sauteb<strong>in</strong>, M. G. Vigorita, Bioorganic and Medic<strong>in</strong>al Chemisty 2005, 13, 4243-4252.<br />
[4] H. Liu, Z. Li, T. Anthonsen, Molecules 2000, 5, 1055-1061.<br />
[5] S. Kasmi-Mir, A. Djafri, L. Paqu<strong>in</strong> J., Hamel<strong>in</strong>, M. Rahmouni, Molecules 2006, 11, 597-602.<br />
60 Thursday 17:40 - 20:10 Poster 003
Nanoscaled phosphors based on metal (II) and gadol<strong>in</strong>ium<br />
mixed borates doped with dysprosium (III) ions<br />
Andrii Shyichuk, Stefan Lis<br />
Faculty of Chemistry – Adam Mickiewicz University – Umultowska 89b – Poznań – POL<br />
andrii.shyichuk@gmail.com<br />
Summary<br />
Mixed borate-based nanophosphors of general formula MeMe’2Gd2(BO3)4, where:<br />
Me, Me’ = Ca, Sr, Ba, were obta<strong>in</strong>ed by the sol-gel Pech<strong>in</strong>i method. Accord<strong>in</strong>g to<br />
Scherrer XRD analysis, the size of particles was about 50 nm. The dope of Dy 3+<br />
resulted <strong>in</strong> white emission. The phosphors can be excited by 350 nm near-ultraviolet<br />
light. The emission color can be tuned between yellowish-white, bluish-white and almost<br />
pure white, what was confirmed with CIE chromaticity diagrams. The materials<br />
can f<strong>in</strong>d potential applications <strong>in</strong> lum<strong>in</strong>escent tubes and light emitt<strong>in</strong>g diodes.<br />
Structure<br />
The composition of the materials was kept as MeMe’2Gd2−xDyx(BO3)4, where Me,<br />
Me’ = Ca, Sr, Ba. The details of the synthesis procedure are described <strong>in</strong> our paper<br />
[1]. The materials were studied by means of powder X-ray diffraction (XRD), spectrofluorimetry<br />
<strong>in</strong> the visible range and lum<strong>in</strong>escence lifetime measurements. In the<br />
case of Me = Me’ the XRD patterns of the studied compounds matched the related<br />
entries of JCPDS database. However, <strong>in</strong> the case of different Me and Me’ the peaks <strong>in</strong><br />
XRD patterns were located between the peaks of appropriate references. The width<br />
of peaks was much smaller than the shifts. It means, that new structures conta<strong>in</strong><strong>in</strong>g<br />
both Me and Me’ were formed and no mixture of two phases was present. Sherrer<br />
XRD analysis [2] showed particles size of about 50 nm.<br />
Photolum<strong>in</strong>escence<br />
The excitation spectra of the samples conta<strong>in</strong>ed maxima <strong>in</strong> the spectral range of 330-<br />
400 nm, correspond<strong>in</strong>g to 4f-4f transitions from the ground state of 6 H 15/2 to 4 F 7/2,<br />
6 F9/2, 4 G 21/2, 4 H 15/2, 4 K 15/2, 4 P 3/2, 4 P 7/2 levels of Dy 3+ . The emission was<br />
represented by two ma<strong>in</strong> bands at 486 and 577 nm correspond<strong>in</strong>g to transitions from<br />
4 F9/2 Dy 3+ level to 6 H 15/2 and 6 H 13/2 levels, respectively. The decay times varied<br />
with<strong>in</strong> the range of 2-2.5 ms and the lum<strong>in</strong>escence decay curves were monoexponential.<br />
The color of emission (characterized by CIE 1931 color coord<strong>in</strong>ates) l<strong>in</strong>early changed<br />
<strong>in</strong> the series of Ba3Gd2(BO3)4, Ba2SrGd2(BO3)4, BaSr2Gd2(BO3)4, Sr3Gd2(BO3)4,<br />
CaSr2Gd2(BO3)4, Ca2SrGd2(BO3)4, Ca3Gd2(BO3)4 from yellowish-white to bluishwhite<br />
be<strong>in</strong>g very close to pure white (D65 standard source) <strong>in</strong> all cases. Additional<br />
excitation bands aris<strong>in</strong>g from transitions from the ground state of 8 S 7/2 to 6 I 15/2 and<br />
6 P7/2 level of Gd 3+ were present <strong>in</strong> spectra of Gd-based compounds. Those bands<br />
were located at 272.8 and 310 nm, respectively. No emission from Gd 3+ was observed.<br />
It means that efficient energy transfer occurred from Gd 3+ to the Dy 3+ dope ions.<br />
[1]<br />
A.A. Shyichuk, S. Lis, J. Rare Earth 2011, 29 (12), 1161.<br />
[2]<br />
A. Patterson, Phys. Rev. 1939, 10, 56.<br />
[3]<br />
C. Kodaira, H.F. Brito, O.L. Malta, O.A. Serra, J. Lum<strong>in</strong>. 2003, 101, 11.<br />
[4]<br />
H. Mataki, Rare earth-metal nanocluster doped organic/<strong>in</strong>organic optical nanocomposites<br />
(thesis), Waseda University, Tokyo 2007.<br />
Poster 004 Thursday 17:40 - 20:10 61
A versatile approach for coat<strong>in</strong>g oxidic surfaces with a range<br />
of nanoparticulate materials.<br />
Jan Poppe, Stefanie Gabriel, Lydia Liebscher, Stephen G. Hickey, Alexander Eychmüller<br />
Physical Chemistry and Electrochemistry – TU Dresden – Bergstraße 66b – Dresden –<br />
GER<br />
jan.poppe@chemie.tu-dresden.de<br />
A versatile and effective method by which a wide range of nanoparticulate materials<br />
can be attached to a variety of oxidic surfaces is presented. After synthesiz<strong>in</strong>g the<br />
nanocrystals (PbS, CdSe, CdSe@CdS core shell, Au) via standard hot <strong>in</strong>jection routes,<br />
the stabiliz<strong>in</strong>g ligands are exchanged to 3-mercatopropyl-trimethoxysilane (MPTMS).<br />
The ligand exchange is monitored us<strong>in</strong>g FTIR-spectroscopy and transmission electron<br />
microscopy (TEM). The modified nanocrystals were then applied to different oxidic<br />
substrates, yield<strong>in</strong>g homogeneous and dense particle films. The effectiveness of this<br />
coat<strong>in</strong>g procedure is then compared with the commonly employed deposition methods<br />
by means of electrochemical measurements and scann<strong>in</strong>g electron microscopy imag<strong>in</strong>g<br />
and found to be vastly superior <strong>in</strong> its particle deposition efficiency. The applicability<br />
of this methodology is further verified by deposit<strong>in</strong>g a layer of PbS nanoparticles onto<br />
a silica sphere colloidal crystals to modify its optical properties.<br />
SEM image of PbS nanoparticles attached to a electrochemically grown ZnO substrate.<br />
62 Thursday 17:40 - 20:10 Poster 005
Complexes of Manganese, Iron and Cobalt with Sterically<br />
Demand<strong>in</strong>g Indenyl Ligands<br />
Miyuki Maekawa ∗ , Constant<strong>in</strong> Daniliuc † , Matthias Freytag ∗ , Peter Jones ∗ ,<br />
Marc Walter ∗<br />
∗ Institut für Anorganische und Analytische Chemie – TU Braunschweig – Hagenr<strong>in</strong>g 30 –<br />
Braunschweig – GER<br />
† Organisch-Chemisches Institut – Westfälische Wilhelms-Universität Münster –<br />
Corrensstrasse 40 – Münster – GER<br />
m.maekawa@tu-bs.de<br />
Indenyl complexes have been used <strong>in</strong> wide range applications such as polymerization [1]<br />
and hydrosilylation, [2] and r<strong>in</strong>g substituents can vary their properties. Although <strong>in</strong>denyl<br />
ligands are also monoanionic, formal six-electron ligands that are often considered<br />
close analogues of the cyclopentadienyl anion, they have been explored to a<br />
lesser extent. Several substituted <strong>in</strong>denyl systems have been reported, but examples<br />
with bulky alkyl substituted derivative have relatively limited, e.g. C9H5(iPr)2 [3] ,<br />
C9H5(tms)2 [3] and C9H6(cHex) [4] .<br />
Here we report on the preparation of the series of manganese, iron and cobalt complexes<br />
bear<strong>in</strong>g stericaly demand<strong>in</strong>g 1,3-disubstitueted <strong>in</strong>denyl ligands, C9H5(tBu)2<br />
(1) and C9H5(cHex)2 (2). The <strong>in</strong>fluence of bulky alkyl groups on structure and electronic<br />
properties of these metallocene will be presented. [5] Although the cone angles<br />
and electronic properties of each ligands are similar to 1,2,4-(tBu)3C5H2 (Cp’), [6]<br />
<strong>in</strong>denyl iron half sandwich complexes are only stable at low temperature. This will<br />
be demonstrated for 1-FeI us<strong>in</strong>g suitable trapp<strong>in</strong>g experiments. [5]<br />
trapp<strong>in</strong>g experiment of <strong>in</strong>denyl iron half sandwich complexwith CO<br />
[1]<br />
T. E. Ready, J. C. W. Chien, M. D. Rausch, J. Organomet. Chem. 1999, 583, 11.<br />
[2]<br />
H. Brunner, K. Fisch, Angew. Chem. Int. Ed. 1990, 29, 1131.<br />
[3]<br />
C. A. Bradley, S. Flores-Torres, E. Lobkovsky, H. D. Abruña, P. J. Chirik, Organometallics<br />
2004, 23, 5322.<br />
[4]<br />
C. Krüger, F. Lutz, M. Nolte, G. Erker, M. Aulbach, J. Organomet. Chem. 1993, 452, 79.<br />
[5]<br />
M. Maekawa, C. G. Daniliuc, M. Freytag, P. G. Jones, M. D. Walter, Dalton Trans. 2012, 41,<br />
10317.<br />
[6]<br />
A. Glöckner, H. Bauer, M. Maekawa, T. Bannenberg, C. G. Daniliuc, P. G. Jones, Y. Sun, H.<br />
Sitzmann, M. Tamm, M. D. Walter, Dalton Trans. 2012, 41, 6614.<br />
Poster 006 Thursday 17:40 - 20:10 63
Compatibility Studies Of Poly(Ether Imide) - Liquid<br />
Crystall<strong>in</strong>e (4-[4-(Dodesiloksi) Benzoyloxy] Benzoic Acid<br />
Mixtures By Viscometry and Fourier Transform Infrared<br />
Spectroscopy<br />
Fatih Cakar, Selma Ozkal, Hale Ocak, Belkıs Bilg<strong>in</strong>-Eran, Ozlem Cankurtaran,<br />
Ferdane Karaman<br />
Chemistry – Yildiz Technical University – Istanbul – TUR<br />
ffatihcc@yahoo.com<br />
Liquid crystals (LCs) have more order than isotropic liquid state, but less order<br />
than solid crystall<strong>in</strong>e state and exhibit properties between of them. [1] They have<br />
been studied for many years not only because of their technological importance but<br />
also because of their extraord<strong>in</strong>ary physical properties such as dielectric and optical<br />
anisotropy, flow properties, and response to external fields. [2]<br />
Polyether imides such as Ultem, a well-known class of eng<strong>in</strong>eer<strong>in</strong>g thermoplastic polymers,<br />
offer exceptional thermal, chemical and mechanical stability and are available<br />
<strong>in</strong> large quantities. [3] Their cost is similar to other thermoplastic polymers that offer<br />
similar performance and significantly more economical than small batch thermoplastic<br />
polymers. Polyether imides have higher diffusivity selectivity due to their fused<br />
r<strong>in</strong>g structure and rigid backbone. Their high glass transition temperatures allow<br />
higher pressure and temperature applications without plastic deformation. [4]<br />
Mix<strong>in</strong>g is very important <strong>in</strong> modern technologies for process<strong>in</strong>g of materials composed<br />
of many different chemical components. Polymer and liquid crystal mixtures are an<br />
important area of <strong>in</strong>terest <strong>in</strong> science and eng<strong>in</strong>eer<strong>in</strong>g because of its many applicat<br />
ions <strong>in</strong> <strong>in</strong>dustry. Miscibility can be detected by a number of techniques. Among these<br />
techniques, it is well known that determ<strong>in</strong>ation of the viscometry of a dilute solution<br />
is a simple and quick method for determ<strong>in</strong><strong>in</strong>g the miscibility. Fourier transform<br />
<strong>in</strong>frared spectroscopy (FTIR) is one of the many techniques that have been applied<br />
to <strong>in</strong>vestigate specific molecular bond<strong>in</strong>g <strong>in</strong>teractions <strong>in</strong> polymer blends. [5] In the case<br />
of immiscible systems, the spectrum of the blend reflects the appropriate addition of<br />
the IR spectrum of the two <strong>in</strong>dividual components. In the case of miscible or partially<br />
miscible polymer blends, the IR spectrum would show formation of new bands as the<br />
results of miscibility; and disappearance of some component bands. Shifts <strong>in</strong> the<br />
specific bands would give <strong>in</strong>formation on the switches from component specific bonds<br />
to the bonds between components.<br />
This study deals with the determ<strong>in</strong>ation of the miscibility of poly (ether imide) (Ultem)<br />
and their mixtures with liquid crystall<strong>in</strong>e (4-[4-(Dodesiloksi) benzoyloxy] benzoic<br />
acid (4DBBA)) compounds <strong>in</strong> dilute solutions. Mixtures of variable compositions<br />
from 0 to 100 wt were prepared by solvent cast<strong>in</strong>g. Their miscibility was <strong>in</strong>vestigated<br />
by us<strong>in</strong>g viscometry and FTIR.<br />
[1]<br />
N. Sen, Current Science 2000, 79(10), 1417.<br />
[2]<br />
N.Y. Canli, F. Yakuphanoğlu, B. Bilg<strong>in</strong>-Eran, Optoelectronics and Advanced Materials-Rapid<br />
Communications 2009, 3(7), 731.<br />
[3]<br />
M.K. Ghosh K. L. Mittal, Polyimides: Fundamentals and Applications, Marcel Dekker, New<br />
York, 1996.<br />
[4]<br />
F. Cakar, O. Cankurtaran, Polymer Bullet<strong>in</strong> 2005, 55, 95.<br />
[5]<br />
M.T. Kalichevsky, J.M.V. Blanshard, Carbohydrate Polymers 1993, 20, 107.<br />
64 Thursday 17:40 - 20:10 Poster 007
Synthesis and characterization of InSb nanowires for<br />
thermoelectric applications<br />
Katarzyna Hnida ∗ , William Töllner † , Tim Böhnert † , Kornelius Nielsch † ,<br />
Grzegorz Sulka ∗ , Marian Jaskuła ∗<br />
∗ Department of Physical Chemistry & Electrochemistry – Jagiellonian University –<br />
Ingardena 3 – Cracow – POL<br />
† Institute of Applied Physics – University of Hamburg – Jungiusstrasse 11 –<br />
Hamburg – GER<br />
hnida@chemia.uj.edu.pl<br />
Over the past few years, simulations, theoretical calculations and laboratory tests<br />
suggested that there is a relationship between the size of nanostructures (nanodots,<br />
nanowires and nanotubes) and efficiency of thermoelectric materials. [1, 2] Thus, if developed<br />
relatively <strong>in</strong>expensive and not very complicated methods for the preparation<br />
of thermoelectric nanostructures they could have a wide practical application.<br />
Electrodeposition is the method of choice to synthesize nanoeng<strong>in</strong>eered thermoelectric<br />
materials because of low operat<strong>in</strong>g and capital costs, high deposition rates, near<br />
room temperature operation, and the ability to tailor the properties of materials by<br />
adjust<strong>in</strong>g deposition conditions.<br />
Indium antimonide (InSb) is a small band gap semiconductor with high carrier mobility<br />
and small effective mass, and is widely use <strong>in</strong> optical detectors, high-speed electronic<br />
devices, and magnetic field sensors. Different methods have been used to fabricate<br />
InSb nanowires, such as physical and chemical vapor deposition (PVD, CVD),<br />
vapor-liquid-solid (VLS), and hydrothermal methods. Comparatively, the pulse electrodeposition<br />
process us<strong>in</strong>g porous anodic alum<strong>in</strong>um oxide (AAO) templates, is an<br />
effective and <strong>in</strong>expensive method of fabricat<strong>in</strong>g nanowires.<br />
In this work, we have fabricated a nanowire-based device us<strong>in</strong>g laser lithography<br />
to measure the Seebeck coefficient and resistance of an InSb nanowire. The InSb<br />
nanowire was synthesized us<strong>in</strong>g template assisted pulse electrodeposition method.<br />
Acknowledgments This work was supported by the International PhD-studies programme<br />
at the Faculty of Chemistry Jagiellonian University with<strong>in</strong> the Foundation<br />
for Polish Science MPD Programme co-f<strong>in</strong>anced by the EU European Regional Development<br />
Fund.<br />
[1] M. S. Dresselhaus et. al., Low dimensional thermoelectricity, <strong>in</strong>: T. M. Tritt (Ed.), Semiconductors<br />
and Semimetals: Recent Trends <strong>in</strong> Thermoelectric Materials Research III, vol. 71,<br />
Academic Press, San Diego, CA, 2001, 1-121, Chap. 1<br />
[2] R. Saito, G. Dresselhaus, M. S. Dresselhaus, Physical Properties of Carbon Nanotubes, Imperial<br />
College Press, London, 1998.<br />
Poster 008 Thursday 17:40 - 20:10 65
Synthesis and characterization of new monomer and ATRP<br />
<strong>in</strong>itiators- towards conduct<strong>in</strong>g polymer brushes<br />
Karol Wolski, Michał Szuwarzyński, Szczepan Zapotoczny<br />
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Cracow – POL<br />
wolski@chemia.uj.edu.pl<br />
Advanced polymeric materials like polymer brushes are very promis<strong>in</strong>g for design<strong>in</strong>g<br />
novel organic solar cells. Organic photovoltaic cells are cheaper than commonly used<br />
silicon cells however they are less efficient. The key issue <strong>in</strong> design<strong>in</strong>g of new efficient<br />
materials is undisturbed transport of charge carriers to appropriate electrodes<br />
<strong>in</strong> the cell. The structure of conductive polymer brushes can provide directional<br />
and effective transport of such charge carriers formed along s<strong>in</strong>gle polymer cha<strong>in</strong>s.<br />
We report here synthesis of essential compounds for Surface-Initiated Atom Transfer<br />
Radical Polymerizations (ATRP) applied for template polymerization of conjugated<br />
polymers. [1] We present the synthesis of a monomer which has both −C=C− and<br />
−C≡C− groups <strong>in</strong> its structure and the pyrid<strong>in</strong>e r<strong>in</strong>g. In addition, two relatively<br />
short ATRP <strong>in</strong>itiators, which can form SAMs on the gold substrate are synthesized.<br />
Physicochemical characterisation of the new compounds is presented. AFM images<br />
of the polymer brushes of the selected monomers obta<strong>in</strong>ed by “graft<strong>in</strong>g from” method<br />
with application of the new <strong>in</strong>itiators are also shown.<br />
Acknowledgment: The authors would like to thank Polish M<strong>in</strong>istry of Science and<br />
Higher Education for the f<strong>in</strong>ancial support (“Ideas Plus”; grant no. IdP2011 000561).<br />
[1] M. Szuwarzyński, J. Kowal, S. J. Zapotoczny, Mater. Chem. 2012, 22, 20179-20181.<br />
66 Thursday 17:40 - 20:10 Poster 009
R<strong>in</strong>g open<strong>in</strong>g polymerization of organic carbonats us<strong>in</strong>g CO2<br />
- carbene adducts as effective organo catalyst<br />
Annika Reitz , Dirk Kuckl<strong>in</strong>g, René Wilhelm<br />
Chemie – Universität Paderborn – Warburgerstraße 100 – Paderborn – GER<br />
areitz@mail.upb.de<br />
Many modern applications of polymers are <strong>in</strong> biological systems. Therefore, residual<br />
metals should be avoided and the polymer itself should be degradable. Polytrimethylene<br />
carbonate is slightly more stable than polylactide but still biodegradable <strong>in</strong> reasonable<br />
span of time and therefore a good choice for stents or similar applications.<br />
S<strong>in</strong>ce the homopolymer of trimethylencarbonate shows a very low glass temperature<br />
copolymerization improves the mechanical properties and multiplies the uses of Polytrimethylencarbonat.<br />
Highly reactive carbenes can be used as efficient organo catalyst<br />
but their moisture and air sensibility is a major drawback. Especially their great diversity<br />
due to the effect of substituents makes them a great advantage. The use of<br />
adducts, especially those of CO2, is a major improvement, as they are air stable and<br />
easy to handle.<br />
The polymerization was carried out <strong>in</strong> bulk with benzylalcohol as <strong>in</strong>itiator and the<br />
CO2 adduct of 1,3 Bis(2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene as<br />
catalyst. To improve the polymerization microwave energy is used. In this microwave<br />
assisted polymerization the turnover <strong>in</strong>creases while the polydispersity stays low.<br />
The polymers are characterized by NMR and IR spectroskopy, ESI-IMS-MS and GPC.<br />
Their molecular weight, polydispersity and end groups will be discussed.<br />
chemical equation of polymerization<br />
Poster 010 Thursday 17:40 - 20:10 67
Investigat<strong>in</strong>g Thermodynamic Interactions of<br />
4-[4-((S)-Citronellyloxy) Benzoyloxy] Benzoic Acid (SBBA)<br />
Liquid Crystal with Some Solvents by Inverse Gas<br />
Chromatography<br />
Ismail Erol, Fatih Cakar, Hale Ocak, Belkis Bilg<strong>in</strong>-Eran, Ozlem Cankurtaran,<br />
Ferdane Karaman<br />
Chemistry – Yildiz Technical University – Istanbul – TUR<br />
ismailerol21@gmail.com<br />
Liquid crystals (LCs) represent a fasc<strong>in</strong>at<strong>in</strong>g state of matter with wide technical<br />
applications <strong>in</strong> display <strong>in</strong>dustry and optoelectronics, significant importance for the<br />
development of new functional materials, nanopattern<strong>in</strong>g, tissue eng<strong>in</strong>eer<strong>in</strong>g, sensor<br />
and biosensor applications, and also provid<strong>in</strong>g a fundamental concept <strong>in</strong> biological<br />
self-assembly. This is due to the dual nature of LCs, comb<strong>in</strong><strong>in</strong>g features of anisotropic<br />
crystall<strong>in</strong>e solids and isotropic liquids, enabl<strong>in</strong>g their soft self-assembled and ordered<br />
structures to respond to external stimuli, but also to their ability of self-heal<strong>in</strong>g of<br />
defects formed. [1]<br />
Inverse gas chromatography (IGC) is now widely used to exam<strong>in</strong>e the physicochemical<br />
properties of different materials of both liquid and solid. The term “<strong>in</strong>verse” <strong>in</strong>dicates<br />
that the exam<strong>in</strong>ed material, e.g. a polymer blend or modified silica, placed <strong>in</strong> the<br />
chromatographic column, is of <strong>in</strong>terest <strong>in</strong> contrast to the common analytical gas<br />
chromatographic experiments. Carefully selected test solutes are <strong>in</strong>jected <strong>in</strong>to the<br />
flow of a carrier gas and transported over the surface of, e.g. fiber. The retention<br />
time and the peak elution profiles of Standard solutes, affected by <strong>in</strong>teractions between<br />
the solute and stationary phase, are used to estimate those <strong>in</strong>teractions. [2]<br />
IGC is an easy, fast and economic method to <strong>in</strong>vestigate liquid crystal-solvent <strong>in</strong>teractions.<br />
Us<strong>in</strong>g IGC to study liquid crystal-solvent <strong>in</strong>teractions is new method and<br />
there are only few study <strong>in</strong> literature. In IGC process, there is relevance between<br />
liquid crsytal-solvent <strong>in</strong>teractions and specific retention volumes. [3] Thermodynamic<br />
parameters that obta<strong>in</strong>ed by us<strong>in</strong>g specific retention volume, use to expla<strong>in</strong> liquid<br />
crystal-solvent <strong>in</strong>teractions.<br />
In this study, thermodynamic <strong>in</strong>teractions of 4-[4-((S)-Citronellyloxy ) benzoyloxy]<br />
benzoic acid with some solvents were exam<strong>in</strong>ed by <strong>in</strong>verse gas chromatography method.<br />
Firstly, the specific retention volumes of the solvents were determ<strong>in</strong>ed and the retention<br />
diagrams were plotted for liquid crystal-solvent systems. And then, the weight<br />
fraction activity coefficient, Flory-Hugg<strong>in</strong>s and equation of state <strong>in</strong>teraction parameters,<br />
effective exchange energy parameter, exchange enthalpy and entropy parameters<br />
were calculated at the temperature range which thermodynamical equilibrium occurred.<br />
[1] Shanker G., Nagaraj M., Kocot A., Vij J.K., Prehm M., Tschierske C., “Nematic Phases <strong>in</strong> 1,2,4-<br />
Oxadiazole-Based Bent-Core Liquid Crystals: Is There a Ferroelectric Switch<strong>in</strong>g?”, Adv. Funct.<br />
Mater. 2012, 22(8), 1671-1683.<br />
[2] A. Voelkel, “Inverse gas chromatography <strong>in</strong> the exam<strong>in</strong>ation of acid–base and some other properties<br />
of solid materials”, <strong>in</strong>: A. Dabrowski, V.A. Tertykh (Eds.), Adsorption on New and Modified<br />
Inorganic Sorbents, Studies <strong>in</strong> Surface Science and Catalysis 1996, vol. 99, 465.<br />
[3] Price G.J., Shillcock I.M., “Investigation of Mesophase Transitions <strong>in</strong> Liquid Crystals Us<strong>in</strong>g<br />
Inverse Gas Chromatography”, Can. J. Chem. 1995, 73, 1883-1892.<br />
68 Thursday 17:40 - 20:10 Poster 011
Synthesis, Thermal, and Electrical Properties of Stilbene<br />
Bridged Polymeric Z<strong>in</strong>c Phthalocyan<strong>in</strong>e<br />
Muhammet Kasim Sener ∗ , Hilal Yurtseven ∗ , Mehmet Arif Kaya ∗ , Ahmet Alt<strong>in</strong>dal †<br />
∗ Department of Chemistry – Yildiz Technical University – Istanbul – TUR<br />
† Department of Physics – Yildiz Technical University – Istanbul – TUR<br />
mkasimsener@gmail.com<br />
Polymeric phthalocyan<strong>in</strong>es are very <strong>in</strong>terest<strong>in</strong>g materials s<strong>in</strong>ce they belong to a class<br />
of π-conjugated semiconductor polymers which offer a unique comb<strong>in</strong>ation of properties.<br />
Polymeric phthalocyan<strong>in</strong>es are ma<strong>in</strong>ly prepared via polycyclotetramerization<br />
reactions of bifunctional monomers such as aromatic tetracarbonitriles, various<br />
oxy-, arylenedioxy- and alkylenedioxy-bridged diphthalonitriles, and other nitriles or<br />
tetracarboxylic acid derivatives <strong>in</strong> the presence of metal salts or metals. We report<br />
here, the synthesis and characterization of a new z<strong>in</strong>c conta<strong>in</strong><strong>in</strong>g polymeric phthalocyan<strong>in</strong>e<br />
and its precursor. To understand the semiconduct<strong>in</strong>g and dielectric properties<br />
of polymeric z<strong>in</strong>c phthalocyan<strong>in</strong>e, a systematic <strong>in</strong>vestigation on dc and ac electrical<br />
properties and their variation with temperature and frequency is attempted. Also,<br />
thermal properties of the polymeric z<strong>in</strong>c phthalocyan<strong>in</strong>e is <strong>in</strong>vestigated by differential<br />
scann<strong>in</strong>g calorimetry (DSC) and thermal gravimetric analysis (TGA).<br />
[1]<br />
A. Bilg<strong>in</strong>, C. Yagci, U. Yildiz, E. Ozkazanc, E. Tarcan, Polyhedron 2009, 28, 2268.<br />
[2]<br />
D. Wöhrle, Macromol. Rapid. Commun. 2001, 22, 68.<br />
[3]<br />
D. Wöhrle, U. Marose, R. Knoop, Makromol. Chem. 185, 186, 2209.<br />
[4]<br />
A. Bilg<strong>in</strong>, C. Yagci, U. Yildiz, Macromol. Chem. Phys. 2005, 206,2257.<br />
[5]<br />
A. Bilg<strong>in</strong>, A. Mendi, U. Yildiz, Polymer 2006, 47, 8462.<br />
[6]<br />
Y. A. Kokshorov, A. I. Sherle, A. N. Tikhonov, Synth. Met. 2005, 149, 19.<br />
Poster 012 Thursday 17:40 - 20:10 69
Use of the oxygen carrier Hemerythr<strong>in</strong> for development of<br />
blood substitutes<br />
Mariann K<strong>in</strong>ga Arkosi ∗ , Radu Silaghi-Dumitrescu ∗ , August<strong>in</strong> Catal<strong>in</strong> Mot ∗ ,<br />
Denisa Hathazi ∗ , Iulia Lupan ‡ , Grigore Damian ⋄ , Eva Fischer-Fodor †<br />
∗ Department of Chemistry and Chemical Eng<strong>in</strong>eer<strong>in</strong>g – Babes-Bolyai University –<br />
Arany Janos Str. no. 11 – Cluj Napoca – ROU<br />
† Comprehensive Cancer Center – Ion Chiricuta Cancer Institute –<br />
Republicii Str. no. 34-36 – Cluj Napoca – ROU<br />
‡ Department of Biology – Babes-Bolyai University – Arany Janos Str. no. 11 –<br />
Cluj Napoca – ROU<br />
⋄ Department of Physics – Babes-Bolyai University – Arany Janos Str. no. 11 –<br />
Cluj Napoca – ROU<br />
arkosi.mariann@gmail.com<br />
Blood substitutes are used to carry oxygen and <strong>in</strong>crease the fluid volume <strong>in</strong> the<br />
human cardiovascular system <strong>in</strong> case of emergencies; they must accomplish numerous<br />
conditions concern<strong>in</strong>g stability, oxygen aff<strong>in</strong>ity, toxicity, immunogenic response and<br />
hydrodynamic volume. As opposed to Hemoglob<strong>in</strong> (Hb) based potential artificial<br />
oxygen carriers, Hemerythr<strong>in</strong> (Hr) based blood substitutes haven’t been exam<strong>in</strong>ed and<br />
described extensively and therefore might sound less familiar. My poster presentation<br />
aims to present <strong>in</strong>vestigations of this prote<strong>in</strong> as raw material for artificial oxygen<br />
carriers.<br />
Hr is a prote<strong>in</strong> found <strong>in</strong> mar<strong>in</strong>e <strong>in</strong>vertebrates which b<strong>in</strong>ds oxygen reversibly by the<br />
use of a non-heme diiron center. It is a very promis<strong>in</strong>g alternative to Hb for blood<br />
substitutes because, <strong>in</strong> contrast to Hb, Hr has dist<strong>in</strong>ctly smaller reactivity towards<br />
oxidative and nitrosative stress agents and also shows a remarkably smaller tendency<br />
to generate toxic free radicals <strong>in</strong> such reactions.<br />
In laboratory, the prote<strong>in</strong> was obta<strong>in</strong>ed through overexpression and purification of<br />
recomb<strong>in</strong>ant Phascolopsis Gouldii Hr from Escherichia coli stra<strong>in</strong>s. [1] Strategies for<br />
conversion of Hr <strong>in</strong>to an effective blood substitute typically <strong>in</strong>volved:<br />
i.) PEGylation of the prote<strong>in</strong> surface (wild type and site directed mutagens) primarily<br />
<strong>in</strong> order to decrease immunogenicity;<br />
ii.) glutaraldehyde-assisted polymerization and copolymerization (with Human Serum<br />
Album<strong>in</strong> and the non-heme iron peroxidase Rubrerythr<strong>in</strong>) which resulted <strong>in</strong> high<br />
molecular weight aggregates. [2]<br />
Characterization of the derivatives such as hydrodynamic volume or dioxygen reactivity<br />
(oxygen aff<strong>in</strong>ity, autooxidation rate) was ma<strong>in</strong>ly accomplished us<strong>in</strong>g size exclusion<br />
chromatographic and spectroscopic methods (UV-Vis and EPR). As well, aspects related<br />
to biological activity have already been <strong>in</strong>vestigated. The results of <strong>in</strong> vitro<br />
cytotoxicity assessments on human lymphocytes and HUVEC cells suggest that <strong>in</strong><br />
comparison to Hb derivatives, Hr-based blood substitutes have a better performance<br />
and show a cytoprotective effect. [3]<br />
[1]<br />
C.S. Farmer et al., “A leuc<strong>in</strong>e residue "Gates" solvent but not O2 access to the b<strong>in</strong>d<strong>in</strong>g pocket<br />
of Phascolopsis Gouldii hemerythr<strong>in</strong>.” J. Biol. Chem. 2000. 275(22), 17043-17050.<br />
[2]<br />
A.C. Mot et al., “Towards the Development of Hemerythr<strong>in</strong>-Based Blood Substitutes.” Prote<strong>in</strong><br />
J. 2010 29(6), 387-393.<br />
[3]<br />
E. Fischer-Fodor et al., “Towards hemerythr<strong>in</strong>-based blood substitutes: Comparative performance<br />
to hemoglob<strong>in</strong> on human leukocytes and umbilical ve<strong>in</strong> endothelial cells.” J. Biosci., 2011,<br />
36(2), 215-221.<br />
70 Thursday 17:40 - 20:10 Poster 013
Polymers with Phosphor Conta<strong>in</strong><strong>in</strong>g Side Cha<strong>in</strong>s via<br />
Modular Conjugation as Potential Flame Retardants<br />
Jördis Eisenblätter ∗ , Leonie Barner † , Ulrich Fehrenbacher ∗ ,<br />
Christopher Barner-Kowollik ‡<br />
∗ Environmental Eng<strong>in</strong>eer<strong>in</strong>g – Fraunhofer Institute for Chemical Technology (ICT) –<br />
Joseph-von-Fraunhofer-Strasse 7 – Pf<strong>in</strong>ztal – GER<br />
† Institute for Biological Interfaces (IBG I) – Karlsruhe Institute of Technology (KIT) –<br />
Herrmann-von-Helmholtz-Platz 1 – Eggenste<strong>in</strong>-Leopoldshafen – GER<br />
‡ Institut for Chemical Technology and Polymer Chemistry –<br />
Karlsruhe Institute of Technology (KIT) – Engesserstraße 18 – Karlsruhe – GER<br />
joerdis.eisenblaetter@ict.fraunhofer.de<br />
Polymers are an <strong>in</strong>dispensable part of our lives. They are used for example <strong>in</strong> the<br />
construction <strong>in</strong>dustry, <strong>in</strong> electrical eng<strong>in</strong>eer<strong>in</strong>g, transport, as well as <strong>in</strong> furniture and<br />
textiles. A major problem with the use of polymers, however, is their high flammability<br />
due to their carbon skeleton. Depend<strong>in</strong>g on the application high fire safety<br />
requirements are imposed. Often native polymers can not fulfill this. Hence the<br />
equipment of polymers with flame retardants represents a necessary step to reduce<br />
fire damage. Most of the flame retardants used up to now, however, show two ma<strong>in</strong><br />
problems: Firstly, ma<strong>in</strong>ly halogenated materials are used today as flame retardants<br />
will be prohibited <strong>in</strong> the next few years due to an <strong>in</strong>creas<strong>in</strong>g concern about persistence<br />
<strong>in</strong> the environment and potential negative health effects of these materials. Secondly,<br />
until now most of the flame retardants are <strong>in</strong>corporated <strong>in</strong>to the polymer as additives<br />
to achieve the protection of organic material. A drawback of this method is the<br />
emission of potential environmental harmful substances from the polymer over time.<br />
By b<strong>in</strong>d<strong>in</strong>g organo phosphorus compounds covalently to the polymer backbone, no<br />
emission of flame retardant from the polymer over time can occur. These so-called<br />
reactive flame retardants are homogeneously distributed <strong>in</strong> the polymer, whereby an<br />
agglomeration of the flame retardant component is prevented <strong>in</strong> the polymer. To ga<strong>in</strong><br />
reproducible results, the applied polymers have to possess narrow polydispersities and<br />
functional groups <strong>in</strong> the side cha<strong>in</strong>. Liv<strong>in</strong>g/controlled polymerization techniques like<br />
the reversible addition-fragmentation cha<strong>in</strong> transfer polymerization (RAFT) give access<br />
to excellent control over molecular weight of polymers while be<strong>in</strong>g tolerant to a<br />
wide list of functional groups. [1] Therefore it is possible to prepare well-def<strong>in</strong>ed polymers<br />
conta<strong>in</strong><strong>in</strong>g functional groups <strong>in</strong> the side cha<strong>in</strong>s that can subsequently be modified<br />
further, e.g. to functional groups that can be used for click reactions. Subsequently<br />
functional compounds can be <strong>in</strong>tegrated <strong>in</strong> these polymers by covalent l<strong>in</strong>kages to the<br />
side cha<strong>in</strong>s of the polymer. By l<strong>in</strong>k<strong>in</strong>g functionalized compounds to appropriate functionalized<br />
polymers via 1,3-dipolar cycloaddition described by Huisgen [2] a wide range<br />
of variable polymers can be designed. In this work, various phosphorylated polymers<br />
were prepared via 1,3-dipolar cycloaddition and analyzed via comprehensive thermal<br />
analysis to achieve <strong>in</strong>sight <strong>in</strong>to the characteristics of phosphorylated polymers.<br />
The focus was on the determ<strong>in</strong>ation of the <strong>in</strong>fluence of the chemical structure of the<br />
phosphorus esters on the thermal degradation behavior and the formation of a char<br />
layer. It could be shown that even with a small amount of 30 % can be achieved.<br />
[1] C. Barner-Kowollik, Handbook of RAFT Polymerization, Wiley-VCH, 2008.<br />
[2] R. Huisgen, “K<strong>in</strong>etics and reaction mechanisms: selected examples from the experience of<br />
forty years”, Pure and Applied Chemistry 1989, 613.<br />
Poster 014 Thursday 17:40 - 20:10 71
Metal Nanowire Arrays as Alternative Microelectronic<br />
Interconnectors<br />
Matthias Graf ∗ , Alexander Eychmüller ∗ , Klaus-Jürgen Wolter ‡<br />
∗ Physikalische Chemie & Elektrochemie – Technische Universität Dresden –<br />
Bergstrasse 66b – Dresden – GER<br />
‡ Electronics Packag<strong>in</strong>g Laboratory – Technische Universität Dresden –<br />
Helmholtzstrasse 10 – Dresden – GER<br />
graf@avt.et.tu-dresden.de<br />
S<strong>in</strong>ce the m<strong>in</strong>aturization of microelectronic structures parallel to the performance <strong>in</strong>crease<br />
<strong>in</strong>side these devices are relevant and ongo<strong>in</strong>g processes, meanwhile established<br />
strategies <strong>in</strong> connect<strong>in</strong>g ready-made devices have already been pushed to their geometrical<br />
limits. Apart, technologies as wire bond<strong>in</strong>g or stud bump solder<strong>in</strong>g start<br />
display<strong>in</strong>g limitations when it comes to high performance three-dimensional packag<strong>in</strong>g<br />
with a conventional demand to device reliability. This shows the necessity of<br />
new strategies be<strong>in</strong>g <strong>in</strong>vestigated for electronic packag<strong>in</strong>g. Here<strong>in</strong>, nanomaterials are<br />
considered as promis<strong>in</strong>g candidates s<strong>in</strong>ce they are expected to provide new, possibly<br />
attractive properties for solv<strong>in</strong>g upcom<strong>in</strong>g problems <strong>in</strong> electronic packag<strong>in</strong>g.<br />
We present <strong>in</strong>vestigations on electrochemical synthesis and characterization of templateassisted<br />
electrochemical growth of one-dimensionally elongated metal (Ag, Ni) nanoparticles.<br />
The generated arrays are objected to be applied as macroscopic <strong>in</strong>terconnect<strong>in</strong>g<br />
layers with anisotropic electrical conductivity and sub-µm resolution <strong>in</strong> the vertical<br />
<strong>in</strong>terconnection of microelectronic chips (Flip-chip architectures or 3D chip stacks).<br />
Metal nanowires (NWs) are synthesized by electrodeposit<strong>in</strong>g the desired NW species<br />
<strong>in</strong>to hollow l<strong>in</strong>ear pores of anodized Al2O3. Geometric features as well as surface<br />
chemistry of Al2O3 is thereby variable with<strong>in</strong> a decent range and allows the geometrical<br />
tun<strong>in</strong>g of the NWs. The regular lateral arrangement of pores enables a<br />
homogeneous NW distribution (and thereby a homogeneous transportable current<br />
density through the film) as well as a very small diameter range. For the <strong>in</strong>tegration<br />
of such NW arrays between microelectronic contact structures, the generation of a<br />
reliable contact between contact pad surface and NW is a crucial po<strong>in</strong>t. We propose<br />
the utilization of a th<strong>in</strong> additional adhesive film surround<strong>in</strong>g freestand<strong>in</strong>g NW tips on<br />
both sides of the film to generate a self-adhesive NW film that can easily be lam<strong>in</strong>ated<br />
between two microelectronic chips. The bond<strong>in</strong>g between film and chip is so realized<br />
at the top edge of the pores. Therefore we apply a very strongly b<strong>in</strong>d<strong>in</strong>g polymer<br />
(poly cyanurate) be<strong>in</strong>g able to establish a covalent bond structure to Si/SiO2 surfaces.<br />
In this contribution we focus on the creation process of NWs and the <strong>in</strong>terferences<br />
between synthesis and properties (such as electrical conductivity or crystall<strong>in</strong>ity).<br />
72 Thursday 17:40 - 20:10 Poster 015
Clarification of the sorption behavior of uranium onto mica<br />
and feldspar<br />
Constanze Richter, Madlen Stockmann, V<strong>in</strong>zenz Brendler, Kay Großmann<br />
Helmholtz-Zentrum Dresden-Rossendorf e.V. – Institute of Resource Ecology –<br />
P.O.Box 51 01 19, 01314 Dresden – Dresden – GER<br />
constanze.richter@hzdr.de<br />
As part of long-term safety assessments for radioactive waste disposals, scenarios have<br />
to be considered, which lead to the mobilization of radionuclides from the waste and to<br />
their transport through the repository system. Any repository sites (such as Gorleben)<br />
the sedimentary overburden is an important barrier for radionuclide transport. For<br />
most radionuclides the transport is retarded by sorption on m<strong>in</strong>eral phases. Mica<br />
and feldspars are major components of the Gorleben sediments. However, almost no<br />
sorption parameters are available (www.hzdr.de/res 3 t [1] ) for these systems.<br />
The WEIMAR-project (Further Development of the Smart Kd-Concept for Long-<br />
Term Safety Assessment) shall address these shortcom<strong>in</strong>gs. Batch sorption experiments<br />
and spectroscopic <strong>in</strong>vestigations will allow the assessment, the evaluation as<br />
well as the process<strong>in</strong>g of sorption data for U, Np, La(III) onto muscovite and orthoclase.<br />
Generally, the amount of sorption can depend on the pH-value, ionic strength,<br />
redox potential, concentrations of the contam<strong>in</strong>ant as well as of the sorbent, of complex<strong>in</strong>g<br />
ligands and compet<strong>in</strong>g ions. All batch experiments are carried out under<br />
ambient atmosphere and with 0.01 M NaClO4 as background electrolyte.<br />
For muscovite and orthoclase the background concentration of the sorb<strong>in</strong>g elements,<br />
the tendency of wall sorption and the dissolution behavior has to be determ<strong>in</strong>ed. For<br />
both m<strong>in</strong>erals an optimal solid-to liquid ratio has to be optimized. This means that<br />
the sorption is neither too low nor too high, so the sorption has to be between 5 and<br />
95%. All those problems will be illustrated for the case of U(VI) sorption.<br />
This project is funded by the German Federal M<strong>in</strong>istry of Economics and Technology<br />
(BMWi) under contract number 02 E 11072B<br />
[1] V. Brendler et al., J. Cont. Hydrol. 2003, 61, 281-291.<br />
Poster 016 Thursday 17:40 - 20:10 73
Carbon dioxide - a suitable material for hydrogen storage<br />
Peter Sponholz , Dörthe Mellmann, Henrik Junge, Matthias Beller<br />
Leibniz-Institute for Catalysis Rostock – Albert-E<strong>in</strong>ste<strong>in</strong>-Str. 29a – Rostock – GER<br />
Peter.Sponholz@catalysis.de<br />
Advancements <strong>in</strong> hydrogen technology such as the generation of hydrogen, its storage<br />
and its conversion to electrical energy are the prerequisite for the application of<br />
hydrogen as power source (Figure 1). Recently, the use of carbon dioxide or bicarbonate<br />
as suitable storage materials for hydrogen has received considerable attention.<br />
As a significant advantage this cycle is reversible and susta<strong>in</strong>able. The liquid formic<br />
acid affiliates high hydrogen content (4.4% by mass) with a good stability. A cycle<br />
compris<strong>in</strong>g of the storage of hydrogen <strong>in</strong> formic acid or formate salts by catalytic<br />
hydrogenation of carbon dioxide or bicarbonate and the release from it by catalytic<br />
dehydrogenation could be realized. We have recently demonstrated for the first time<br />
that both reactions can be coupled lead<strong>in</strong>g to a closed carbon cycle for hydrogen<br />
storage apply<strong>in</strong>g a ruthenium-based catalyst system for the selective hydrogenation<br />
of bicarbonates as well as the selective dehydrogenation of formats. [1] Further we<br />
could show a setup of a “hydrogen-battery” based on hydrogenation of CO2 to formic<br />
acid and its dehydrogenation back to CO2. [2] For the latter reaction <strong>in</strong> a cont<strong>in</strong>uous<br />
flow setup turnover numbers and turnover frequencies are achieved, which meet<br />
already the requirements of hydrogen supply for applications <strong>in</strong> the 100 W range.<br />
Moreover besides the ruthenium based systems both reactions, hydrogenation and<br />
dehydrogenation, can also be catalyzed by more abundant iron catalysts. [3]<br />
Figure 1: Energy cycle with hydrogen production, storage and usage.<br />
[1] A. Boddien, F. Gärtner, C. Federsel, P. Sponholz, D. Mellmann, R. Jackstell, H. Junge, M.<br />
Beller, Angew. Chem. Int. Ed. 2011, 50, 6411-6414.<br />
[2] A. Boddien, C. Federsel, P. Sponholz, D. Mellmann, R. Jackstell, H. Junge, G. Laurenczy, M.<br />
Beller, Energy Environ. Sci. 2012, 5, 8907.<br />
[3] A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H. Junge, P. J. Dyson, G. Laurenczy, R.<br />
Ludwig, M. Beller, Science 2011, 333, 1733-1736.<br />
74 Thursday 17:40 - 20:10 Poster 017
Functionalization of Monodisperse Iron Oxide Nanoparticles<br />
with Aromatic Dendrons<br />
Ekater<strong>in</strong>a Yu. Yuzik-Klimova ∗ , N<strong>in</strong>a V. Kuchk<strong>in</strong>a ∗ , Lyudmila M. Bronste<strong>in</strong> † ,<br />
Z<strong>in</strong>aida B. Shifr<strong>in</strong>a ∗<br />
∗ Group of Macromolecular Chemistry –<br />
A.N. Nesmeyanov Institute of Organoelement Compounds RAS – Vavilov St. 28 –<br />
Moscow – RUS<br />
† Department of Chemistry – Indiana University – 800 E. Kirkwood Av. –<br />
Bloom<strong>in</strong>gton – USA<br />
yu.k.cather<strong>in</strong>e@gmail.com<br />
Magnetic nanoparticles (NPs) have been widely studied because of their potential applications<br />
<strong>in</strong> magnetic storage media, electronic devices, ferrofluids, biosensors, contrast<br />
enhancement agents for magnetic resonance imag<strong>in</strong>g, bioprobes, and catalysis.<br />
The last application, i.e. magnetically recoverable catalysts, attracted considerable<br />
attention because they allow easy separation of catalysts from reaction mixtures and<br />
their repeated use, thus lead<strong>in</strong>g to energy conservation, more environmentally friendly<br />
processes and cheaper target products.<br />
As is known, iron oxide NPs are well stabilized by fatty acids, such as oleic acid,<br />
conta<strong>in</strong><strong>in</strong>g a s<strong>in</strong>gle double bond, but normally more functional groups are required if<br />
catalytic complexes or NPs have to be formed <strong>in</strong> the magnetic NP shell. [1] Here we<br />
report functionalization of iron oxide NPs prepared by thermal decomposition of iron<br />
acetyl acetonate <strong>in</strong> the presence of the second and third generations of rigid aromatic<br />
dendrons bear<strong>in</strong>g the pyrid<strong>in</strong>e moieties and carboxyl focal po<strong>in</strong>t. Functionalization<br />
of as-synthesized magnetic NPs was followed us<strong>in</strong>g transmission electron microscopy<br />
<strong>in</strong>clud<strong>in</strong>g HRTEM, energy dispersive spectroscopy, thermal gravimetric analysis and<br />
Fourier transform <strong>in</strong>frared spectroscopy.<br />
This work was f<strong>in</strong>ancially supported by European Community’s Seventh Framework<br />
Programme [FP7/2007-<strong>2013</strong>] under grant agreement no. CP-IP 246095 and the Russian<br />
Foundation for Basic Research (RFBR) grants (projects No. 11-03-00064 and<br />
12-03-31057).<br />
Structures of second and third generation aromatic dendrons with a carboxyl focal group<br />
and pyrid<strong>in</strong>e moieties<br />
[1] S.H. Gage, B.D. Ste<strong>in</strong>, L.Zh. Nikoshvili, V.G. Matveeva, M.G. Sulman, E.M. Sulman, D.G.<br />
Morgan, E.Yu. Yuzik-Klimova, W.E. Mahmoud, L.M. Bronste<strong>in</strong>, Langmuir, Accepted.<br />
Poster 018 Thursday 17:40 - 20:10 75
Bright and tunable up-conversion lum<strong>in</strong>escence through<br />
cooperative energy transfer <strong>in</strong> Yb 3+ , Tb 3+ and Eu 3+<br />
co-doped LaPO4 nanocrystals<br />
Tomasz Grzyb<br />
Department of Rare Earths – Adam Mickiewicz University – Grunwaldzka 6 – Poznan –<br />
POL<br />
tgrzyb@amu.edu.pl<br />
Up-conversion (UC) [1] of Eu 3+ ions is relatively rare and <strong>in</strong>effective through to their<br />
optical properties. Also the way of Eu 3+ excitation require a cooperative energy<br />
transfer (CET) [2] between Yb 3+ act<strong>in</strong>g as donors and Eu 3+ acceptors, which is<br />
highly dependent on both the properties of the matrix used ions. To <strong>in</strong>crease the<br />
<strong>in</strong>tensity of Eu 3+ UC we have used Tb 3+ ions as co-dopants <strong>in</strong>volved <strong>in</strong> the energy<br />
transfer between Yb 3+ and Eu 3+ . By chang<strong>in</strong>g the Tb 3+ to Eu 3+ molar ratio it<br />
was possible to tune the color of emission from green <strong>in</strong> Tb 3+ -only doped system<br />
through yellow, orange and red with <strong>in</strong>creas<strong>in</strong>g concentration of Eu 3+ ions <strong>in</strong> this<br />
system. Lanthanum phosphate is a good candidate for CET systems and has been<br />
used as host for dopants ions. Nanomaterials were prepared by a microwave assisted<br />
hydrothermal method <strong>in</strong> the presence of ethylenediam<strong>in</strong>etetraacetic acid. Obta<strong>in</strong>ed<br />
products showed UC emission only after their heat<strong>in</strong>g at 900 o C what resulted <strong>in</strong><br />
change of crystallographic structure from hexagonal to monocl<strong>in</strong>ic and the removal<br />
of all water from the system. Also morphology was changed <strong>in</strong> this way. Nanorods<br />
were transformed <strong>in</strong>to spherical-shaped nanocrystals with average sizes around 50<br />
nm. The synthesized nanomaterials were analyzed by X-ray diffraction (XRD) and<br />
transmission electron microscopy (TEM). Spectroscopic properties were determ<strong>in</strong>ed<br />
from excitation and emission spectra. Measured lum<strong>in</strong>escence decays showed the<br />
energy transfer processes that occurred. The mechanism ly<strong>in</strong>g beh<strong>in</strong>d the observed<br />
spectroscopic properties was proposed.<br />
Fund<strong>in</strong>g for this research was provided by the National Science Centre (grant no.<br />
DEC-2011/03/D/ST5/05701).<br />
[1] F. Auzel, Chem. Rev. 2004, 104 139-173.<br />
[2] T. Grzyb, A. Gruszeczka, R.J. Wiglusz, Z. Śniadecki, B. Idzikowski, S. Lis, J. Mater. Chem.<br />
2012, 22, 22989-22997.<br />
76 Thursday 17:40 - 20:10 Poster 019
Compar<strong>in</strong>g the Mechanical Properties of Unsaturated<br />
Polyester Composites Conta<strong>in</strong> Different Additives and Fillers<br />
Özgür Ceylan, Mehmet Arif Kaya, Mithat Çelebi, Hüsey<strong>in</strong> Yıldırım<br />
Polymer Eng<strong>in</strong>eer<strong>in</strong>g – Yalova Üniversitesi – Rahmi Üstel Caddesi – Yalova – TUR<br />
ceylanozgur@yahoo.com<br />
Unsaturated polyester res<strong>in</strong>s are low molecular weight thermosett<strong>in</strong>g materials conta<strong>in</strong><strong>in</strong>g<br />
double bonds and derived from unsaturated dibasic acid (or anhydride) and<br />
glycols. It was known that first composite plastics were produced by us<strong>in</strong>g glass fiber<br />
and unsaturated polyester res<strong>in</strong>s <strong>in</strong> 1940. [1]<br />
Nowadays, researchers have been perform<strong>in</strong>g studies on especially mechanical properties<br />
of unsaturated polyester based composites that conta<strong>in</strong> different additives and<br />
fillers. However, most researches were based on only one k<strong>in</strong>d of additive or filler. [2,3]<br />
It was not general that compar<strong>in</strong>g mechanical properties caused by different fillers and<br />
additives <strong>in</strong> the same study. Thus, <strong>in</strong> this study our aim is to compare the effects of<br />
different additives and fillers on mechanical properties. A serie of polyester composites<br />
which conta<strong>in</strong> different additives and fillers were prepared and their mechanical<br />
properties such as tensile strength, modulus of elasticity, charpy and flexural strength<br />
were evaluated and compared. In this study we used different fillers and additives<br />
such as calsium carbonate, nanoclay, carbon fiber and SBR rubber. SBR rubber dried<br />
<strong>in</strong> oven (50 ◦ C) prior to use. Also we have <strong>in</strong>vestigated the effect of different fill<strong>in</strong>gs<br />
and additives mixtures on mechanical properties of samples prepared. The samples<br />
were prepared by us<strong>in</strong>g same mold.<br />
Key words: Unsaturated Polyester Res<strong>in</strong>, Fillers, Composit, Mechanical Properties<br />
[1] Kirk-Othmer Encyclopedia of Chemical Technology ISBN: 9780471238966<br />
[2] L. Xu, L. J. Lee “K<strong>in</strong>etic analysis and mechanical properties of nanoclay re<strong>in</strong>forced unsaturated<br />
polyester (UP) res<strong>in</strong>s cured at low temperatures”, Polymer Eng<strong>in</strong>eer<strong>in</strong>g & Science 2005, 45 (4),<br />
496-509.<br />
[3] M. Monti, M. Natali, R. Petrucci, J. M. Kenny, L. Torre, “Carbon Nanofibers for Stra<strong>in</strong> and<br />
Impact Damage Sens<strong>in</strong>g <strong>in</strong> Glass Fiber Re<strong>in</strong>forced Composites Based on an Unsaturated Polyester<br />
Res<strong>in</strong>” Polymer Composites, 32 (5), 766-775.<br />
Poster 020 Thursday 17:40 - 20:10 77
Phase transfer of gold nanoparticles from aqueous to organic<br />
solution<br />
Beata Tkacz-Szczesna, Marc<strong>in</strong> Rosowski, Katarzyna Soliwoda, Grzegorz Celichowski,<br />
Jaroslaw Grobelny<br />
Department of Materials Technology and Chemistry – University of Lodz –<br />
Pomorska 163 St., 90-236 Lodz – Lodz – POL<br />
btkacz@uni.lodz.pl<br />
Gold nanoparticles (AuNPs) have potential application <strong>in</strong> the areas of electronic,<br />
optics, optoelectronics, catalysis, biomedic<strong>in</strong>e etc., because of their size and shapedependent<br />
chemical, optical and electrical properties. Some of the application require<br />
water based colloids while the other ones organic. The simple and reproducible<br />
method for obta<strong>in</strong><strong>in</strong>g organic colloids is a phase-transfer of AuNPs from water solution<br />
to nonpolar solvent. In order to transfer nanoparticles to organic media it is<br />
necessary to use a modifier – a compound that physically or chemically b<strong>in</strong>ds to the<br />
AuNPs surface. It’s role is to provide stabilization of the nanoparticles <strong>in</strong> the organic<br />
phase. Moreover, this technique allows to use well-characterized nanoparticles,<br />
various modifiers (e.g. thiol, alkylam<strong>in</strong>es, carboxy acids, dithiophosphoric acids) and<br />
solvents (e.g. hexane, toluene, chloroform, dichlorobenzene). In this presentation<br />
the ma<strong>in</strong> idea of phase-transfer method will be shown. The size, size distribution<br />
and stability of gold nanoparticles <strong>in</strong> organic media were tested by Dynamic Light<br />
Scatter<strong>in</strong>g (DLS) measurements. UV-Vis spectroscopy was used to determ<strong>in</strong>ate the<br />
efficiency of described method. By the use a phase-transfer method it is possible to<br />
obta<strong>in</strong> AuNPs <strong>in</strong> organic solvents. Nanoparticles <strong>in</strong> organic media can be used as <strong>in</strong>k<br />
component for pr<strong>in</strong>t<strong>in</strong>g electronics or sp<strong>in</strong> coated layers.<br />
Scientific work supported by MNiSW, funds for science <strong>in</strong> 2011-2014 allocated for the cofounded<br />
<strong>in</strong>ternational project<br />
jgrobel@uni.lodz.pl<br />
78 Thursday 17:40 - 20:10 Poster 021
Molecular magnetism <strong>in</strong> cage-like silsesquioxanes conta<strong>in</strong><strong>in</strong>g<br />
3d-transition metal atoms<br />
Mar<strong>in</strong>a Dronova ∗ , Oksana Koplak ‡ , Elena Shub<strong>in</strong>a ∗ , Aleksey Kiril<strong>in</strong> † ,<br />
Mikhail Levitsky ∗ , Aleksey Bilyachenko ∗ , Aleksey Dmitriev ‡ , Artem Talantsev ‡<br />
∗ Laboratory of metal hydrides –<br />
A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences –<br />
Vavilova/28 – Moscow – RUS<br />
† Department of hetero-organic chemistry –<br />
Lomonosov Moscow University of F<strong>in</strong>e Chemical Technology –<br />
prospect Vernadskogo/86 – Moscow – RUS<br />
‡ Laboratory of magnetochemistry and sp<strong>in</strong> dynamics –<br />
Institute of Problems of Chemical Physics of Russian Academy of Sciences –<br />
prospect Akademika Semenova/1 – Chernogolovka, Moscow region – RUS<br />
dronovamar<strong>in</strong>a@gmail.com<br />
Cage-like silsesquioxanes conta<strong>in</strong><strong>in</strong>g Cr(III), Fe(III), Mn(II) and Cu(II) ions, have<br />
been prepared by common method of partial nucleophilic cleavage of polymeric metallasiloxanes.<br />
All synthesized compounds have been structurally characterized by X-ray diffraction<br />
analyses. We have established dependence of magnetic properties of the compounds<br />
on quantity and type of metal ions as well as structural peculiarities of the cage.<br />
There was made a comparison of magnetic properties for polymeric and cage-like<br />
cobalt-conta<strong>in</strong><strong>in</strong>g silsesquioxanes. A correlation between metal content and value of<br />
<strong>in</strong>tradimeric exchange <strong>in</strong>teraction J has been found out.<br />
This work was supported by RFBR (project 11-03-00646)<br />
Poster 022 Thursday 17:40 - 20:10 79
Fabrication of Ordered and Bamboo-type TiO2 Nanopore<br />
Arrays via Pulse Anodization<br />
Joanna Kapusta-Kołodziej , Grzegorz D. Sulka, Marian Jaskuła<br />
Faculty of Chemistry, Department of Physical Chemistry and Electrochemistry –<br />
Jagiellonian University – Ingardena 3 – 30-060 Kraków – POL<br />
kapusta@chemia.uj.edu.pl<br />
Nowadays, nanotechnology is <strong>in</strong>terdiscipl<strong>in</strong>ary branch of sciences, which develops<br />
rapidly and <strong>in</strong>tensively. Among all new nanomaterials, enormous efforts have been<br />
devoted to titanium dioxide (TiO2) especially <strong>in</strong> nanoporous/nanotubular forms due<br />
to a successful comb<strong>in</strong>ation of functional chemical and physical properties with a<br />
well controllable nanoarchitecture, which make its one of the most important material<br />
highly desirable for diverse applications. Titanium dioxide it is now the subject<br />
of <strong>in</strong>tensive studies because of its potential and promise usefulness <strong>in</strong> bone growth<br />
and regeneration, environmental applications, solar cells, catalysis, lithium <strong>in</strong>sertion<br />
and extraction, dielectrics, optoelectronics and sensors. Tak<strong>in</strong>g <strong>in</strong>to the above mentioned<br />
importance of this nanostructured material, fabrication of titanium dioxide on<br />
a nanometer size scale has fundamental and practical importance and, therefore these<br />
materials have ga<strong>in</strong>ed a lot of attention of the scientific community. [1]<br />
It is well known that among all synthetic procedures, anodic oxidation is an excellent<br />
approach to fabricate TiO2 nanopore arrays due to its simplicity, low cost,<br />
self-order<strong>in</strong>g process and facility of morphology control. Under the right conditions,<br />
this technique leads to highly ordered nanopore or nanotubube arrays. A typical<br />
nanostructured anodic titania film, fabricated <strong>in</strong> this way, exhibits close-packed array<br />
of hexagonally arranged tubes or cells conta<strong>in</strong><strong>in</strong>g pores <strong>in</strong> each cell center. [2] A<br />
particular advantage for many further purposes is that grown oxide layers formed via<br />
electrochemical anodization can be directly used as nanostructured electrodes.<br />
Multi-sectional anodic titanium dioxide, consist<strong>in</strong>g of alternat<strong>in</strong>g bamboo-shaped and<br />
smooth-walled sections, different from the typical nanopore/nanotube arrays, could<br />
be obta<strong>in</strong>ed by chang<strong>in</strong>g the anodization potential dur<strong>in</strong>g the pore growth process. In<br />
this work we report multi-sectional TiO2 nanopore arrays with bamboo-like features<br />
fabricated by pulse anodization (PA) carried out under specific alternat<strong>in</strong>g-voltage<br />
conditions. The anodic oxide layers with a structural modulation of pores were formed<br />
by the two-step electrochemical anodization at room temperture <strong>in</strong> an ethylene glycol<br />
solution conta<strong>in</strong><strong>in</strong>g NH4F (0.38 wt%) and H2O (1.79 wt%). It is expected that these<br />
novel nanostructured architectures with a higher surface area, compared to the typical<br />
TiO2 nanopore/nanotube arrays, could have various applications <strong>in</strong> the area of energy<br />
conversion and storage.<br />
Acknowledgments<br />
This research was partially supported by the Polish M<strong>in</strong>istry of Science and High<br />
Education (Grant No. N N204 213340).<br />
[1] M. Bayoumi, B. G. Ateya, Electrochem. Commun. 2006, 8, 38-46.<br />
[2] G. D. Sulka, J. Kapusta-Kołodziej, A. Brzózka, M. Jaskuła, Electrochim. Acta 2010, 55,<br />
4359-4367.<br />
80 Thursday 17:40 - 20:10 Poster 023
Synthesis of Substituted<br />
5,6,7,8-Tetrahydroqu<strong>in</strong>azol<strong>in</strong>-2-am<strong>in</strong>e Compounds via<br />
One-Pot Method<br />
Ece Tosun, Fatma Tülay Tugcu<br />
Department of Chemistry – Yildiz Technical University, Faculty of Science – İstanbul –<br />
TUR<br />
ftugcu@yildiz.edu.tr<br />
Qu<strong>in</strong>azol<strong>in</strong>e derivatives, as the nitrogen-conta<strong>in</strong><strong>in</strong>g heterocycles, are extremely important<br />
compounds with high biological activities as antimicrobial, anti<strong>in</strong>flammatory,<br />
antihyperlipidemic, antihypertensive and anticonvulsant properties. [1-3] They have an<br />
important place <strong>in</strong> the area of heterocyclic compounds because of their presence <strong>in</strong><br />
the structures of macrocyclic complex drugs, their applications <strong>in</strong> <strong>in</strong>dustry and usage<br />
<strong>in</strong> pharmaceutical researches due to their biological properties.<br />
Therefore, <strong>in</strong> this study, some new substituted qu<strong>in</strong>azol<strong>in</strong>e derivatives which are considered<br />
that may possess biological activity have been obta<strong>in</strong>ed via one-pot multicomponent<br />
method by us<strong>in</strong>g hetaryl carboxaldehydes, guanid<strong>in</strong>e carbonate and 4methylcyclohexanone;<br />
and the structures of all these synthesized compounds have<br />
been clarified with spectral data: [4]<br />
Thanks for Yıldız Technical University Scientific Research Projects Coord<strong>in</strong>ation’s support<br />
<strong>in</strong> this study. Project No: 2012-01-02-GEP05.<br />
[1] S. Muthadı, J. Bandı, M. Chıdara, S. R. Muthadı, K.U. Sankar, V.M. Reddy, Scientific Journal<br />
of Pharmacy 2011, 1(1), 30-37.<br />
[2] X. Li, M. Hilgers, M. Cunn<strong>in</strong>gham, Z. Chen, M. Trzoss, Z. Zhang, L. Kohnen, T. Lam, C.<br />
Creighton, G. C. Kedar, K. Nelson, B. Kwan, M. Stidham, V. Brown-Driver, K. J. Shaw, J. F<strong>in</strong>n,<br />
Bioorganic & Medic<strong>in</strong>al Chemistry Letters 2011, 21, 5171-5176.<br />
[3] N. M. Abdel Gawad, H. H. Georgey, R. M. Youssef, N. M. El-Sayed, European J. of Medic<strong>in</strong>al<br />
Chemistry 2010, 45, 6058-6067.<br />
[4] L. Rong, H. Han, H. Wang, H. Jiang, S. Tu, J. Heterocyclic Chem. 2009, 46, 152,.<br />
Poster 024 Thursday 17:40 - 20:10 81
Towards bionanotechnology -<br />
diatom biosilica for nanoparticle assembly<br />
Anne Jantschke ∗ , Cathleen Fischer ∗ , Alexander Eychmüller † , Eike Brunner ∗<br />
∗ Bioanalytische Chemie – TU Dresden – Bergstr. 66 – Dresden – GER<br />
† Physikalische Chemie – TU Dresden – Bergstraße 66b – Dresden – GER<br />
anne.jantschke@chemie.tu-dresden.de<br />
Nanoparticle arrays are of <strong>in</strong>creas<strong>in</strong>g <strong>in</strong>terest ow<strong>in</strong>g to their various potential applications<br />
<strong>in</strong> optics, (opto)electronics, photovoltaics, and catalysis. The comb<strong>in</strong>ation<br />
of metal and semiconductor nanoparticles with biological materials, especially materials<br />
with ordered structures, provides various opportunities for the design of new<br />
materials that comb<strong>in</strong>e natural structural characteristics with the special properties<br />
of nanoparticles.<br />
Diatom biosilica offers a number of advantageous properties: It consists of microand<br />
nanostructured amorphous silica. The shape and pattern<strong>in</strong>g of diatom biosilica<br />
is genetically controlled and precisely reproduced from generation to generation. Approximately<br />
200 000 diatom species are found <strong>in</strong> nature and provide us with a huge<br />
variety of different structures.<br />
The poster will give an overview about ongo<strong>in</strong>g research on diatom based bionanotechnology:<br />
i) Assembly, characterization and applications of diatom biosilica decorated with<br />
noble metal and semiconductor nanoparticles<br />
ii) Regioselective assembly of nanoparticles onto diatom biosilica<br />
iii) DNP-NMR-measurements on diatom biosilica us<strong>in</strong>g TOTAPOL to characterize<br />
the diatom surface<br />
iv) Grow<strong>in</strong>g diatoms with Au@SiO2-nanoparticles: <strong>in</strong>-vivo-studies<br />
v) Deposit<strong>in</strong>g th<strong>in</strong> metal films<br />
CLSM image of CdTe nanoparticles regioselectively<br />
assembled onto diatom biosilica of Stephanopyxis turris<br />
A. Jantschke, A.-K. Herrmann, V. Lesnyak, A. Eychmüller, E. Brunner, “Decoration of Diatom<br />
Biosilica with Small (
Deposition of gold nanoparticles by the use of electrospray<br />
technique<br />
Marc<strong>in</strong> Rosowski , Beata Tkacz-Szczesna, Katarzyna Soliwoda, Grzegorz Celichowski,<br />
Jaroslaw Grobelny<br />
Department of Materials Technology and Chemistry – University of Lodz –<br />
Pomorska 163 St – Lodz – POL<br />
mrosowski@uni.lodz.pl<br />
One of the novel method of gold nanoparticles (AuNP) deposition from water colloid<br />
is electrospray<strong>in</strong>g. The technique is based on spray<strong>in</strong>g of liquid, controlled by electrical<br />
forces. An important feature and advantage of this method is that the evaporation<br />
of solvent is very quick that it is possible to deposit particles <strong>in</strong> dry conditions. It can<br />
be extremely important when solvents can cause damage of the structure of a solid<br />
substrate. The surface density of nanoparticles on the sample can be controlled by<br />
chang<strong>in</strong>g different electrospray<strong>in</strong>g parameters e.g. flow rate, time, voltage, distance<br />
between a nozzle and substrate, operation mode (s<strong>in</strong>gle jet/ multi jet), nanoparticles<br />
concentration and a solvent system <strong>in</strong> sprayed solution The <strong>in</strong>fluence of these parameters<br />
on the coverage of AuNP on the sample coverage was <strong>in</strong>vestigated. By the use<br />
of electrospray deposition method it is possible to obta<strong>in</strong> sample coverage up to 90<br />
percent and even more (multiple layer) if it will be necessary. Deposited <strong>in</strong> this way<br />
AuNP can be used <strong>in</strong> a wide range of application such as electronics, biomedic<strong>in</strong>e,<br />
optics, optoelectronics and catalyze.<br />
Scientific work supported by MNiSW, funds for science <strong>in</strong> 2011-2014 allocated for the cofounded<br />
<strong>in</strong>ternational project.<br />
jgrobel@uni.lodz.pl<br />
Poster 026 Thursday 17:40 - 20:10 83
Optimization of operat<strong>in</strong>g parameters for sensitive and rapid<br />
detection of hydrogen peroxide us<strong>in</strong>g a silver nanowire array<br />
sensor<br />
Elżbieta Kurowska, Grzegorz D. Sulka, Marian Jaskuła<br />
Department of Physical Chemistry and Electrochemistry – Jagiellonian University –<br />
Ingardena 3 – Krakow – POL<br />
kurowska@chemia.uj.edu.pl<br />
Nanoelectrochemistry is a relatively new branch of science that comb<strong>in</strong>es broad spectrum<br />
of fast and <strong>in</strong>expensive, highly selective and sensitive electrochemical research<br />
with a fabrication and test<strong>in</strong>g of nanomaterials. A rapid development of nanoelectrochemistry<br />
is a consequence of a faster transfer of electrons between the electrode<br />
based on nanomaterials and test substances (faster current response), and a high surface<br />
to volume ratio of nanomaterials that <strong>in</strong>creases the sensitivity of chemical sensors<br />
(lower detection and determ<strong>in</strong>ation limits than those achieved for sensors based on<br />
bulk materials). The development of nanotechnology requires fabrication of novel<br />
nanomaterials and m<strong>in</strong>iaturization of devices, that is particularly important <strong>in</strong> application<br />
areas such as bioanalysis and medic<strong>in</strong>e, where a small size, high diagnostic<br />
device sensitivity and selectivity are highly desirable features.<br />
This research was focused on optimization of fabricat<strong>in</strong>g method used for the synthesis<br />
of a non-enzymatic electrochemical sensor based on silver nanowire arrays for determ<strong>in</strong>ation<br />
of hydrogen peroxide <strong>in</strong> the presence of <strong>in</strong>terfer<strong>in</strong>g substances. Such sensors<br />
are characterized by a low determ<strong>in</strong>ation limit, rapid current response, high sensitivity,<br />
high selectivity and long-term stability. In real systems such as human blood, a<br />
determ<strong>in</strong>ed substance is usually accompanied by a very diverse mixture of chemical<br />
compounds, which often disturb significantly a signal of the electrochemical sensor.<br />
We believe that the fabricated hydrogen peroxide sensors based on silver nanowire<br />
arrays or nanoporous th<strong>in</strong> films will be <strong>in</strong>sensitive to <strong>in</strong>terfer<strong>in</strong>g substances. Moreover,<br />
they can accurate determ<strong>in</strong>e the actual concentration of H2O2 <strong>in</strong> test samples<br />
and allow to control the appropriate level of blood glucose <strong>in</strong> test patients.<br />
The nanostructured electrochemical H2O2 sensors were prepared by cathodic electrodeposition<br />
of silver <strong>in</strong>side the nanoporous anodic alum<strong>in</strong>um oxide (AAO) templates.<br />
The AAO templates were synthesized via a simple and cost-effective two-step<br />
anodization of alum<strong>in</strong>um. After suitable treatment, free stand<strong>in</strong>g silver nanowire arrays<br />
were obta<strong>in</strong>ed and <strong>in</strong>vestigated as amperometric sensors for the detection and<br />
determ<strong>in</strong>ation of hydrogen peroxide. Typical electrochemical techniques, <strong>in</strong>clud<strong>in</strong>g<br />
cyclic voltammetry and chronoamperometry were applied for exam<strong>in</strong>ation of nanostructured<br />
sensors. The CV tests were used to select an appropriate potential for the<br />
reduction of hydrogen peroxide. The chronoamperometric measurements carried out<br />
<strong>in</strong> a phosphate buffer solution were used to study the response of electrochemical sensors<br />
to different concentrations of H2O2. The effects of the temperature, pH, volume<br />
of added portions, concentration of hydrogen peroxide <strong>in</strong> a s<strong>in</strong>gle portion and the<br />
time <strong>in</strong>terval between successive add<strong>in</strong>g portions were studied.<br />
Acknowledgements<br />
The research was partially carried out with the equipment purchased thanks to the<br />
f<strong>in</strong>ancial support of the European Regional Development Fund <strong>in</strong> the framework of<br />
the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-<br />
12-023/08).<br />
84 Thursday 17:40 - 20:10 Poster 027
Enzymatic regulation of adhesive functions of<br />
peptide-polymer conjugates<br />
Maria Meißler ∗ , Andreas Taden † , Hans G. Börner ∗<br />
∗ Department of Chemistry, Laboratory for Organic Synthesis of Functional Systems –<br />
Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 – Berl<strong>in</strong> – GER<br />
† Adhesive Technologies – Henkel AG und Co.KG aA – Henkelstr. 67 – Düsseldorf – GER<br />
maria.meissler@chemie.hu-berl<strong>in</strong>.de<br />
Functional peptide-polymer conjugates are of great importance <strong>in</strong> material science.<br />
Comb<strong>in</strong>ation of peptides that b<strong>in</strong>d specific <strong>in</strong>organic surfaces with synthetic polymers<br />
results <strong>in</strong> bioconjugates for a broad scope of <strong>in</strong>dustrial applications. Furthermore, it<br />
is of peculiar <strong>in</strong>terest to control and regulate the adhesive process of the bioconjugates<br />
on the surface. A possibility of enzyme-activated peptide-polymer conjugates could<br />
be presented already, whereas Tyros<strong>in</strong>ase is used to “switch on” adhesive functions<br />
of a mussel-glue derived peptide segment, lead<strong>in</strong>g to bioconjugates that adhere to<br />
steel. [1]<br />
Here<strong>in</strong>, we present an approach for the specific suppression of adhesive functions of<br />
bioconjugates on <strong>in</strong>organic surfaces. Synthesis of peptide-PEO conjugates conta<strong>in</strong><strong>in</strong>g<br />
a known metal b<strong>in</strong>d<strong>in</strong>g peptide sequence leads to an efficient coat<strong>in</strong>g of a specific<br />
material, which can be measured with quartz crystal microbalance (QCM). Introduction<br />
of a designed doma<strong>in</strong> <strong>in</strong>to the system results <strong>in</strong> negation of the adhesive<br />
process by <strong>in</strong>terference with the active b<strong>in</strong>d<strong>in</strong>g site (Figure 1). Enzymatic treatment<br />
“switches on” the b<strong>in</strong>d<strong>in</strong>g doma<strong>in</strong> and therefore recovers the adhesive properties of<br />
the peptide-polymer conjugates.<br />
Figure 1: Schematic representation of enzymatic regulation of adhesive functions of<br />
peptide-polymer conjugates.<br />
[1] Patrick Wilke, Hans G. Börner, ACS Macro Lett. 2012, 1, 871-875.<br />
Poster 028 Thursday 17:40 - 20:10 85
About nano- magnetic- photopolimerized microvessels <strong>in</strong><br />
controlled drug delivery<br />
Adam Budniak, Maciej Mazur<br />
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
adam.budniak@student.uw.edu.pl<br />
The possibility of delivery medication just to specific, diseased tissue would be a great<br />
change <strong>in</strong> medic<strong>in</strong>e, especially for treatment of cancer. It would not only enable to<br />
limit <strong>in</strong>toxication of organism and improve effectiveness of therapy, but it also ease<br />
to use well-known, strong drugs, which are too noxious to arrange them <strong>in</strong> great scale.<br />
The way to solve this problem could be the encapsulation of medic<strong>in</strong>e by neutral<br />
to health polymer <strong>in</strong> order to decrease the <strong>in</strong>itial contact of patient with the cure.<br />
For specific direct<strong>in</strong>g drug-carrier, it is crucial to modify it and as the result enable<br />
to affect with external magnetic field. At the end, microvessels must be opened <strong>in</strong><br />
special way, harmless for patient.<br />
Dur<strong>in</strong>g the presentation, there will be <strong>in</strong>troduced the method of synthesis of pollypyrole<br />
microvessels [1] with adsorbed magnetic nanoparticles [2] and exemplary way<br />
for selective release of medic<strong>in</strong>e. The author will also present advantages of application<br />
of photopolymerization method <strong>in</strong> comparison to chemical synthesis with use of<br />
template. [3]<br />
Fig. 1. Polypyrolle microvessels with adsorbed magnetic nanoparticles.<br />
[1] K. Kijewska, G. J. Blanchard, J. Szlachetko, J. Stolarski, A. Kisiel, A. Michalska, K.Maksymiuk,<br />
M. Pisarek, P. Majewski, P. Krysiński, M. Mazur, Chem. Eur. J. 2012, 18, 310-320.<br />
[2] P. Majewski, "Sythesis, sort<strong>in</strong>g and chemical modifications of the surface of magnetic ferrite<br />
nanoparticles", Master thesis at Chemistry Faculty <strong>in</strong> the field of physical chemistry, Warsaw,<br />
June 2007.<br />
[3] D.Kubacka, P. Krysiński, G. J. Blanchard, J. Stolarski, M. Mazur, J. Phys. Chem. B 2010,<br />
114, 14890–14896.<br />
86 Thursday 17:40 - 20:10 Poster 029
Nitroxide-Mediated Controlled Radical Polymerization as a<br />
Method of Synthesis of the Novel Amphiphilic Polymers<br />
Joanna Szafraniec, Szczepan Zapotoczny, Maria Nowakowska<br />
Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry –<br />
Jagiellonian University – Ingardena 3 – 30-060 Cracow – POL<br />
joanna.szafraniec@uj.edu.pl<br />
Nitroxide-mediated controlled radical polymerization (NMP) is rapidly developed<br />
technique <strong>in</strong> response to <strong>in</strong>creas<strong>in</strong>g need for new polymeric materials. It is metal<br />
free technique which enable effective polymerization of a broad range of monomers<br />
with control of molecular weight and structure of polymers.<br />
Amphiphilic polyelectrolytes attract attention due to their wide range of practical applications<br />
result<strong>in</strong>g from the presence of hydrophilic groups which make them soluble<br />
<strong>in</strong> water and chromophores which make them photoactive. To reduce the contact of<br />
hydrophobic with hydrophilic medium, polymer spontaneously aggregates <strong>in</strong> aqueous<br />
solution form<strong>in</strong>g doma<strong>in</strong>s consisted of packed chromophores <strong>in</strong> which poorly soluble<br />
organic compounds can be solubilized. It makes such systems can be used as<br />
nanoconta<strong>in</strong>ers or nanoreactors. For applications of the copolymer it is important<br />
to have stable core of the micelle. It is believed that the core is better stabilized by<br />
many short arms than by one long block of chromophores.<br />
Novel amphiphilic polymers were synthesized via nitroxide-mediated controlled radical<br />
polymerization us<strong>in</strong>g 4-hydroxy-2,2,6,6-tetramethylpiperid<strong>in</strong>-1-oxy (HTEMPO)<br />
free radical. The polymers dissolved <strong>in</strong> water self-assembly form<strong>in</strong>g hydrophobic doma<strong>in</strong>s,<br />
which consist of highly packed hydrophobic arms. Presented results <strong>in</strong>clude<br />
characterization of such aggregates.<br />
Acknowledgements<br />
Joanna Szafraniec acknowledges the f<strong>in</strong>ancial support from the project Interdiscipl<strong>in</strong>ary<br />
PhD Studies “Molecular sciences for medic<strong>in</strong>e” (co-f<strong>in</strong>anced by the European<br />
Social Fund with<strong>in</strong> the Human Capital Operational Programme).<br />
Poster 030 Thursday 17:40 - 20:10 87
Synthesis of Aryl Im<strong>in</strong>othiazolid<strong>in</strong>one Compounds via<br />
Multicomponent Reaction (Non-solvent) That is Suitable for<br />
The Green Chemistry<br />
Gizem Kahraman, Fatma Tülay Tugcu<br />
Department of Chemistry – Yildiz Technical University, Faculty of Science – İstanbul –<br />
TUR<br />
gizemkahramann@gmail.com<br />
Heterocyclic compounds and derivatives, show<strong>in</strong>g very rapid development of organic<br />
chemistry and constitute a part of <strong>in</strong>creas<strong>in</strong>g importance day by day. As a member<br />
of the r<strong>in</strong>g conta<strong>in</strong><strong>in</strong>g heteroatoms such as nitrogen, sulfur and oxygen thiazolid<strong>in</strong>one<br />
derivative compounds are ga<strong>in</strong><strong>in</strong>g importance due to antifungal, antitubercular, anticancer,<br />
anti-<strong>in</strong>flammatory, and antimicrobial activities. [1-3] Therefore, <strong>in</strong> this case,<br />
the synthesis of such compounds is extremely important.<br />
At the same time, the biologically active compounds very useful <strong>in</strong> the identification<br />
and optimization of the multicomponent reaction type is provided significant<br />
improvements <strong>in</strong> the discovery of pharmaceutical products us<strong>in</strong>g. [4]<br />
Therefore, the study was <strong>in</strong>itiated, may be considered to possess biological activity,<br />
a new aryl substituted im<strong>in</strong>othiazolid<strong>in</strong>one derivatives; thiophene-2-carboxaldehyde,<br />
aryl thiourea, and chloroacetic acid are obta<strong>in</strong>ed us<strong>in</strong>g the multicomponent reaction<br />
method, [5] structures of all compounds is illum<strong>in</strong>ated with spectral data:<br />
Thanks for Yıldız Technical University Scientific Research Projects Coord<strong>in</strong>ation’s support<br />
<strong>in</strong> this study. Project No: 2010-01-02-GEP01.<br />
[1]<br />
S. P. S<strong>in</strong>gh, S. S. Parmar, K. Raman, V. I. ve Stenberg, Chemical Reviews 1981, 81, 175-203.<br />
[2]<br />
A. Verma, K. S. Saraf, European Journal of Medic<strong>in</strong>al Chemistry 2008, 43, 897-905.<br />
[3]<br />
M. Rahman, S. Mukhtar, W. Ansari, G. Lemiere, European Journal of Medic<strong>in</strong>al Chemistry<br />
2005, 40, 173-184.<br />
[4]<br />
A. Döml<strong>in</strong>g, I. Ugi, Angewandte Chemie International Edition 2000, 39, 3169-3210.<br />
[5]<br />
S. Kasmi-Mir, A. Djafri, L. Paqu<strong>in</strong>, J. Hamel<strong>in</strong>, M. Rahmouni, Molecules 2006, 11, 597-602.<br />
88 Thursday 17:40 - 20:10 Poster 031
Silicone membranes as a new corneal epithelial culture bed<br />
Maria Grolik ∗ , Danuta Kuźmicz ∗ , Krzysztof Szczubiałka ∗ , Bogumił Wowra † ,<br />
Dariusz Dobrowolski † , Edward Wylęgała † , Maria Nowakowska ∗<br />
∗ Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Cracow – POL<br />
† Department of Ophthalmology – District Railway Hospital – Panewnicka 65 –<br />
Katowice – POL<br />
grolikm@chemia.uj.edu.pl<br />
The ma<strong>in</strong> aim of the project is development of novel biodegradable and resorbable<br />
polymeric supports for corneal epithelial cells and to determ<strong>in</strong>e their physicochemical,<br />
mechanical and biological properties. The diseases of cornea each year affect 15<br />
million people worldwide accord<strong>in</strong>g to World Health Organization (WHO) estimates<br />
and are often sight-threaten<strong>in</strong>g. At present, the only generally accepted therapy<br />
is the transplantation of the cornea from human donors. However, this treatment<br />
has several drawbacks. The ma<strong>in</strong> one is limited number of human donors therefore<br />
the science is look<strong>in</strong>g for some alternatives. Regeneration of epidermal tissue can<br />
restore and life-save cornea. Corneal tissue is usually cultured on human amniotic<br />
membrane (AM). [1] The supports obta<strong>in</strong>ed from AM show good properties, however,<br />
AM is difficult to obta<strong>in</strong>, expensive, and therefore cannot be used on a large scale.<br />
The new hybrid organic - <strong>in</strong>organic materials used to synthesize the supports are<br />
natural polymers, with chitosan as the ma<strong>in</strong> component crossl<strong>in</strong>ked with genip<strong>in</strong> and<br />
by the addition of collagen and new silicone surfactant (DAP EG<br />
2 D undecyl<br />
2 ). F<strong>in</strong>d<strong>in</strong>g<br />
an alternative support for cultur<strong>in</strong>g corneal cells would be a great breakthrough <strong>in</strong> the<br />
surgery of the cornea and would certa<strong>in</strong>ly result <strong>in</strong> an <strong>in</strong>creased number of sight-sav<strong>in</strong>g<br />
surgeries performed.<br />
[1] D. Dobrowolski, E. Wylęgała, B. Wowra, A. Nowińska, “Application of autologous cultivated<br />
corneal epithelium for restor<strong>in</strong>g of corneal surface.” Acta Ophthalmol. 2010, 88, 246.<br />
[2] M. Grolik, K. Szczubiałka, B. Wowra, D. Dobrowolski, B. Orzechowska-Wylęgała, E. Wylęgała,<br />
M. Nowakowska, “Hydrogel membranes based on genip<strong>in</strong>-cross-l<strong>in</strong>ked chitosan blends for corneal<br />
epithelium tissue eng<strong>in</strong>eer<strong>in</strong>g.” J Mater Sci: Mater Med 2012, 23, 1991-2000.<br />
Project operated with<strong>in</strong> the Foundation for Polish Science Team Programme co-f<strong>in</strong>anced by the<br />
EU European Regional Development Fund, PolyMed, TEAM/2008-2/6 and the National Science<br />
Centre for fund<strong>in</strong>g of research project no 2011/01/N/ST5 /05544.<br />
Poster 032 Thursday 17:40 - 20:10 89
Silver nanoparticles adsorption on solid surfaces for various<br />
ionic strengths<br />
Katarzyna Kubiak, Zbigniew Adamczyk<br />
Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences –<br />
Niezapom<strong>in</strong>ajek 8, 30-239 – Cracow – POL<br />
nckubiak@cyf-kr.edu.pl<br />
Silver nanoparticles exhibit a number of unique properties <strong>in</strong>volv<strong>in</strong>g high antibacterial<br />
and catalytic activities <strong>in</strong> oxidation processes. Silver particle monolayers also f<strong>in</strong>d<br />
practical applications <strong>in</strong> medic<strong>in</strong>e, biology, pharmacology and catalysis, <strong>in</strong> surfaceenhanced<br />
Raman scatter<strong>in</strong>g (SERS) and metal-enhanced fluorescence (MEF) [1,2].<br />
Stable silver nanoparticle sol was synthesized by the reduction of silver nitrate with<br />
sodium borohydride and sodium citrate. Characterization of this sol <strong>in</strong>volved the<br />
ext<strong>in</strong>ction spectrum and solid weight content. Electrophoretic mobilities and the diffusion<br />
coefficient (hydrodynamic diameter) of particles were also measured us<strong>in</strong>g the<br />
dynamic light scatter<strong>in</strong>g - DLS. It was determ<strong>in</strong>ed that the hydrodynamic diameter<br />
of particles was constant and equal to 11 nm for ionic strengths <strong>in</strong> the range of 10 −5<br />
M NaCl to 3 x 10 −2 M NaCl (for pH=5.5), confirm<strong>in</strong>g a high stability of the sol. On<br />
the other hand, the zeta potential of particles (calculated us<strong>in</strong>g the Henry’s model)<br />
varied between -48 mV for 10 −5 M to -39 mV for ionic strength of 3·10 −2 M NaCl and<br />
the same pH. Additionally, the UV-Vis method was used to study the stability of the<br />
silver particle sol as a function of its bulk concentration. Particle shape and size distribution<br />
were also measured by the Atomic Force Microscopy (AFM) and Scann<strong>in</strong>g<br />
Electron Microscopy (SEM). Us<strong>in</strong>g these methods the k<strong>in</strong>etics of particle adsorption<br />
on mica and silicon modified by cationic polyelectrolyte: poly(allylam<strong>in</strong>e hydrochloride)<br />
- PAH was quantitatively evaluated. The <strong>in</strong>fluence of the ionic strengths and<br />
the sol concentration was systematically studied. The k<strong>in</strong>etic runs obta<strong>in</strong>ed <strong>in</strong> these<br />
measurements were adequately reflected for the entire range of times and bulk concentration<br />
by the random sequential adsorption (RSA) model.<br />
[1] M. Oćwieja, Z. Adamczyk, K. Kubiak, J. Colloid Interface Sci. 2012, 376, 1.<br />
[2] K. Aslan, J.R. Lakowicz, Ch.D. Geddes, J. Phys. Chem. B. 2005, 109, 6247.<br />
90 Thursday 17:40 - 20:10 Poster 033
Liquid crystals - synthesis and properties of mesogenic Ni(II)<br />
complexes<br />
Katarzyna Purtak, Adam Krówczyński, Ewa Górecka<br />
Department of Chemistry – University of Warsaw – Żwirki and Wigury St. 101 –<br />
Warsaw – POL<br />
kasia.purtak@gmail.com<br />
New Ni(II) metallomesogens are described, hav<strong>in</strong>g their chelat<strong>in</strong>g centre constructed<br />
from two non-identical fragments: enam<strong>in</strong>oketone and barbiturylidenomethylenoam<strong>in</strong>e<br />
r<strong>in</strong>gs, thus low Cs symmetry. Various side cha<strong>in</strong>s were attached to the mesogenic<br />
core. Despite a triangular molecular shape, almost all synthesised coupounds<br />
exhibit a liquid crystall<strong>in</strong>e hexagonal disordered columnar phase (Colh) with high<br />
clear<strong>in</strong>g temperature. The ability to create the columnar phase is propably connected<br />
with the permanent dipole moment appear<strong>in</strong>g <strong>in</strong> the non-symmetric molecules<br />
and dipole-dipole <strong>in</strong>teractions between molecules <strong>in</strong> columns.<br />
Discotic liquid crystal phase<br />
A. Krówczyński, P. Krzyczkowska, M. Salamończyk, E. Górecka, D. Pociecha, J. Szydłowska,<br />
“Mesogenic Ni(II) complexes of Cs symmetry form<strong>in</strong>g Colh phase by dipole-dipole <strong>in</strong>teraction”,<br />
Liquid Crystals 2012, 39(6), 729-737<br />
Poster 034 Thursday 17:40 - 20:10 91
Regioselective synthesis of highly functionalized<br />
1,3-oxaz<strong>in</strong>-2-ones via electrophilic cyclization of N -Cbz<br />
protected propargylic am<strong>in</strong>es<br />
Alicia Monleón, José Ramón Pedro, Gonzalo Blay<br />
Química Orgànica – Universitat de València – Doctor Mol<strong>in</strong>er, 50 – Burjassot – ESP<br />
alicia.monleon@uv.es<br />
The activation of a carbon-carbon triple bond towards a nucleophilic attack has been<br />
widely carried out us<strong>in</strong>g transition metals as catalysts [1] or electrophiles as reagents.<br />
The utilization of this latter activation method leads to functionalized structures with<br />
high synthetic value. [2]<br />
We have recently reported a convenient strategy for the synthesis of chiral nonracemic<br />
N -Cbz protected propargylic am<strong>in</strong>es 1 by the addition of term<strong>in</strong>al alkynes to im<strong>in</strong>es<br />
generated <strong>in</strong> situ from α -amidosulfones catalyzed by diethylz<strong>in</strong>c and a BINOL-type<br />
ligand. [3]<br />
The electrophilic activation of the triple bond <strong>in</strong> this k<strong>in</strong>d of compounds 1 followed<br />
by the <strong>in</strong>tramolecular nucleophilic attack of the carbamate group should allow the<br />
synthesis of highly functionalized cyclic structures. A 6-endo cyclization process<br />
should lead to oxaz<strong>in</strong>one moieties, a very important type of scaffold present <strong>in</strong> a great<br />
variety of biologically active compounds. [4] Despite the <strong>in</strong>creased attention on these<br />
6-membered r<strong>in</strong>g heterocyclic structures, only a few synthetic strategies have been<br />
developed. [5]<br />
In this communication, we present the regioselective electrophilic cyclization of N -Cbz<br />
protected propargylic am<strong>in</strong>es 1 to afford highly functionalized 3,4-dihydro-2H -1,3oxaz<strong>in</strong>-2-ones<br />
2 which are suitable start<strong>in</strong>g materials for further desirable reactions.<br />
F<strong>in</strong>ancial support from the M<strong>in</strong>isterio de Ciencia e Innovación and FEDER (CTQ2009-<br />
13083), Generalitat Valenciana (ACOMP/2012/212) and ISIC/2012/001is acknowledged.<br />
A M thanks the Generalitat Valenciana for a pre-doctoral grant.<br />
[1] a) T. Saito, S. Ogawa, N. Takei, N. Kutsumura, T. Otani, Org. Lett. 2011, 13, 1098-1101; b)<br />
M. Bian, W. Yao, H. D<strong>in</strong>g, C. Ma, J. Org. Chem. 2010, 75, 269-272.<br />
[2] A. K. Verma, S. P. Shukla, J. S<strong>in</strong>gh, V. Rustagi, J. Org. Chem. 2011, 76, 5670-5684.<br />
[3] G. Blay, A. Br<strong>in</strong>es, A. Monleón, J.R. Pedro, Chem. Eur. J. 2012, 18, 2440-2444.<br />
[4] a) R. Nicoletti, E. Buomm<strong>in</strong>o, A. De Filippis, M. P. Lopez-Gresa, E. Manzo, A. Carella, M.<br />
Petrazzuolo, M. A. Tufano, World J. Microbiol. Biotechnol. 2008, 24, 189-195; b) M. Inami,<br />
I. Kawamura, S. Tsujimoto, F. Nishigaki, S. Matsumoto, Y. Naoe, Y. Sasakawa, M. Matsuo, T.<br />
Manda, T. Goto, Cancer Lett. 2002, 181, 39-45.<br />
[5] a) A. Arfaoui, I. Beltaïef, H. Amri, Synthetic Communications 2011, 41, 1536-1543; b) M.<br />
Pattarrozzi, C. Zonta, Q. B. Broxterman, B. Kapte<strong>in</strong>, R. de Zorzi, L. Randaccio, P. Scrim<strong>in</strong>, G.<br />
Lic<strong>in</strong>i, Org. Lett. 2007, 9, 2365-2368. R. Robles-Machín, J. Adrio, J. C. Carretero, J. Org.<br />
Chem. 2006, 71, 5023-5026.<br />
92 Thursday 17:40 - 20:10 Poster 035
Synthesis of Oleate Capped Gadol<strong>in</strong>ium Oxide Nanocrystals<br />
Madlen Schmudde, Christian Goroncy, Christ<strong>in</strong>a Graf<br />
Institut für Chemie und Biochemie –<br />
Physikalische und Theoretische Chemie, Freie Universität Berl<strong>in</strong> – Takustr. 3 –<br />
14195 Berl<strong>in</strong> – GER<br />
madlen.schmudde@fu-berl<strong>in</strong>.de<br />
Nowadays magnetic resonance imag<strong>in</strong>g (MRI) is widely used <strong>in</strong> modern medic<strong>in</strong>e.<br />
Unfortunately, the resolution and sensitivity of this technique are quite low, so that<br />
contrast agents are necessary to improve the results of MRI. [1] Quite promis<strong>in</strong>g results<br />
as new contrast agents for MRI give gadol<strong>in</strong>ium oxide nanoparticles, which could be an<br />
alternative to today cl<strong>in</strong>ically ma<strong>in</strong>ly used gadol<strong>in</strong>ium chelates. [2] These nanoparticles<br />
could give a higher contrast because of their higher ion concentration and provide<br />
superior possibilities for functionalization. [3]<br />
In the present study a simple synthetic route for the preparation of oleate capped<br />
gadol<strong>in</strong>ium oxide nanocrystals was developed. This synthesis is based on the thermal<br />
decomposition of a metal oleate precursor <strong>in</strong> a high boil<strong>in</strong>g solvent, which is already<br />
well established for the preparation of many other metal oxide nanoparticles. [4]<br />
Accord<strong>in</strong>gly, a gadol<strong>in</strong>ium oleate precursor was decomposed <strong>in</strong> octadecene or alternatively<br />
<strong>in</strong> trioctylam<strong>in</strong>e at 320 ◦ C or 350 ◦ C to yield 2.5 nm to 3.5 nm diameter<br />
spherical gadol<strong>in</strong>ium oxide nanoparticles. The nanoparticles were characterized by<br />
high-resolution transmission electron microscopy (HRTEM) and dynamic light scatter<strong>in</strong>g<br />
(DLS). By us<strong>in</strong>g X-ray powder diffraction (XRD) measurements show that<br />
the particles are highly crystall<strong>in</strong>e. The surface functionalization with the capp<strong>in</strong>g<br />
agent oleate was verified by IR spectroscopy. This simple preparation method for<br />
highly stable gadol<strong>in</strong>ium oxide nanoparticles provides a wide scope for further surface<br />
modifications by ligand exchange reactions as well as the opportunity for dop<strong>in</strong>g<br />
the <strong>in</strong>organic core with other rare metal ions provid<strong>in</strong>g an additional fluorescence<br />
function.<br />
[1]<br />
H. B. Na, I. C. Song, T. Hyeon, Adv. Mater. 2009, 21, 2133-2148.<br />
[2]<br />
G. H. Lee, Y. Chang, T.-J. Kim, Eur. J. Inorg. Chem. 2012, 1924-1933.<br />
[3]<br />
N. J. J. Johnson, W. Oakden, G. J. Stanisz, R. S. Prosser, F. C. J. M. van Veggel, Chem. Mat.<br />
2011, 23, 3714-3722.<br />
[4]<br />
J. Park, K. J. An, Y. S. Hwang, J. G. Park, H. J. Noh, J. Y. Kim, J. H. Park, N. M. Hwang,<br />
T. Hyeon, Nat. Mater. 2004, 3, 891-895.<br />
Poster 036 Thursday 17:40 - 20:10 93
Up-conversion of REPO4 nanocrystals doped with<br />
Yb 3+ /Er 3+ , Yb 3+ /Tm 3+ and Yb 3+ /Tb 3+ ions<br />
Dom<strong>in</strong>ika Przybylska ∗ , Rafał Wiglusz †<br />
∗ Department of Rare Earths, Faculty of Chemistry – Adam Mickiewicz University –<br />
Grunwaldzka 6, 60-780 Poznan – Poznań – POL<br />
† Institute for Low Temperature and Structure Research – Polish Academy of Sciences –<br />
P.O. Box 937, 50-442 Wroclaw – Wroclaw – POL<br />
dom<strong>in</strong>ika1936@gmail.com<br />
Up-conversion is one of the most <strong>in</strong>vestigated phenomenon <strong>in</strong> lanthanide doped nanomaterials.<br />
Lum<strong>in</strong>escent properties of lanthanide ions (Ln 3+ ) are the result of energy<br />
transfer (ET) processes between them. Lanthanide ions may convert energy from the<br />
ultraviolet range to the visible light (down-conversion). However, reversed process<br />
is also possible, where absorbed light from the near-<strong>in</strong>frared range is converted <strong>in</strong>to<br />
visible wavelengths due to up-conversion. Up-conversion (UC) it is a phenomenon <strong>in</strong><br />
which the sequential absorption of two or more photons leads to the emission of light<br />
at shorter wavelengths than the excitation wavelength (anti-Stokes type emission) [1]<br />
In recent years, UC was <strong>in</strong>tensively studied <strong>in</strong> nanocrystall<strong>in</strong>e systems. [2,3] They have<br />
a high potential for <strong>in</strong>dustrial and biological applications, e.g. can be used as biological<br />
assays. [4,5]<br />
Rare earth (RE = Y, La or Gd) phosphates are especially <strong>in</strong>terest<strong>in</strong>g for bioapplications<br />
and as hosts for lum<strong>in</strong>escent Ln 3+ ions because of their relatively high<br />
biocompatibility. Also up-conversion <strong>in</strong> this systems could be effective. [6] REPO4<br />
nanocrystals doped with Yb 3+ /Er 3+ , Yb 3+ /Tm 3+ and Yb 3+ /Tb 3+ ions were synthesized<br />
by co-precipitation method. The best reaction conditions, <strong>in</strong> order to obta<strong>in</strong><br />
small size of the crystals, were estimated and glycer<strong>in</strong> solution was used as the reaction<br />
medium. The result of this reaction ware nanocrystals composed from nanorods<br />
with thickness up to 10 nm and length around 500 nm. Measured excitation and<br />
emission spectra as well as lum<strong>in</strong>escence decays were base for spectroscopic studies<br />
and were used to <strong>in</strong>vestigate energy transfer processes. Structural and morphological<br />
properties were exam<strong>in</strong>ed us<strong>in</strong>g X-ray diffraction (XRD) and transmission electron<br />
microscopy (TEM). Synthesized nanomaterials showed bright yellow (Yb 3+ /Er 3+ ),<br />
blue (Yb 3+ /Tm 3+ ) and green (Yb 3+ /Tb 3+ ) up-conversion emission.<br />
Fund<strong>in</strong>g for this research was provided by the National Science Centre (grant no.<br />
DEC-2011/03/D/ST5/05701).<br />
[1]<br />
F. Auzel, Chem. Rev. 2004, 104, 139-73.<br />
[2]<br />
S. Heer, O. Lehmann, M. Haase, H.-U.H.-U. Güdel, Angew.<br />
3179-3182.<br />
[3]<br />
S. Zeng, J. Xiao, Q. Yang, J. Hao, J. Mater. Chem. 2012.<br />
Chem. Int. Ed. 2003, 42,<br />
[4]<br />
F. Wang, D. Banerjee, Y. Liu, X. Chen, X. Liu, Analyst 2010, 135, 1839-54.<br />
[5]<br />
M.E. Lim, Y.-l<strong>in</strong>g Lee, Y. Zhang, J.J.H. Chu, Biomaterials 2011, 3-11.<br />
[6]<br />
T. Grzyb, A. Gruszeczka, R.J. Wiglusz, Z. Śniadecki, B. Idzikowski, S. Lis, J. Mater. Chem.<br />
2012, 22, 22989-22997.<br />
94 Thursday 17:40 - 20:10 Poster 037
Synthesis and characterization of polysiloxanes th<strong>in</strong> films<br />
Agnieszka Puciul-Mal<strong>in</strong>owska, Vladyslav Kuryltso, Szczepan Zapotoczny<br />
Department of Chemistry – Jagiellonian Uniwersity – Ingardena 3 – Krakow – POL<br />
puciul@chemia.uj.edu.pl<br />
Dur<strong>in</strong>g the last few years the <strong>in</strong>terest of the formation of microcapsules that may serve<br />
as conta<strong>in</strong>ers for drug delivery or photorectors for conversion of sunlight energy is still<br />
grow<strong>in</strong>g. Due to that there is a very great <strong>in</strong>terest of formation of flexible coat<strong>in</strong>gs<br />
for that microcapsules. For that purpose the great material are polysiloxanes because<br />
of their biocompability and very high flexibility of the cha<strong>in</strong>s. Their water-soluble<br />
properties also cause that these polymers are very well suited for that purpose. .<br />
This work presents the polysiloxane film formation on model surfaces obta<strong>in</strong>ed by<br />
Electrostatic Self-Assembly “layer-by-layer” method and its characterization. Atomic<br />
Force Microscopy and Spectroscopic Ellipsometry were used to determ<strong>in</strong>e dependence<br />
of the film thickness from the number of bilayers. In addition the impact on film<br />
topography of different types of ris<strong>in</strong>g, namely stream of the water and sonication,<br />
was observed. The films will be further used as functional coat<strong>in</strong>gs for photochemical<br />
applications.<br />
The authors would like to thank Polish M<strong>in</strong>istry of Science and Higher Education for<br />
the f<strong>in</strong>ancial support (“Ideas Plus” grant no. IdP2011 000561).<br />
Poster 038 Thursday 17:40 - 20:10 95
Selective Growth of Trigonal and Hexagonal Shaped Silver<br />
Micro Nano Platelets at the Water/Oil Interface<br />
Eike Gericke ∗ , Stefan Weidemann † , Roman Bansen ‡ , Torsten Boeck ‡ ,<br />
Franziska Emmerl<strong>in</strong>g ⋄ , Klaus Rademann ∗<br />
∗ Institute for Chemistry – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 –<br />
Berl<strong>in</strong> – GER<br />
† Institute for Physics – Humboldt-Universität zu Berl<strong>in</strong> – Newtonstr. 15 – Berl<strong>in</strong> – GER<br />
‡ Leibniz-Institute for Crystal Growth – Max-Born-Str. 2 – Berl<strong>in</strong> – GER<br />
⋄ BAM Bundesanstalt für Materialprüfung – Richard-Willstätter-Str. 11 – Berl<strong>in</strong> – GER<br />
eike.gericke@chemie.hu-berl<strong>in</strong>.de<br />
A particle synthesis method for the shape selective growth of th<strong>in</strong> silver micro nano<br />
platelets at the water/oil <strong>in</strong>terface is presented. In this case no additives are needed<br />
to reach the shape selectivety. The seed dependence of the growth, as well as the<br />
ripen<strong>in</strong>g k<strong>in</strong>etics, give the full procedure control.<br />
This method pursues former results for shape selective growth <strong>in</strong> particle dimensions [1]<br />
and proposses a more detailed mechanistic model [2] than before.<br />
The experiments were evaluated for reagent concentrations between 10 −3 and 10 −2<br />
mol/l and <strong>in</strong> a reaction time w<strong>in</strong>dow from 30 m<strong>in</strong>utes to 3 days with ESEM, FESEM,<br />
AFM and XRD.<br />
We show that the shape selective production of silver particles <strong>in</strong> this set up is possible<br />
and give a detailed machanistic propose. Possible applications could be oxidation and<br />
oxygenation catalysis, microelectronics ore analytical usages for SERS.<br />
[1] A. Wang, H. Y<strong>in</strong>, M. Ren, Y. Liu, T. Jiang, Appl. Surf. Sci. 2008, 254, 6527.<br />
[2] M. S. J<strong>in</strong>, Q. Kuang, X. G. Han, S. F. Xie, Z. X. Xie, L. S. Zheng, J. Solid State Chem. 2010,<br />
183, 1354.<br />
96 Thursday 17:40 - 20:10 Poster 039
Asbestos <strong>in</strong> environmental soil samples<br />
Sylwia Lipiecka, Katarzyna Makowska, Zuzanna Kowalkiewicz, Włodzimierz Urbaniak<br />
Faculty of Chemistry – Adam Mickiewicz University <strong>in</strong> Poznan –<br />
Umultowska Street 89 B – Poznan – POL<br />
sylwia.lipiecka@gmail.com<br />
Asbestos as well-known harmful material [1] should be controled <strong>in</strong> environment. Admittedly,<br />
the largest health risk is related with presence of this m<strong>in</strong>eral <strong>in</strong> the air, but<br />
other elements of environment, e.g. soil or water, could be also contam<strong>in</strong>ated with<br />
asbestos fibers and cause secondary fibers emission <strong>in</strong>to atmosphere and exposure . [2]<br />
Asbestos analyses, practically limited only to air samples, base ma<strong>in</strong>ly on obsolete<br />
methods and the new solutions, especially for liquid and soil samples despite the<br />
market requirements, aren’t sufficiently developed.<br />
Asbestos contam<strong>in</strong>ation <strong>in</strong> soil could be the result of precipitation with fibers from the<br />
air, elution from asbestos-cement materials for example roof sheets, from debris dur<strong>in</strong>g<br />
removal work and asbestos-waste disposal. For confirmation of correctness of executed<br />
work and safety for people health is required the environmental monitor<strong>in</strong>g. [3] Results<br />
of analyses are also important by adm<strong>in</strong>istrative decisions regard<strong>in</strong>g the sites.<br />
The elaborated method [4] enables the asbestos determ<strong>in</strong>ation <strong>in</strong> soil and liquid samples<br />
with use the phase contrast optical microscope. This is a relatively fast and easy<br />
and not expensive analysis. The suitable sample preparation, all asbestos characteristics<br />
considered, assures <strong>in</strong>creas<strong>in</strong>g of <strong>in</strong>vestigations. [5]<br />
We would like to present the study of asbestos separation from soil samples, which<br />
have a very complex matrix and f<strong>in</strong>d<strong>in</strong>gs for quantitative asbestos determ<strong>in</strong>ation by<br />
phase contrast microscopy. With use the proposed method s<strong>in</strong>ce 2009 the environmental<br />
monitor<strong>in</strong>g of area next to farm build<strong>in</strong>g with asbestos cement roof is made<br />
and the results would be the part of the presentation.<br />
[1] Virta R. L., “Asbestos: Geology, M<strong>in</strong>eralogy, M<strong>in</strong><strong>in</strong>g, and Uses”, U.S. Geological Survey, Open-<br />
File Report 02-149, Version 1.0, 2002.<br />
[2] A. Domaszewicz, S. Lipiecka, W. Urbaniak, “Problems <strong>in</strong> asbestos analyses <strong>in</strong> environmental<br />
and bulk samples, Integrated waste management”, PZiTS, Poznan, 2009.<br />
[3] Lipiecka S., Szeflińska K., Narożny M., Eitner K., Urbaniak W. “Asbestos dust <strong>in</strong> municipal<br />
environment”, Przegląd Komunalny, 3/2012 (246), Publisher Abrys, 2012.<br />
[4] S. Lipiecka, A. Domaszewicz, B. Staniszewski, W. Urbaniak, “Asbestos Determ<strong>in</strong>ation”, Polish<br />
Patent 2012 (Application P-389368, 2009).<br />
[5] S. Lipiecka, A. Domaszewicz, K. Szeflińska, W. Urbaniak, “Method of asbestos separation <strong>in</strong><br />
soil samples and determ<strong>in</strong>ation by optical microscope”, Ars Separatoria Acta 2009/2010, ISSN<br />
1731-6340, No. 07, 85-98.<br />
Poster 040 Thursday 17:40 - 20:10 97
Antioxidant characteristics of the plant extracts from traffic<br />
polluted and unpolluted areas<br />
Marija Ilic ∗ , Snezana Jovanovic ∗ , Strah<strong>in</strong>ja Simonovic ∗ , Violeta Mitic ∗ ,<br />
Vesna Stankov-Jovanovic ∗ , Snezana Nikolic-Mandic †<br />
∗ Department of Chemistry – University of Niš, Faculty of Sciences and Mathematics –<br />
Visegradska 33 – Nis – SER<br />
† Department of Analytical Chemistry – University of Belgrade, Faculty of Chemistry –<br />
Studentski trg 12-14 – Belgrade – SER<br />
marija.fertico@gmail.com<br />
Plants have specific chemical composition which depends on plant species, habitat and<br />
series of environmental factors. Certa<strong>in</strong>ly, one of the major factors is traffic pollution.<br />
Term traffic pollution refers mostly to the form of air pollution com<strong>in</strong>g from vehicles.<br />
Several studies have confirmed l<strong>in</strong>k between pollution and plants metabolism,<br />
which means changes <strong>in</strong> production of certa<strong>in</strong> compounds by permanently exposure<br />
to pollutants. The aim of the present research study was exam<strong>in</strong>ation of antioxidant<br />
activity, total phenol and total flavonoid content <strong>in</strong> plants from two localities: near<br />
ma<strong>in</strong> road (polluted environment, Sicevacka gorge, route Nis-Sofia) and natural environmental<br />
(Ploce, unpolluted nearby area). The plant species: Anthemis t<strong>in</strong>ctoria,<br />
Stenactis annua, Crepis foetida and Artemisia vulgaris were the most abundant <strong>in</strong><br />
polluted area, recognized as remedies <strong>in</strong> traditional medic<strong>in</strong>e and therefore have become<br />
the subject of the study. In estimation of antioxidant characteristics, DPPH and<br />
ABTS assays (based on free radical scaveng<strong>in</strong>g) and Total reduc<strong>in</strong>g power of ferrous<br />
to ferri ion were used (TRP). Determ<strong>in</strong>ation of total phenols was performed by Fol<strong>in</strong>-<br />
Ciocalteau assay, and determ<strong>in</strong>ation of total flavonoids was based on usage of AlCl3<br />
which forms colored complexes with flavonoids. Investigated methanol extracts were<br />
obta<strong>in</strong>ed by ultrasonic extractions. The results which expressed ability of samples to<br />
scavenge DPPH radical (EC50 values) and ABTS radical cation (Trolox equvalents)<br />
are very similar; extract samples from polluted area, showed higher activity except<br />
for C. foetida aga<strong>in</strong>st DPPH, where the reverse dependence was registered. In regard<br />
to TRP, higher values for samples from polluted area <strong>in</strong> comparison to those from<br />
natural environmental were obta<strong>in</strong>ed. Contents of phenols and flavonoids were higher<br />
<strong>in</strong> plants which grew near magistral road. Surpris<strong>in</strong>gly, obta<strong>in</strong>ed results showed that<br />
plants <strong>in</strong> potentially polluted environment possessed higher antioxidant activity and<br />
higher flavonoids and phenols content.<br />
Acknowledgements: The research was supported by the Serbian M<strong>in</strong>istry of Education,<br />
Science and Technology Development (Grant no 172051).<br />
Keywords: Traffic polluted, antioxidant characteristics, Anthemis t<strong>in</strong>ctoria, Stenactis<br />
annua, Crepis foetida, Artemisia vulgaris<br />
98 Thursday 17:40 - 20:10 Poster 041
Changes <strong>in</strong> gene expression <strong>in</strong> frog heart after exposition to<br />
heavy metal ions<br />
Marta Kaczor-Kamińska<br />
Chair of Medical Biochemistry – Jagiellonian University Medical College – Kopernika 7 –<br />
Krakow – POL<br />
marta.b.kaczor@uj.edu.pl<br />
Heavy metal ions (Cd, Hg, Pb) are environmentally persistent tox<strong>in</strong>s. There are<br />
three ma<strong>in</strong> reasons contribut<strong>in</strong>g <strong>in</strong>to their high toxicity <strong>in</strong> liv<strong>in</strong>g organisms: 1) high<br />
aff<strong>in</strong>ity for thiol-, histydyl-, am<strong>in</strong>o- and carboxyl groups of am<strong>in</strong>o acid residues <strong>in</strong><br />
prote<strong>in</strong>s (changes <strong>in</strong> structural and catalytic properties of prote<strong>in</strong>s), 2) effect on the<br />
antioxidant potential of cells - a reduced level of glutathione can ultimately produce<br />
oxidative stress, 3) their compet<strong>in</strong>g with metal cations of active sites of prote<strong>in</strong>s, what<br />
leads to <strong>in</strong>hibition or modification of a prote<strong>in</strong> activity. The ma<strong>in</strong> objective of the<br />
study was to <strong>in</strong>vestigate changes <strong>in</strong> the activity and expression of γ-cystathionase<br />
(CST) and sulfurtransferase 3-mercaptopyruvate (MPST), enzymes participat<strong>in</strong>g <strong>in</strong><br />
the non-oxidative metabolism of cyste<strong>in</strong>e, and the expression of mitochondrial and<br />
cytoplasmic superoxide dismutase <strong>in</strong> hearts of frogs - Pelophylax ridibundus exposed<br />
to lead (28 mg Pb/l;10 days) and cadmium (40 and 80 mg Cd/l; 4 or 10 days) and<br />
Xenopus laevis (X. tropicalis) exposed to mercury (1.353 mg Hg/l; 7, 10 or 14 days).<br />
The results confirmed changes <strong>in</strong> the expression of genes encod<strong>in</strong>g for CST and MPST<br />
<strong>in</strong> the heart. An <strong>in</strong>creased expression of the CST gene was observed <strong>in</strong> hearts of frogs<br />
exposed to mercury ions, while lead and cadmium ions had no effect and the expression<br />
was comparable to that seen <strong>in</strong> the control group. The expression of the MPST gene<br />
<strong>in</strong> the heart was decreased <strong>in</strong> response to exposure to all of the <strong>in</strong>vestigated ions.<br />
Furthermore, changes <strong>in</strong> expression were correlated with a decrease <strong>in</strong> MPST specific<br />
activity accompanied by a decrease <strong>in</strong> the level of sulfane sulfur. The exposition to<br />
cadmium and lead ions resulted <strong>in</strong> the <strong>in</strong>crease <strong>in</strong> the content of total glutathione and<br />
the ratio of GSH/GSSG <strong>in</strong> the heart. These effects all together suggest that cyste<strong>in</strong>e is<br />
directed to the synthesis of glutathione and is less readily available for the production<br />
of sulfane sulfur through the MPST-dependent pathway. It was also observed that<br />
the expression of gene for the cytosolic superoxide dismutase was <strong>in</strong>creased after the<br />
exposure to the <strong>in</strong>vestigated ions, possibly <strong>in</strong> response to an elevated level of reactive<br />
oxygen species.<br />
Poster 042 Thursday 17:40 - 20:10 99
Synthesis and Photophysicochemical Properties of Novel<br />
Z<strong>in</strong>c Phthalocyan<strong>in</strong>es<br />
Ali Erdogmus, Erkan Kırbac, Goknur Yasa, A. Lütfi Ugur, Ibrahim Erden<br />
Chemistry – Yildiz Technical University – Davutpasa Campus – Istanbul – TUR<br />
erdogmusali@hotmail.com<br />
Phthalocyan<strong>in</strong>es (Pcs) are remarkable macrocyclic compounds hav<strong>in</strong>g magnificent<br />
physical and chemical properties. They are usually synthesized start<strong>in</strong>g from the<br />
appropriate phthalonitriles and their derivatives or their substitution yield as metalfree<br />
phthalociyan<strong>in</strong>e and metallophthalocyan<strong>in</strong>es which obta<strong>in</strong>ed especially <strong>in</strong> high<br />
temperatures with the presence of a suitable anhydrous metal salt. [1,2] Metallophthalocyan<strong>in</strong>es<br />
(MPcs) have potential applications <strong>in</strong> many areas such as <strong>in</strong> medic<strong>in</strong>al<br />
and material science. [3,4] MPcs enjoy usage <strong>in</strong> pr<strong>in</strong>t<strong>in</strong>g <strong>in</strong>ks, catalysis, display devices,<br />
data storage, chemical sensors, gas sensors, solar cells, organic light emitt<strong>in</strong>g<br />
devices (OLED), PDT and photonic devices. [5,6] In this study, we report the synthesis,<br />
characterization of different substituted z<strong>in</strong>c phthalocyan<strong>in</strong>es. The new compounds<br />
have been characterized by elemental analysis, UV, FT-IR, 1H-NMR spectroscopy<br />
and mass spectra. The effect of fluor<strong>in</strong>e, brom<strong>in</strong>e and chlor<strong>in</strong>e substitituents on<br />
photophysical and photochemical properties were reported. The s<strong>in</strong>glet oxygen, photodegradation,<br />
fluorescence quantum yield, triplet quantum yield and triplet life time<br />
of the complexes <strong>in</strong> DMF, THF, DMSO were determ<strong>in</strong>ed. Fluorescence quantum<br />
yields for the complexes ranged from 0.19 to 0.30.<br />
[1]<br />
C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyan<strong>in</strong>es -Properties and Applications, vols. 1-4,<br />
VCH, New York, 1989-1996.<br />
[2]<br />
N.B. McKeown, Phthalocyan<strong>in</strong>e Materials-Synthesis, Structure and Function, Cambridge<br />
University Press, New York, 1998.<br />
[3]<br />
K. Kadish, K. M. Smith, R. Guilard, editors. The porphyr<strong>in</strong> Handbook, vol. 15-20, Boston:<br />
Academic Press, 2003.<br />
[4]<br />
K. Morishige, S. Tomoyasu, G. Iwani, “Adsorption of CO, O2, NO2, and NH3 by metallophthalocyan<strong>in</strong>e<br />
monolayers supported on graphite”, Langmuir 1997, 13, 5184-5188.<br />
[5]<br />
F. H. Moser, L. R. Thomas, Phthalocyan<strong>in</strong>e compounds, New York: Re<strong>in</strong>hold, 1963, 123-145.<br />
[6]<br />
T. Tom<strong>in</strong>aga, K. Hayashi, N. Toshima “Construction of a ‘sequential potential field’ by [Cu(pc)]/<br />
[Zn(pc)] double-layered th<strong>in</strong> film: application to electrochromic and electrolum<strong>in</strong>escent devices”,<br />
J. Porphyr. Phtalocyan. 1997, 1, 239-249.<br />
100 Thursday 17:40 - 20:10 Poster 043
Spectroscopic analysis of Xylella fastidiosa biofilms<br />
Bärbel Abt ∗ , M.A. Cotta † , D.M. Murillo Munar † , R. Janissen † , B.C. Niza Silva ‡ ,<br />
A.A. de Souza ‡ , G.S. Lorite ⋄ , C. Kranz ∗ , B. Mizaikoff ∗<br />
∗ Analytische und Bioanalytische Chemie – Universität Ulm – Ulm – GER<br />
† Instituto Física Gleb Watagh<strong>in</strong> – UNICAMP – Camp<strong>in</strong>as – BRA<br />
‡ Instituto Agronômico – Centro de Citricultura Sylvio Moreira – Cordeiropolis – BRA<br />
⋄ Institute of Biomedic<strong>in</strong>e – University of Oulu – Oulu – FIN<br />
baerbel.abt@uni-ulm.de<br />
Xylella fastidiosa (Xf) is a gram-negative phytopathogen bacterium that particularly<br />
affects the xylem vessels of citrus plants by vascular occlusion. This causes diseases<br />
such as Pierce’s disease or citrus variegated chlorisis (CVC). [1] Substantial economic<br />
losses of annually exceed<strong>in</strong>g $ 100 million for the citrus <strong>in</strong>dustry may be attributed<br />
to Xylella fastidiosa. As an important step toward fully understand<strong>in</strong>g this bacterium,<br />
the genome of Xylella fastidiosa has recently been sequenced <strong>in</strong> part by our<br />
collaborators. [2] Yet, the molecular mechanisms <strong>in</strong>volved <strong>in</strong> colonization of the xylem<br />
by this phytopathogen, and <strong>in</strong> particular the <strong>in</strong>volved biofilm formation rema<strong>in</strong> little<br />
understood.<br />
A vested <strong>in</strong>terest <strong>in</strong> the role of biomolecules dur<strong>in</strong>g biofilm formation is not only<br />
limited to agricultural aspects. Consider<strong>in</strong>g that biofilms play an important role<br />
for many bacterial-caused diseases, the relevance of <strong>in</strong>vestigat<strong>in</strong>g the adsorption and<br />
colonization of bacteria at surfaces, and the associated biofilm formation with respect<br />
to the <strong>in</strong>volved prote<strong>in</strong>s and biomolecules is evident. [3-5] For this purpose disulfide<br />
bonds play an important role for the formation of biofilms. [6]<br />
In the present study, spectroscopic techniques were used to <strong>in</strong>vestigate the chemical<br />
and structural properties of the biomolecules <strong>in</strong>volved <strong>in</strong> Xf biofilm formation.<br />
Spectroscopic techniques and <strong>in</strong> particular <strong>in</strong>frared attenuated total reflection (IR-<br />
ATR) spectroscopy were used to characterize <strong>in</strong> detail the growth media of Xf and<br />
its molecular components. On the basis of the characterization of the media, a better<br />
understand<strong>in</strong>g on the formation of biofilms by Xf and the molecular components<br />
may be derived. Experimental and analytical procedures will be accompanied by<br />
first results on the characterization of growth media with IR-ATR spectroscopy and<br />
complementary spectroscopic techniques.<br />
[1] A. H. Purcell and D. L. Hopk<strong>in</strong>s, “Fastidious xylemlimited bacterial plant pathogens”, Annual<br />
review of phytopathology 1996, 34(c), 131-151.<br />
[2] The Xylella fastidiosa Consortium of the Organization for Nucleotide Sequenc<strong>in</strong>g and Analyisis,<br />
“The genome sequence of the plant pathogen Xylella fastidiosa”, Nature 2000, 406(13), 151-159.<br />
[3] G. S. Lorite, A. A. de Souza, D. Neubauer, B. Mizaikoff, C. Kranz, and M. A. Cotta, “On the role<br />
of extracellular polymeric substances dur<strong>in</strong>g early stages of Xylella fastidiosa biofilm formation.”<br />
Colloids and surfaces. B, Bio<strong>in</strong>terfaces <strong>2013</strong>, 102, 519-25.<br />
[4] G. S. Lorite, C. M. Rodrigues, A. A. de Souza, C. Kranz, B. Mizaikoff, and M. A. Cotta, “The<br />
role of condition<strong>in</strong>g film formation and surface chemical changes on Xylella fastidiosa adhesion<br />
and biofilm evolution.”, J Colloid Interface Sci 2011, 359(1), 289-295.<br />
[5] R. M. Donlan and J. W. Costerton, “Biofilms: Survival Mechanisms of Cl<strong>in</strong>ically Relevant<br />
Microorganisms”, Cl<strong>in</strong>ical Microbiology Reviews 2002, 15(2), 167-193.<br />
[6] C. A. Santos, M. A. S. Toledo, D. B. B. Trivella, L. L. Beloti, D. R. S. Schneider, A. M. Saraiva,<br />
A. Crucello, A. R. Azzoni, A. A. Souza, R. Aparicio, and A. P. Souza, “Functional and structural<br />
studies of the disulfide isomerase DsbC from the plant pathogen Xylella fastidiosa reveals a redoxdependent<br />
oligomeric modulation <strong>in</strong> vitro.” The FEBS journal 2012, 279(20), 3828-3843<br />
Poster 044 Thursday 17:40 - 20:10 101
New Diselenooxalato Complexes<br />
Structure, EPR and TG/DTA studies<br />
Mike Neumann ∗ , Uwe Schilde † , Peter Strauch ∗<br />
∗ Institute of Chemistry, Inorganic Material Chemistry – University of Potsdam –<br />
Karl-Liebknecht-Str. 24-25 – Potsdam – GER<br />
† Institute of Chemistry, Inorganic Chemistry – University of Potsdam –<br />
Karl-Liebknecht-Str. 24-25 – Potsdam – GER<br />
mike.neumann@uni-potsdam.de<br />
The chemistry of coord<strong>in</strong>ation compounds with thiooxalato ligands and <strong>in</strong> particular<br />
with the dithiooxalato ligand is well-<strong>in</strong>vestigated. [1] In contrast the synthesis and<br />
characterisation of selenium and tellurium analogs is widely unexplored. Only the<br />
synthesis of two diselenooxalato complexes, bis(benzyltriphenylphosphonium)bis(1,2diselenooxalato)metallate(II)<br />
(M = Ni, Cu), and the structure of the Ni-complex as<br />
well as the preparation of the diselenooxalato ligand <strong>in</strong> form of the potassium salt<br />
have been published yet. [2,3]<br />
Here we present new complexes of the [cation]2[Ni(dso)2] type, as well as the related<br />
diselenosquarato analogs, and their structures (Fig. 1). The paramagnetic copper(II)<br />
complexes (S = 1/2, I = 3/2) are well-suited to be studied by EPR-spectroscopy.<br />
TG/DTA and XRD measurements will give <strong>in</strong>formation about the thermal behaviour<br />
of the complexes and their potential as possible precursors <strong>in</strong> material science.<br />
Figure 1: X-Ray structure of the mononuclear (K(18-Crown-6))2[Pd(dso)2] complex.<br />
[1]<br />
W. Dietzsch, P. Strauch, E. Hoyer, Coord. Chem. Rev. 1992, 121, 43.<br />
[2]<br />
P. Strauch,<br />
S. Abram, U. Drutkowski, Inorg.<br />
Naturforsch. 1978, 33b, 461.<br />
Chim. Acta 1998, 278, 118.<br />
[3]<br />
C. Matz, R. Mattes, Z.<br />
102 Thursday 17:40 - 20:10 Poster 045
Ultrasound effects on adsorption of Cu(II) on<br />
methyl-sulfonated Lagenaria vulgaris shell<br />
Maja Stanković, Nenad Krstić, Jelena Mitrović, Ružica Nikolić, Miljana Radović,<br />
Danijela Bojić, Aleksandar Bojić<br />
Department of Chemistry – Faculty of Sciences and Mathematics, University of Niš –<br />
Visegradska 33 – Niš – SRB<br />
majstan@gmail.com<br />
The rapid <strong>in</strong>dustry development leads to ris<strong>in</strong>g of the contam<strong>in</strong>ation of available water<br />
resources, while <strong>in</strong>creas<strong>in</strong>g of global population requires new sources of dr<strong>in</strong>k<strong>in</strong>g water.<br />
Therefore, the challenge for scientists is to f<strong>in</strong>d cheap, efficient, environmental-friendly<br />
materials for removal of pollutants from <strong>in</strong>dustrial and communal/atmospheric wastewaters.<br />
In this study, methyl-sulfonated shell of Lagenaria vulgaris (msLVB) was <strong>in</strong>vestigated<br />
as a novel, low-cost biosorbent for the removal of copper from aqueous<br />
solutions with and without the assistance of ultrasound. Lagenaria vulgaris shell<br />
represents a lignocellulosic material with ability for b<strong>in</strong>d<strong>in</strong>g metal cations due to<br />
presence of hydroxyl, carboxylic, lactonic and phenolic groups <strong>in</strong> its structure, while<br />
treatment with formaldehyde and sodium-sulphite was used to <strong>in</strong>troduce sulphonic<br />
groups, known by significant ion-exchang<strong>in</strong>g capacity. Sorption k<strong>in</strong>etics was <strong>in</strong>vestigated<br />
<strong>in</strong> batch conditions, us<strong>in</strong>g 125 mL of the solution with 50.0 mg L -1 of Cu(II)<br />
ions, 4.0 g L -1 of msLVB, at pH 5.0 and 25 o C. The experiments were performed<br />
us<strong>in</strong>g magnetic stirrer on 200 rpm or ultrasonic bath with the frequency of 40 kHz.<br />
The sorption was considerably <strong>in</strong>creased <strong>in</strong> the presence of ultrasound (Fig. 1). The<br />
k<strong>in</strong>etic data fitted very well the pseudo-second-order k<strong>in</strong>etic model.<br />
Effect of mix<strong>in</strong>g on adsorption capacity of msLVB for Cu(II) ions<br />
Poster 046 Thursday 17:40 - 20:10 103
Treatment of Basic Dye from Textile Wastewaters by<br />
Sulfonated Polymers<br />
Mehmet Arif Kaya, Mithat Çalebi, Özgür Ceylan, Hüsey<strong>in</strong> Yildirim<br />
Polymer Eng<strong>in</strong>eer<strong>in</strong>g – Yalova University – Yalova – TUR<br />
marifkaya@gmail.com<br />
The textile <strong>in</strong>dustry consumes huge volumes of water <strong>in</strong> different wet processes and as<br />
a result it was obta<strong>in</strong>ed significant amount of colourful wastewater from dye process.<br />
In dy<strong>in</strong>g process, various dyes can be used such as acidic, reactive, basic, disperse,<br />
azo, diazo, antraquionone-based and metal complex dyes accord<strong>in</strong>g to fabric types. [1]<br />
Basic dyes are cationic soluble salts of coloured bases. Basic dyes are applied to<br />
substrate with anionic character where electrostatic attractions are formed. Basic<br />
dyes are powerful colour<strong>in</strong>g agents. It’s applied to polyacrylonitrile, modified nylons,<br />
modified polyesters, paper. They are generally water soluble. [2]<br />
In this study, treatment of basic dye (Basic Red 481) from local textile mill was<br />
<strong>in</strong>vestigated by different sulfonated polymers at different pHs.<br />
Key words: basic dye, textile dye, decolorization, sulfonated polymer<br />
Removal of Basic Red 46 by sulfonated polymers after 2 hour. K: Control.<br />
[1] A. Tuba, G.Tuğba, G. Afife, D Gönül, M. Ülkü, “Decolorization of textile azo dyes by ultrasonication<br />
and microbial removal”, Desal<strong>in</strong>ation 2010, 255, 154-158.<br />
[2] V.K. Gupta, Suhas, “Application of low-cost adsobents for dye removal-A review”, Journal of<br />
Environmental Management 2009, 90, 2313-2342.<br />
104 Thursday 17:40 - 20:10 Poster 047
Removal of Phenolic Derivatives from Wastewater us<strong>in</strong>g<br />
Photocatalytic Membranes<br />
Crist<strong>in</strong>a Orbeci, Gheorghe Nechifor, Ion Untea<br />
Department of Analytical Chemistry and Environmental Eng<strong>in</strong>eer<strong>in</strong>g –<br />
“Politehnica” University of Bucharest – 1-7 Gh. Polizu Street – Bucharest – ROU<br />
crist<strong>in</strong>a27ccc@yahoo.com<br />
The presence of phenol and phenolic derivatives <strong>in</strong> water <strong>in</strong>duces toxicity, persistence<br />
and bioaccumulation <strong>in</strong> plant and animal organisms and is a risk factor for human<br />
health. In consequence, the identification and monitor<strong>in</strong>g of these compounds detectable<br />
<strong>in</strong> dr<strong>in</strong>k<strong>in</strong>g water and surface waters are imperative.<br />
Available technologies deal<strong>in</strong>g with phenolic compounds <strong>in</strong>clude the advanced oxidation<br />
processes (AOPs), based on the formation of very active hydroxyl radicals,<br />
which react quickly with the organic contam<strong>in</strong>ant. AOPs present the advantage of<br />
completely remov<strong>in</strong>g organic contam<strong>in</strong>ants from the environment, not only from the<br />
aqueous phase, by transform<strong>in</strong>g them <strong>in</strong>to other organic compounds with low toxicity<br />
and f<strong>in</strong>ally <strong>in</strong>to <strong>in</strong>nocuous <strong>in</strong>organic species. The technologies for remov<strong>in</strong>g phenolic<br />
derivatives based on membranes and photocatalytic processes play an important<br />
role. [1] Among the AOPs, the photocatalytic process is one of the most attractive<br />
methods because the reagent components are easy to handle and non-toxic to the<br />
environment. [2] Separation membranes have become essential parts of human life because<br />
of their grow<strong>in</strong>g <strong>in</strong>dustrial applications <strong>in</strong> high technology such as biotechnology,<br />
nanotechnology and membrane based separation and purification. [3-5]<br />
This paper presents a hybrid method for an advanced removal of low biodegradable<br />
organic compounds from water, by comb<strong>in</strong><strong>in</strong>g the separation selectivity of membranes<br />
with the high oxidation efficiency of the photocatalytic process. The hybrid process for<br />
the disposal of phenolic compounds from aqueous solutions comb<strong>in</strong>es the selectivity<br />
of membranes with high efficiency and the photocatalytic process.<br />
[1] Fei Feng, Zhenliang Xu, Xiaohuan Li, Went<strong>in</strong>g You, Yang Zhen Advanced treatment of dye<strong>in</strong>g<br />
wastewater towards reuse by the comb<strong>in</strong>ed Fenton oxidation and membrane bioreactor process,<br />
Journal of Environmental Sciences 2010, 22 (11), 1657-1665;<br />
[2] Lifen Liu, Guohua Zheng, Fengl<strong>in</strong> Yang, Adsorptive removal and oxidation of organic pollutants<br />
from water us<strong>in</strong>g a novel membrane, Chemical Eng<strong>in</strong>eer<strong>in</strong>g Journal 2010, 156 (3), 553-556;<br />
[3] Bui Xuan Thanh, Vo Thi Kim Quyen, Nguyen Phuoc Dan, Removal of Non-Biodegradable<br />
Organic Matters from Membrane Bioreactor Permeate By Oxidation Processes, Journal of Water<br />
Susta<strong>in</strong>ability 2011, 1 (3), 289–299;<br />
[4] Xiaob<strong>in</strong> Wanga, Xiongfu Zhanga, Haiou Liua, K<strong>in</strong>g Lun Yeungb, J<strong>in</strong>qu Wang, Preparation<br />
of titanium silicalite-1 catalytic films and application as catalytic membrane reactor, Chemical<br />
Eng<strong>in</strong>eer<strong>in</strong>g Journal, 2010, 156, 562-570;<br />
[5] Huab<strong>in</strong>g Jianga, Guoliang Zhanga, Tao Huanga, J<strong>in</strong>yuan Chena, Qidong Wangb, Q<strong>in</strong> Mengc,<br />
Photocatalytic membrane reactor for degradation of acid red B wastewater, Chemical Eng<strong>in</strong>eer<strong>in</strong>g<br />
Journal 2010, 156, 571-577.<br />
Poster 048 Thursday 17:40 - 20:10 105
The impact of the extraction of magnesium on chang<strong>in</strong>g of<br />
the optical properties of chrysotile fibers<br />
Katarzyna Makowska, Sylwia Lipiecka, Zuzanna Kowalkiewicz, Włodzimierz Urbaniak<br />
Faculty of Chemistry – Adam Mickiewicz University – Umultowska 89B – Poznań – POL<br />
katarzyna.makowska6@gmail.com<br />
Chrisotile is an <strong>in</strong>organic fibrous m<strong>in</strong>eral naturally occur<strong>in</strong>g <strong>in</strong> the nature. A s<strong>in</strong>gle<br />
fiber is composed of two layers - hexagonal magnesium hydroxide layer and tetragonal<br />
silicalayer form<strong>in</strong>g a “tube” with a diameter of 25-30 nm and a center channel with a<br />
diameter of about 5 nm. Chrysotile fibers are present <strong>in</strong> tightly packed bundles, but<br />
are bound together only by weak van der Waals <strong>in</strong>teractions, and therefore can be<br />
readily separated by mechanical actions. [1]<br />
Chrysotile has specific optical properties which can be observed <strong>in</strong> Polarised Light<br />
Microscopy (PLM). It is a very simple method of identification of asbestos fibers.<br />
PLM allows, not only, to dist<strong>in</strong>guish asbestos from other materials, but also the<br />
various types of asbestos from each other. Us<strong>in</strong>g liquid of known refractive <strong>in</strong>dex<br />
(for chrysotile nc = 1.55) can be seen optical properties such as: dispersion sta<strong>in</strong><strong>in</strong>g,<br />
pleochroism, birefr<strong>in</strong>gence, ext<strong>in</strong>ction, ext<strong>in</strong>ction angle and sign of elongation. [2] If<br />
the tested fibers do not display any of these characteristics can exclude presence of<br />
asbestos <strong>in</strong> the material.<br />
This study presents how extraction of magnesium from brucite layer has changed the<br />
optical properties of chrysotile asbestos. In the experiment were tested pure chrisotile<br />
fibers and chrysotile fibers after <strong>in</strong>cubation with <strong>in</strong>organic acids, organic acid and also<br />
with the addition of fluoride ions.<br />
[1] J. Addison “Asbestos , Analysis of”, Meyers R. A. Environmental analysis and remediation.<br />
USA N.Y., John Wiley & Sons, Inc., 1998, 1, 413-434.<br />
[2] G. Stroszejn-Mrowca “Identification of asbestos <strong>in</strong> bulk materials by polarysed light microscopy<br />
and phase contrast: method and results”, Occupational Medic<strong>in</strong>e, 2003, 54 (6), 567-572<br />
106 Thursday 17:40 - 20:10 Poster 049
Study of the PM10 concentration variations at the crossroad<br />
of busy roads <strong>in</strong> Poznan<br />
Maciej Narozny, Krystian Eitner, Wlodzimierz Urbaniak<br />
Department of Analytical Chemistry – Adam Mickiewicz University – Grunwaldzka 6 –<br />
Poznan – POL<br />
narozny@amu.edu.pl<br />
The movement of motor vehicles is one of the ma<strong>in</strong> sources of suspended matter <strong>in</strong><br />
urban areas. Additionally the lack of adequate monitor<strong>in</strong>g stations of this type of air<br />
pollution causes impossibility to estimation the risks and analysis of the situation.<br />
Dur<strong>in</strong>g the period from October 2011 to June 2012, PM10 concentrations were measured<br />
<strong>in</strong> the center of Poznan, at the crossroad of busy roads. The measurements<br />
took place <strong>in</strong> four series, each with a different time of year (fall, w<strong>in</strong>ter, spr<strong>in</strong>g, summer)<br />
and lasted seven days. Measurement time was 8 hours from 8 am to 16 pm.<br />
Sampl<strong>in</strong>g was carried out us<strong>in</strong>g portable real - time aerosol monitor the DustTrak II<br />
8530. Additionally were measured meteorological factors such as temperature, humidity,<br />
pressure, w<strong>in</strong>d strength and direction us<strong>in</strong>g a weather station Oregon Scientific<br />
WMR 200th. Dur<strong>in</strong>g the measurements also identified the <strong>in</strong>ternal combustion car<br />
traffic pass<strong>in</strong>g through crossroad. Mean daytime concentration of PM 10 ranged from<br />
17 µg/m 3 to 421 µg/m 3 . The study shows that the concentration of PM10 is strongly<br />
dependent on the weather and the number of vehicles. This shows how much the people<br />
of urban areas are exposed to the effects of dust, which <strong>in</strong> the long term negative<br />
impact on human health.<br />
Poster 050 Thursday 17:40 - 20:10 107
Ultrasound-assisted Synthesis of Naphthapyranes Catalyzed<br />
by Copper Triflate<br />
Kadir Turhan, S. Arda Ozturkcan, Zuhal Turgut<br />
Department of Chemistry – Yildiz Technical University – Davutpasa Street –<br />
34210 Esenler, Istanbul – TUR<br />
turhankadir@yahoo.com<br />
Active oxygen heterocycles takes <strong>in</strong>terest because they are an important class of natural<br />
compounds such as Mollug<strong>in</strong> and Nigrol<strong>in</strong>ea benzopyranes which exhibit<strong>in</strong>g a<br />
wide spectrum of pharmaceutical and biological properties such as antitumor and<br />
antibacterial activities. [1,2] Naphthapyranes are important biologically active heterocyclic<br />
compounds, which possess analgesic, anti-<strong>in</strong>flammatory, antifungal, antiviral,<br />
cytotoxic, anti-oxidative, and 5-lipoxygenase <strong>in</strong>hibitory activities. [3-7]<br />
Ultrasonic-assisted organic synthesis (UAOS) as a green synthetic approach is a powerful<br />
technique that is be<strong>in</strong>g used more accelerates organic reactions. [8] UAOS can be<br />
highly effective and it is applicable to a wide range of practical reactions. In order to<br />
expand the application of ultrasound <strong>in</strong> the synthesis of heterocyclic compound, we<br />
wish to report a general, rapid, productive and environment-friendly method for the<br />
synthesis of naphthapyranes.<br />
Triflates are effective and recoverable homogeneous catalysts for the modern synthesis.<br />
Recently, rare earth metal triflates, a new type of Lewis acid, are broadly used <strong>in</strong><br />
organic reactions due to their low toxicity, high stability, ease of handl<strong>in</strong>g, water<br />
tolerance, and recoverability from water. To the best of our knowledge, this study<br />
reports a new procedure for the synthesis of naphthapyranes us<strong>in</strong>g Cu(OTf)2 as a<br />
green catalyst under ultrasound irradiation.<br />
[1]<br />
S. Claessens, B. Kesteleyn, T. Nguyen Van, N. De Kimpe, Tetrahedron 2006, 62 (35), 8419.<br />
[2]<br />
V. Rukachaisirikul, K. Tadpetch, A. Watthanaphanit, N. Saengsanae, S. Phongpaichit, Journal<br />
of Natural Products 2005, 68 (8), 1218.<br />
[3]<br />
L. Q. Wu, W. L. Li, F. L. Yan, Journal of Heterocyclic Chemistry 2010, 47 (5), 1246.<br />
[4]<br />
L.-Q. Wu, L.-M. Yang, X. Wang, F.-L. Yan, Journal of the Ch<strong>in</strong>ese Chemical Society 2010,<br />
57, 738.<br />
[5]<br />
G. C. Nandi, S. Samai, R. Kumar, M. S. S<strong>in</strong>gh, Tetrahedron 2009, 65 (34), 7129.<br />
[6]<br />
A. K. Bhattacharya, K. C. Rana, M. Mujahid, I. Sehar, A. K. Saxena, Bioorganic & Medic<strong>in</strong>al<br />
Chemistry Letters 2009, 19 (19), 5590.<br />
[7]<br />
A. Kumar, S. Sharma, R. A. Maurya, J. Sarkar, Journal of Comb<strong>in</strong>atorial Chemistry 2009,<br />
12 (1), 20.<br />
[8]<br />
G. H. Mahdav<strong>in</strong>ia, S. Rostamizadeh, A. M. Amani, Z. Emdadi, Ultrasonic Sonochemistry<br />
2009, 16 (1), 7.<br />
This study was f<strong>in</strong>ancially supported by YILDIZ TECHNICAL UNIVERSITY, Coord<strong>in</strong>ation<br />
of Scientific Research Projects with the project number of 2012-01-02-GEP01.<br />
108 Thursday 17:40 - 20:10 Poster 051
Electroreduction of aliphatic chlorides at silver cathodes <strong>in</strong><br />
water, acetonitryle and mixed water-acetonitryle<br />
Agnieszka Brzózka ∗ , Anna Brudzisz † , Grzegorz Sulka †<br />
∗ Faculty of Non-Ferrous Metals – AGH University of Science and Technology –<br />
30 Mickiewicza Av. – Krakow – POL<br />
† Department of Physical Chemistry & Electrochemistry – Jagiellonian University –<br />
Ingardena 3 – Krakow – POL<br />
brzozka@agh.edu.pl<br />
As a result of widespread use <strong>in</strong> <strong>in</strong>dustry and <strong>in</strong> various household products and<br />
poor biodegradability chlor<strong>in</strong>ated aliphatic hydrocarbons are frequently found <strong>in</strong> soils,<br />
dr<strong>in</strong>k<strong>in</strong>g waters and gaseous emissions at levels that, <strong>in</strong> water sediments, can be as<br />
high as 150 ppb. Contam<strong>in</strong>ation of dr<strong>in</strong>k<strong>in</strong>g water by chlor<strong>in</strong>ated aliphatic hydrocarbons<br />
is particularly dangerous <strong>in</strong> view of their toxicity or even carc<strong>in</strong>ogenic nature and<br />
hence efficient remediation technologies are highly desired. Indeed, the development<br />
of degradation technologies for water pollutants is an active area of research, and<br />
various methods are already known for the abatement of halogenated compounds. [1]<br />
The electrocatalytic reductive dehalogenation of organic halides has been extensively<br />
<strong>in</strong>vestigated as a technology for the detoxification and disposal of halogenated hydrocarbons<br />
<strong>in</strong> <strong>in</strong>dustrial effluents. In comparison to other reductive pathways such<br />
as chemical, catalytic, and photochemical dehalogenation this method appears as<br />
a very promis<strong>in</strong>g approach be<strong>in</strong>g <strong>in</strong>tr<strong>in</strong>sically milder, more selective, and easier to<br />
run. However, the reduction of organic halides at the most commonly used cathodes<br />
occurs at very negative potentials, where a concomitant reduction of water might<br />
take place. Experimental evidence is presented that Ag exhibits a powerful electrocatalytic<br />
activity for the dehalogenation of polyhalogenated hydrocarbons to less, or<br />
non-halogenated hydrocarbons with positive shifts of the peak potentials as compared<br />
to glassy carbon. [2]<br />
The process of reduction C2H4Cl2 was <strong>in</strong>vestigated by cyclic voltammetry at glassy<br />
carbon and silver electrodes (bulk and nanowires <strong>in</strong> the form of nanobrushes) <strong>in</strong> H2O,<br />
acetonitryle (ACN) and mixed H2O/ACN with LiClO4, tetraethylammonium perchlorate<br />
and tetrabutylammonium fluoride as a support<strong>in</strong>g electrolyte. Silver nanowire<br />
array have been successfully fabricated us<strong>in</strong>g anodic alum<strong>in</strong>a oxide templates by a<br />
direct-current electrodeposition from a commercially available plat<strong>in</strong>g solution. The<br />
porous anodic alum<strong>in</strong>a membranes were prepared by a two-step anodiz<strong>in</strong>g process.<br />
The morphology of samples was studied us<strong>in</strong>g a field emission scann<strong>in</strong>g electron microscope<br />
(FE-SEM). To confirm the chemical composition of obta<strong>in</strong>ed Ag nanowires,<br />
the EDAX analysis was performed. In order to test the long-term stability of the<br />
silver nanowires, cyclic voltamperometry experiments were repeatedly carried out on<br />
the Ag-nanowire electrode, without renewal of Ag nanowires.<br />
Acknowledgement:<br />
This research was partially supported by the National Science Centre (Grant No<br />
2011/01/N/ST5/02510). The research was partially carried out with the equipment<br />
purchased thanks to the f<strong>in</strong>ancial support of the European Regional Development<br />
Fund <strong>in</strong> the framework of the Polish Innovation Economy Operational Program (contract<br />
no. POIG.02.01.00-12-023/08).<br />
[1]<br />
G. Fiori, S. Rond<strong>in</strong><strong>in</strong>i, G. Sello, A. Vertova, M. Cirja, L. Conti, J. Appl. Electrochem. 2005,<br />
35, 363-68.<br />
[2]<br />
S. Ardizzone, G. Cappelletti, P. R. Muss<strong>in</strong>i, S. Rond<strong>in</strong><strong>in</strong>i, L. M. Doubova, J. Electroanal.<br />
Chem. 2002, 532, 285-293.<br />
Poster 052 Thursday 17:40 - 20:10 109
Charge Transfer K<strong>in</strong>etics of SnS-Nanoparticle Monolayers<br />
Susann Kittler, Jan Poppe, Stephen G. Hickey, Alexander Eychmüller<br />
Physikalische Chemie und Elektrochemie – TU Dresden – Bergstraße 66b – Dresden –<br />
GER<br />
susann.kittler@chemie.tu-dresden.de<br />
Scarcity of fossil fuels, a ris<strong>in</strong>g demand for power and a grow<strong>in</strong>g ecological sensitivity<br />
are only three of the reasons as to why renewable energy sources are of great <strong>in</strong>terest.<br />
Photovoltaic devices have a huge potential but the level of efficiency is presently only<br />
about 25 % for epitaxial solar cells.<br />
In 1991 O’Regan and Grätzel published a new solar cell construction called a dye<br />
sensitized solar cell (DSSC). [1] As the role of the dye is as the light harvest<strong>in</strong>g component,<br />
semiconductor nanoparticles can be used <strong>in</strong> their stead giv<strong>in</strong>g rise to a quantum<br />
dot sensitised solar cell (QDSSC). Primarily compound semiconductors nanoparticles<br />
such as CdS, CdSe and PbS have been well <strong>in</strong>vestigated as possible sensitizer materials.<br />
T<strong>in</strong>(II) sulfide (SnS) as a IV-VI semiconductor represents a material with high potential<br />
for photovoltaic applications, because of its good chemical stability under normal<br />
work<strong>in</strong>g conditions, high absorption coefficient (α > 104 cm-1) and position of a direct<br />
and <strong>in</strong>direct bandgap (1.09 and 1.3 eV respectively) <strong>in</strong> the wavelength range of<br />
<strong>in</strong>terest for solar harvesters. [2]<br />
In this work SnS particles have been deposited onto a transparent conduct<strong>in</strong>g glass<br />
substrate (<strong>in</strong>dium t<strong>in</strong> oxide, ITO) through the use of bifunctional organic compounds.<br />
The SnS-layers were then characterisized by scann<strong>in</strong>g electron microscopy (SEM), absorption<br />
spectroscopy and different voltammetric and amperometric methods under<br />
square wave modulated illum<strong>in</strong>ation.<br />
SEM-picure of a SnS-NP monolayer<br />
[1] B. O’Regan, M. Grätzel, Nature 1991, 353, 737.<br />
[2] S. G. Hickey, C. Waurisch, B. Rell<strong>in</strong>ghaus, A. Eychmüller, Journal of the American Chemical<br />
Society 2008, 130, 14978.<br />
110 Thursday 17:40 - 20:10 Poster 053
NMR Spectroscopy <strong>in</strong> Nuclear Safety Research<br />
Jérôme Kretzschmar ∗ , Astrid Barkleit ∗ , V<strong>in</strong>zenz Brendler ∗ , Eike Brunner †<br />
∗ Institut für Ressourcenökologie – Helmholtz-Zentrum Dresden-Rossendorf –<br />
Bautzner Landstr. 400 – Dresden – GER<br />
† Bioanalytische Chemie – Technische Universität Dresden – Bergstr. 66 –<br />
Dresden – GER<br />
j.kretzschmar@hzdr.de<br />
Radioactive elements can be emitted to the environment for several reasons. There<br />
are natural uranium and thorium compounds (and their decay products) <strong>in</strong> rock<br />
formations, which can be released by geologic alteration or m<strong>in</strong><strong>in</strong>g processes. As<br />
a consequence of energy production <strong>in</strong> nuclear power plants over the last decades,<br />
huge amounts of nuclear waste were produced. If this waste is not stored adequately,<br />
radionuclides can enter the geo- or biosphere. Study<strong>in</strong>g the transport behaviour of<br />
these radioactive elements and their fission products is the key aspect of our research.<br />
Here, rocks and natural m<strong>in</strong>eral phases as well as organic molecules as potential<br />
b<strong>in</strong>d<strong>in</strong>g sites are objects of <strong>in</strong>vestigation.<br />
Both, NMR spectroscopic structure elucidation of environmentally relevant complexes<br />
of lanthanides, act<strong>in</strong>ides and selenium as well as the verification of results obta<strong>in</strong>ed<br />
by other techniques <strong>in</strong> former studies, are the aims of this work.<br />
The study of large biomolecules such as prote<strong>in</strong>s or humic acids is rather complicated.<br />
Therefore, compounds which are themselves potential complex<strong>in</strong>g agents or at least<br />
possess structural similarities to larger molecules, are used as model substances, for<br />
<strong>in</strong>stance glutathione (a tripeptide) or citrate.<br />
Different one- and two-dimensional solution and solid state NMR methods will be<br />
applied to dedicated systems, supplied by TRLFS, ATR FT-IR and EXAFS. Where<br />
possible, the radionuclides are supposed to be replaced by <strong>in</strong>active analogues or isotopes.<br />
In the case of selenium [1] , the sp<strong>in</strong>–1/2 nucleus of Se-77 is well suited to be<br />
directly observed by NMR spectroscopy.<br />
[1] <strong>in</strong> cooperation with Erica Brendler, Institut für Analytische Chemie, Technische Universität<br />
Bergakademie Freiberg<br />
Poster 054 Thursday 17:40 - 20:10 111
Catalytic dehydrogenation of liquid organic hydrogen<br />
carriers for a decentralized energy storage application<br />
Kathar<strong>in</strong>a Obesser, A. Bösmann, P. Wasserscheid<br />
Institute of Chemical Reaction Eng<strong>in</strong>eer<strong>in</strong>g – University Erlangen-Nuremberg –<br />
Egerlandstr. 3 – Erlangen – GER<br />
kathar<strong>in</strong>a.obesser@crt.cbi.uni-erlangen.de<br />
Liquid organic hydrogen carriers (LOHC) provide an efficient and convenient way<br />
for hydrogen storage and transportation. [1,2] LOHC compounds like N-ethylcarbazole<br />
(NEC) can be loaded with hydrogen by catalytic hydrogenation of unsaturated bonds. [3]<br />
The orig<strong>in</strong>at<strong>in</strong>g energy-rich Dodecahydro-N-ethylcarbazole (H12-NEC) is liquid at<br />
ambient conditions and can be handled very similar to diesel fuel. When energy is<br />
demanded, the stored hydrogen is released <strong>in</strong> a catalytic dehydrogenation reaction<br />
while the energy-lean compound is regenerated (Figure 1).<br />
This LOHC approach is a promis<strong>in</strong>g technology for long-term stor<strong>in</strong>g local and temporary<br />
energy overproduction from regenerative sources. With<strong>in</strong> the context of the<br />
Bavarian Hydrogen Center the construction of a pilot plant for domestic energy supply<br />
is planned <strong>in</strong> order to demonstrate the functionality and potential of the hydrogen<br />
storage system. For the near-term realization of the project the usage of catalysts<br />
which are commercially available <strong>in</strong> large quantities is crucial. The screen<strong>in</strong>g of various<br />
commercial catalysts for efficient dehydrogenation of H12-NEC under relatively<br />
mild conditions is presented.<br />
Figure 1 The LOHC system N-ethylcarbazole / Dodecahydro-N-ethylcarbazole: typical<br />
parameters for the reversible hydrogenation and dehydrogenation process. [1]<br />
[1]<br />
D. Teichmann, K. Stark, K. Müller, G. Zöttl, P. Wasserscheid, W. Arlt, Energy Environ. Sci.<br />
2012, 5, 9044-9054.<br />
[2]<br />
D. Teichmann, W. Arlt, P. Wasserscheid, , Freymann, Energy Environ. Sci. 2011, 4, 2767-<br />
2773.<br />
[3]<br />
F. Sotoodeh, K. J. Smith, Ind. Eng. Chem. Res. 2010, 49, 1018-1026.<br />
112 Thursday 17:40 - 20:10 Poster 055
Synthesis and Structural Analysis of Some New<br />
Hexahomotrioxacalix[3]arene Derivatives Based on<br />
Terpyrid<strong>in</strong>e Units<br />
Claudia Lar ∗ , Anamaria Terec ∗ , Ion Neda † , Ion Grosu ∗<br />
∗ Department of Organic Chemistry –<br />
Faculty of Chemistry and Chemical Eng<strong>in</strong>eer<strong>in</strong>g, Babes Bolyai University –<br />
Arany Janos 11 – Cluj Napoca – ROU<br />
† Institut fur Anorganische und Analytische Chemie –<br />
Technische Universitat Braunschweig – Hagenr<strong>in</strong>g 30 – Braunschweig – GER<br />
cl_lar@yahoo.com<br />
Anion recognition, complexation and transport were recognised recently as a very important<br />
part of supramolecular chemistry. [1] In order to develop more specific function<br />
or recognition, supramolecular chemists have widely used calixarene derivatives as a<br />
platform and have selectively <strong>in</strong>troduced a variety of groups <strong>in</strong>to the upper and lower<br />
rims. Calix[n]arenes are known as build<strong>in</strong>g blocks [2] <strong>in</strong> supramolecular chemistry and<br />
can be used as molecular scaffolds for the synthesis of more elaborated structures. In<br />
this work, the synthesis and structural aspects of some hexahomotrioxacalix[3]arene<br />
derivatives [3] based on terpyrid<strong>in</strong>e units (Scheme 1) are discussed.<br />
This work was possible with the f<strong>in</strong>ancial support of the Sectoral Operational Programme<br />
for Human Resources Development 2007-<strong>2013</strong>, co-f<strong>in</strong>anced by the European<br />
Social Fund, under the project number POSDRU 89/1.5/S/60189 with the title “Postdoctoral<br />
Programs for Susta<strong>in</strong>able Development <strong>in</strong> a Knowledge Based Society”.<br />
Scheme 1<br />
[1] (a) “Supramolecular Chemistry of Anions” A. Bianchi, K. Bowman-James, E. Garcia-Espana,<br />
Eds., Wiley-VCH: New York, 1997; (b) “Supramolecular Chemistry-Concepts and Perspectives”<br />
J. M. Lehn, VCH: We<strong>in</strong>heim, 1995.<br />
[2] (a) “Calixarenes 2001” Z. Asfari, V. Bohmer, J. Harrowfield, J. Vicens, Eds., Kluwer Academic:<br />
Dordrecht, 2001; (b) “Calixarenes: A Versatile Class of Macrocyclic Compounds” J. Vicens,<br />
V.Bohmer, Eds., Kluwer Academic; Dordrecht, 1991.<br />
[3] (a) J. Kang, N. Cheong, Bull. Korean Chem. Soc. 2002, 23, 995-997; (b) M. Dudic, P.<br />
Lhotak, I. Stibor, H. Dvorakova, K. Lang, Tetrahedron 2002, 58, 5475-5482; (c) P. Zlatuskova, I.<br />
Stibor, M. Tkadlecova, P. Lhotak, Tetrahedron 2004, 60, 11383-11390.<br />
Poster 056 Thursday 17:40 - 20:10 113
Reevaluation of Fulvene Based Self Replicat<strong>in</strong>g Diels-Alder<br />
System<br />
Ilhan Sevim, Gunter von Kiedrowski<br />
Chair of Organic Chemistry I. Bioorganic Chemistry – Ruhr-Universität Bochum –<br />
NC 2/172 Universitätsstrasse 150 – Bochum – GER<br />
Ilhan.Sevim@ruhr-uni-bochum.de<br />
Chemical systems which have the ability of catalayz<strong>in</strong>g their own formations by the<br />
product templates are def<strong>in</strong>ed as chemical self replicat<strong>in</strong>g systems. Effective self<br />
replicat<strong>in</strong>g systems without the aid of enzymes or external cofactors have attracted<br />
the scientists‘ attention both for their potentials of synthetic applications and understand<strong>in</strong>g<br />
of the orig<strong>in</strong> of life. To understand these systems several artificial ones<br />
have been demonstrated over the last two decades. The aims of these studies were to<br />
understand the efficiency of the systems and structural <strong>in</strong>formation transfer which are<br />
created dur<strong>in</strong>g the reaction. With these concerns, fulvene and maleimide based self<br />
replicat<strong>in</strong>g Diels-Alder system mediated by the hydrogen bond<strong>in</strong>g has been <strong>in</strong>vestigated<br />
with the help of k<strong>in</strong>etic NMR measurements. The high efficiency of the system<br />
has brought us to <strong>in</strong>vestigate the asymmetric version of the system. Different substituted<br />
maleimides have been used with this aim. The diastereomeric distribution of<br />
these reactions have showed some imbalances compared with the ma<strong>in</strong> reaction and<br />
this has brought us to reevaluate the ma<strong>in</strong> reaction. This study conta<strong>in</strong>s the reevaluation<br />
of fulvene and maleimide based self replicat<strong>in</strong>g Diels-Alder system with much<br />
more detailed NMR and HPLC analysis. The efficiency of the different diastereomers<br />
and their autocatalytic and cross-catalytic properties are still under <strong>in</strong>vestigation.<br />
114 Thursday 17:40 - 20:10 Poster 057
The <strong>in</strong>fluence of water molecule coord<strong>in</strong>ation to a metal ion<br />
on water hydrogen bonds<br />
Majda Mis<strong>in</strong>i ∗ , Jelena Andrić † , Dragan N<strong>in</strong>ković † , Milan Milovanović ∗ , Snežana Zarić ⋄<br />
∗ Department of Chemistry – University of Belgrade – Studentski trg 12-16 – Belgrade –<br />
SRB<br />
† Innovation center, Department of Chemistry – University of Belgrade –<br />
Studentski trg 12-16 – Belgrade – SRB<br />
‡ ICTM – University of Belgrade – Njegoševa 12 – Belgrade – SRB<br />
⋄ Department of Chemistry – Texas A and M University – P.O. Box 23874 –<br />
Doha – QAT<br />
majdamis<strong>in</strong>i@gmail.com<br />
Interactions of water molecules with ions, molecules and <strong>in</strong>terfaces, have been <strong>in</strong>tensively<br />
studied. [1] Pure liquid water has a very complex hydrogen bond network nature<br />
and this is still <strong>in</strong> the process of be<strong>in</strong>g clarified us<strong>in</strong>g spectroscopic techniques and<br />
computational methods. [2]<br />
In this work the <strong>in</strong>fluence of cation on water hydrogen bonds was studied by analyz<strong>in</strong>g<br />
crystal structures from Cambridge Structural Database and by high level ab<br />
<strong>in</strong>itio calculations. [3] The hydrogen bonds of the water molecules <strong>in</strong> the first hydration<br />
shell of the cation were compared with the hydrogen bonds of free water molecules.<br />
To the best of our knowledge this is the first work report<strong>in</strong>g on the strength of the<br />
hydrogen bonds of the first hydration shell of metal cations based on the data <strong>in</strong> the<br />
crystal structures from the CSD. The results of statistical analysis of data from CSD,<br />
show that the MLOH/O <strong>in</strong>teractions have a larger tendency towards shorter H. . . O<br />
distances and l<strong>in</strong>ear orientations, which is typical of stronger hydrogen bonds. The<br />
results of calculation show that water coord<strong>in</strong>ation to a metal ion has a remarkable<br />
<strong>in</strong>fluence on hydrogen bonds. Positively charged complexes form quite strong hydrogen<br />
bonds, the hydrogen bond energy of [Zn(H2O)6] 2+ complex with water molecule<br />
([Zn(H2O)6] 2+ ...OH2) is -21.89 kcal/mol, which is several times stronger than the<br />
hydrogen bond of non-coord<strong>in</strong>ated water, -4.77 kcal/mol (HOH...OH2).<br />
Moreover, the hydrogen bond of the aqua ligand has a strong <strong>in</strong>fluence on the stability<br />
and coord<strong>in</strong>ation number of a complex. These results can be important for all the<br />
systems where a water molecule is <strong>in</strong> contact with metal cations, from biomolecules<br />
to materials.<br />
[1] G. R. Desiraju, Angew. Chem., Int. Ed. 2010, 49, 2.<br />
[2] R. Bukowski, K. Szalewicz, G. C. Groenenboom, A. van der Avoird, Science 2007, 315.<br />
[3] J. M. Andrić, G. V. Janjić, D. B. N<strong>in</strong>ković, S.D. Zarić, Physical Chemistry Chemical Physics<br />
2012, 14, 10896.<br />
Poster 058 Thursday 17:40 - 20:10 115
Multicomponent organogelator liquid system based<br />
organogels: A tough competition between gelation and<br />
crystallization<br />
Eva-Maria Schön ∗ , Iti Kapoor ∗ , Jürgen Bachl ∗ , Dennis Kühbeck ∗ , Carlos Cativiela † ,<br />
Subhadeep Saha ‡ , Rahul Banerjee ‡ , Stefano Roelens ⋄ , José Juan Marrero-Tellado # ,<br />
David Díaz Díaz ∗,†<br />
∗ Institut für Organische Chemie – Universität Regensburg – Universitätsstraße 31 –<br />
Regensburg – GER<br />
† Departamento de Química Orgánica, ISQCH – Universidad de Zaragoza - CSIC – Pedro<br />
Cerbuna 12 – Zaragoza – ESP<br />
‡ Physical/Materials Chemistry Division – National Chemical Laboratory – Dr. Homi<br />
Bhabha Road – Pune – IND<br />
⋄ Istituto di Metodologie Chimiche, Consiglio Nazionale della Ricerche, Dipart. di<br />
Chimica – Universitá di Firenze – Via della Lastruccia 13 – Firenze – ITA<br />
# Instituto Universitario de Bio-Orgánica “Antonio González” – Universidad de La<br />
Laguna – Astrofísico Francisco Sánchez 2 – La Laguna, Tenerife – ESP<br />
Eva-Maria.Schoen@chemie.uni-regensburg.de<br />
As physical gels have attracted much attention <strong>in</strong> the last years [1] we present here<br />
new organogels derived from methanolic solution of (1R,2R)-1,2-diam<strong>in</strong>ocyclohexane<br />
L-tartrate. [2]<br />
In comparison with other organogelators, the system presented here (Figure 1 A) has<br />
several feautures which makes it unique: 1) Simple, small and commercially available<br />
chiral build<strong>in</strong>g blocks are the base of the multicomponent gelator system; 2) each<br />
s<strong>in</strong>gle component of the multicomponent solution and its stoichiometry is crucial for<br />
the formation of the organogels and their stability; 3) contrarily to usual way where<br />
the gelation phenomenon takes place dur<strong>in</strong>g cool<strong>in</strong>g-down from high temperatures,<br />
here the gels are result<strong>in</strong>g from warm<strong>in</strong>g up the isotropic solution from low temperatures;<br />
4) although the organogels are composed of low molecular weight components<br />
and consequently hold together by non-covalent <strong>in</strong>teractions, they are not thermoreversible.<br />
This system exemplifies the delicate equilibrium between solution and crystallization<br />
that def<strong>in</strong>es the gel phase (Figure 1 B).<br />
Figure 1:A) Components of the new gelator liquid system. B) Ilustration of the<br />
competition between gelation and crystallization.<br />
[1]<br />
R. G. Weiß, P. Terech, “Molecular Gels: Materials with Self-Assembled Fibrillar Networks”,<br />
Spr<strong>in</strong>ger: NY 2006.<br />
[2]<br />
I. Kapoor, E.-M. Schoen, J. Bachl, D. Kühbeck, C. Cativiela, S. Saha, R. Banerjee, S. Roelens,<br />
J. J. Marrero-Tellado, D. Díaz Díaz, Soft Matter 2012, 8, 3446-3456.<br />
116 Thursday 17:40 - 20:10 Poster 059
Host-guest properties of some cage molecules<br />
Adrian Woiczechowski-Pop ∗ , Anamaria Terec ∗ , Christ<strong>in</strong>e Baudequ<strong>in</strong> † ,<br />
Yvan Ramondenc † , Ion Grosu ∗<br />
∗ Depart. of Organic Chem., Centre of Supramol. Organic and Organometallic Chem. –<br />
Babes-Bolyai University – Arany Janos 11 – Cluj-Napoca – ROU<br />
† Institut de Recherche en Chimie Organique F<strong>in</strong>e de Rouen – Université de Rouen –<br />
Rue Tesniére 76130 – Rouen - Mont Sa<strong>in</strong>t Aignan – FRA<br />
adi_w2001@yahoo.com<br />
Development of synthetic host compounds, comb<strong>in</strong>ed with the numerous studies <strong>in</strong><br />
host-guest chemistry, led to the conclusion that the three-dimensional cage molecules<br />
can be <strong>in</strong>volved <strong>in</strong> specifically directed complex<strong>in</strong>g, molecular recognition, and ion<br />
transport through membranes. [1] Recently, coord<strong>in</strong>ation cage molecules have found<br />
applications as nanoreactors [2] or transport vehicles for cytotoxic compounds [3] and<br />
for the stabilization of reactive molecules [4] respectively. The size and the symmetry<br />
of these cages may also display fasc<strong>in</strong>at<strong>in</strong>g host-guest chemistry.<br />
In this work, theoretical and experimental studies (NMR, UV-Vis, fluorescence) concern<strong>in</strong>g<br />
the supramolecular host-guest properties of type I cage molecules have been<br />
performed (Scheme 1). Different organic molecules have been used as guests for<br />
1,3,5-tris(phenyl)benzene 1,3,5-tris(biphenyl)benzene and 2,4,6-tris(phenyl)-1,3,5-triaz<strong>in</strong>e<br />
based macrocycles.<br />
This work was possible with the f<strong>in</strong>ancial support of the Sectoral Operational Programme<br />
for Human Resources Development 2007-<strong>2013</strong>, co-f<strong>in</strong>anced by the European<br />
Social Fund, under the project number POSDRU 89/1.5/S/60189 with the title “Postdoctoral<br />
Programs for Susta<strong>in</strong>able Development In a Knowledge Based Society”<br />
Scheme 1.<br />
[1] (a) C. J. Pedersen, Angew. Chem. Int. Ed. 1988, 27, 1021; (b) F. Ebmeyer, F. Vögtle,<br />
Angew. Chem. Int. Ed. 1989, 28, 79; (c) C. Seel, F. Vögtle, Angew. Chem. Int. Ed. 1991,<br />
30, 442.<br />
[2] (a) M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. Chem. Int. Ed. 2009, 48, 3418; (b)<br />
T. S. Koblenz, J. Wassenaar, J. N. H. Reek, Chem. Soc. Rev. 2008, 37, 247.<br />
[3] (a) O. Zava, J. Mattsson, B. Therrien, P. J. Dyson, Chem. Eur. J. 2010, 16, 1428; (b) B.<br />
Therrien, G. Süss-F<strong>in</strong>k, P. Gov<strong>in</strong>daswamy, A. K. Renfrew, P. J. Dyson, Angew. Chem. Int. Ed.<br />
2008, 47, 3773.<br />
[4] M. Kawano, Y. Kobayashi, T. Ozeki, M. Fujita, J. Am. Chem. Soc. 2006, 128, 6558.<br />
Poster 060 Thursday 17:40 - 20:10 117
Synthesis, structural aspects and ion transport <strong>in</strong>vestigation<br />
of several new [1+1] condensed cyclophane ether<br />
Zafer Söyler ∗ , M. D. Amir † , Naz Mohammed Aghatabay †<br />
∗ Chemistry – Yıldız Technical University – Davutpaşa – İstanbul – TUR<br />
† Chemistry – Fatih University – Büyükçekmece – İstanbul – TUR<br />
zafersoyler@gmail.com<br />
Six novel [1 + 1] condensed 14 membered cyclophane ethers were synthesized via<br />
simple procedure afford<strong>in</strong>g high yields. The o-dibromoxylene and m-dibromoxylene<br />
were <strong>in</strong>corporated to form macrocyclic units by coupl<strong>in</strong>g with the sodium salts of<br />
the diols (3a, 3b, 3c). [1-3] They were characterized by elemental analyses, mass, FT-<br />
IR, 1 H, and 13 C NMR spectral data. Ion transportation and permeability of the<br />
compounds aga<strong>in</strong>st Na + , K + hard ions and Ag + soft ion were also <strong>in</strong>vestigated. [4]<br />
Scheme a: KOH/EtOH, 60 o C, 3h, 90%; b: MeOH/NaBH4 , 12h, 85%; c: Na/THF 75%.<br />
[1] P. Rajakumar, V. Murali, Tetrahedron 2004, 60, 2351-2360.<br />
[2] P. Rajakumar, R. Kanagalatha, Tetrahedron 2006, 62, 9735-9741.<br />
[3] A. H. M. Elwahy, A. A. Abbas, Tetrahedron 2000, 56, 885-895.<br />
[4] P. Rajakumar, A.M. Abdul-Rasheed, Tetrahedron 2005, 61, 5351-5362.<br />
118 Thursday 17:40 - 20:10 Poster 061
Conductometry as a tool <strong>in</strong> research of β-cyclodextr<strong>in</strong><br />
<strong>in</strong>clusion complex<br />
Katarzyna Abramczyk, Adam Bald<br />
Physical Chemistry of Solutions – University of Lódź – Pomorska 163, 90-236 Lódź –<br />
Łódź – POL<br />
kasiabramczyk@<strong>in</strong>teria.pl<br />
Over the last few years, cyclodextr<strong>in</strong>s have become very popular. These macromolecules<br />
belong to the sugar class compounds. They consist of 6-, 7- or 8- units of<br />
α-D(+) glucopyranoses which are connected by α-1,4-glycosidic bonds <strong>in</strong> such a way<br />
that they form a truncated cone shape. The <strong>in</strong>terior of the molecule is hydrophobic<br />
while the exterior has a hydrophilic character. Depend<strong>in</strong>g on the number of sugar<br />
particles, they are denoted α-, β-, γ-cyclodextr<strong>in</strong>. [1]<br />
In literature there are many papers about wide application of cyclodextr<strong>in</strong>s. The extraord<strong>in</strong>ary<br />
properties of these compounds, relative non-toxicity and low price give rise<br />
to great opportunities for us<strong>in</strong>g cyclodextr<strong>in</strong>s <strong>in</strong> chemistry and numerous <strong>in</strong>dustries. [3]<br />
A special attention shouold be paid to their ability to form <strong>in</strong>clusion complexes. In<br />
our team, we focused on the determ<strong>in</strong>ation of the b<strong>in</strong>d<strong>in</strong>g constants and the basic<br />
thermodynamic functions of <strong>in</strong>clusion complexes of β-CD with the sodium salts of<br />
carboxylic acids us<strong>in</strong>g conductivity method.<br />
Toroidal and chemical structure of cyclodextr<strong>in</strong> [2]<br />
[1]<br />
G. Gattuso, S. A. Nepogodiev, J. Fraser Stoddart, Chem. Rev. 1998, 98, 1919-1958.<br />
[2]<br />
A. A. Rafati, N. Hamnabard, E. Ghasemian, Z. B. Noj<strong>in</strong>i, Materials Science and Eng<strong>in</strong>eer<strong>in</strong>g<br />
C 2009, 29, 791–795.<br />
[3]<br />
M. V. Rekharsky, Y. Inoue, Chem. Rev. 1998, 98, 1875-1917.<br />
Poster 062 Thursday 17:40 - 20:10 119
Phenanthrol<strong>in</strong>e derivatives and DNA<br />
Philipp Scharf , Jens Müller<br />
Institut für Anorganische und Analytische Chemie –<br />
Westfälische Wilhelms-Universität Münster – Corrensstraße 28/30 – Münster – GER<br />
philipp.scharf@uni-muenster.de<br />
Functionalization of the nucleic acids DNA and GNA by <strong>in</strong>troduction of artificial<br />
nucleobases is a grow<strong>in</strong>g field with relevance <strong>in</strong> several chemical discipl<strong>in</strong>es (GNA<br />
= glycol nucleic acid). In particular, the use of ligands as nucleobases result<strong>in</strong>g<br />
<strong>in</strong> the formation of metal-mediated base pairs offers the opportunity to modify the<br />
properties of these supramolecular assemblies. This is expected to lead to <strong>in</strong>terest<strong>in</strong>g<br />
applications <strong>in</strong> nanotechnology, e. g. <strong>in</strong> the areas of conductivity or magnetism. [1-4]<br />
1,10-Phenanthrol<strong>in</strong>e and its derivatives are versatile ligands for a variety of transition<br />
metals. [5] Due to its planarity and aromaticity the use of this ligand <strong>in</strong> metal-mediated<br />
base pairs appears to be feasible.<br />
We report the synthesis of a novel build<strong>in</strong>g block of the ligand 1H-imidazo[4,5-f][1,10]phenanthrol<strong>in</strong>e<br />
and its <strong>in</strong>tegration <strong>in</strong>to a DNA oligonucleotide. Thereafter we refer<br />
to the <strong>in</strong>teraction of this oligonucleotide with several metal ions especially regard<strong>in</strong>g<br />
the thermal stability of the formed metal-mediated base pairs.<br />
[1] L. Zhang, A. E. Peritz, P. J. Carroll, E. Meggers, Synthesis 2006, 645-653.<br />
[2] M. K. Schlegel, L. Zhang, N. Pagano, E. Meggers, Org. Biomol. Chem. 2009, 7, 476-482.<br />
[3] K. Seubert, C. F. Guerra, F. M. Bickelhaupt, J. Müller, Chem. Comm. 2011, 47, 11041-11043.<br />
[4] P. Scharf, J. Müller, ChemPlusChem <strong>2013</strong>, 78, 1, 20-34.<br />
[5] A. Benc<strong>in</strong>i, V. Lippolis, Coord. Chem. Rev. 2010, 254, 2096-2180.<br />
120 Thursday 17:40 - 20:10 Poster 063
Cholesterol-Modified Nucleosides as Precursors for<br />
Microtubes Self-Assembly<br />
Anca Petran ∗ , Nicolai Brodersen † , Paula Pescador † , Holger Scheidt ‡ , Louisa Losensky ⋄ ,<br />
Mart<strong>in</strong> Loew ⋄ , Andreas Herrmann ⋄ , Daniel Huster ‡ , Anna Arbuzova ⋄ , Jürgen Liebscher †<br />
∗ Phyisics of Nanostructural Systems –<br />
National Institute for Research and Development of Isotopic and Molecular Technologies –<br />
Donath, nr. 65-103 400293 Cluj-Napoca – Cluj-Napoca – ROU<br />
† Organic Chemistry – Institute of Chemistry, Humboldt-University Berl<strong>in</strong> –<br />
Brook-Taylor-Str. 2 – Berl<strong>in</strong> – GER<br />
‡ Institute of Medical Physics and Biophysics –<br />
Institute of Medical Physics and Biophysics – Haertelstr. 16-18 – Leipzig – GER<br />
⋄ Institute of Biology/Biophysics –<br />
Institute of Biology/Biophysics, Humboldt-University Berl<strong>in</strong> – Invalidenstr. 42 –<br />
Berl<strong>in</strong> – GER<br />
apetran@itim-cj.ro<br />
Molecular self-assembly is the basis of supramolecular chemistry and can lead to a<br />
variety of structural motifs, e. g. to molecular membranes such as <strong>in</strong> phospholipid<br />
double layers. Under certa<strong>in</strong> circumstances such membranes can form nanotubular<br />
structures. Nanotube formation requires highly ordered molecular pack<strong>in</strong>g and<br />
anisotropic <strong>in</strong>termolecular <strong>in</strong>teractions.<br />
In our group a new lipophilic nucleoside 1 (figure 1, a) was synthesized which selfassembled<br />
<strong>in</strong> microtubes after mix<strong>in</strong>g with a simple phospholipid. [1] The SEM image<br />
of such a microtubule reveals a straight structure with an almost uniform outer diameter<br />
of about 300 nm (figure 1, b). The tubes posses open ends and thus are<br />
<strong>in</strong>terest<strong>in</strong>g as potential carriers, e. g. for drugs.<br />
Our target was to synthesize new cholesteryl-nucleoside and nucleobase derivatives<br />
analogous to structure 1. In these compounds we varied cha<strong>in</strong> length of the l<strong>in</strong>ker,<br />
po<strong>in</strong>t of attachment of cholesterol and additional derivatisation of hydroxyl groups.<br />
These variations give us the ability to study the effect of structural motifs on the<br />
ability to form microtubes by mix<strong>in</strong>g with phospholipids.<br />
[1] P. Pescador, N. Brodersen, H. A. Scheidt, M. Loew, G. Holland, N. Bannert, J. Liebscher, A.<br />
Herrmann, D. Huster, A. Arbuzova, Chem. Commun. 2010, 46, 5358.<br />
Poster 064 Thursday 17:40 - 20:10 121
Parallel Interactions at Large Horizontal Displacement <strong>in</strong><br />
Pyrid<strong>in</strong>e-Pyrid<strong>in</strong>e and Benzene-Pyrid<strong>in</strong>e Dimers<br />
Jelena Andric ∗ , Dragan N<strong>in</strong>kovic ∗ , Snežana Zarić ‡<br />
∗ Innovation center, Department of Chemistry – University of Belgrade –<br />
Studentski trg 12-16 – Belgrade – SRB<br />
‡ Department of Chemistry – Texas A and M University – P.O. Box 23874 – Doha – QAT<br />
jelenaandric.chem@gmail.com<br />
Although aromatic–aromatic <strong>in</strong>teractions have been extensively studied, <strong>in</strong>teractions<br />
at a large horizontal displacement (offset) have only been recently reported. [1] The<br />
results <strong>in</strong>dicated the importance of stack<strong>in</strong>g <strong>in</strong>teractions of benzene molecules at<br />
large horizontal displacements and prompted us to study pyrid<strong>in</strong>e–pyrid<strong>in</strong>e and pyrid<strong>in</strong>e–benzene<br />
parallel <strong>in</strong>teractions.<br />
Here<strong>in</strong>, we present the results on the <strong>in</strong>teractions of pyrid<strong>in</strong>e–pyrid<strong>in</strong>e and pyrid<strong>in</strong>e–benzene<br />
molecules <strong>in</strong> the parallel orientation. We analyzed crystal structures<br />
from the Cambridge Structural Database (CSD) and performed DFT calculations. A<br />
study of crystal structures from the CSD and DFT calculations revealed that parallel<br />
pyrid<strong>in</strong>e–pyrid<strong>in</strong>e <strong>in</strong>teractions at large horizontal displacements (offsets) were<br />
preferred, [2] similar to parallel benzene–benzene <strong>in</strong>teractions. [1]<br />
At large horizontal displacements (4.0-5.0 A) <strong>in</strong>teraction energies <strong>in</strong> the benzenebenzene,<br />
pyrid<strong>in</strong>e–pyrid<strong>in</strong>e and pyrid<strong>in</strong>e–benzene dimers are similar; about 2 kcal<br />
mol -1 .<br />
[1]<br />
D. B. N<strong>in</strong>ković, G. V. Janjić, D.Ž . Veljković, D. N. Sredojević, S. D. Zarić, ChemPhysChem<br />
2011, 12, 1-4.<br />
[2]<br />
D. B. N<strong>in</strong>ković, G. V. Janjić, S. D. Zarić, Cryst. Growth Des. 2012, 12, 1060-1063.<br />
122 Thursday 17:40 - 20:10 Poster 065
Improved Synthesis of Ozazol<strong>in</strong>e-Based Chiral Ligands and<br />
Their Application <strong>in</strong> Heteroleptic Transition-Metal<br />
Complexes<br />
Swantje Wiebalck, Gisa Meißner, C<strong>in</strong>dy Glor, Silke Plachetta, Patrick Kuhrt,<br />
C. Christoph Tzschucke<br />
Chemie und Biochemie – Freie Universität Berl<strong>in</strong> – Takustr. 3 – Berl<strong>in</strong> –<br />
swantje@email.de<br />
Oxazol<strong>in</strong>e based structures provide a versatile design pr<strong>in</strong>ciple for the construction<br />
of ligand collections, s<strong>in</strong>ce they can be derived from the chiral pool of natural<br />
am<strong>in</strong>o acids. Protocols for the synthesis of bisoxazol<strong>in</strong>es (box), pyrid<strong>in</strong>oxazol<strong>in</strong>es (pyrox),<br />
and their derivatives 6-methylpyr<strong>in</strong><strong>in</strong>roxazol<strong>in</strong>e (mepyrox) and qu<strong>in</strong>ol<strong>in</strong>oxazol<strong>in</strong><br />
(qu<strong>in</strong>ox) were established.After amide formation, the crucial r<strong>in</strong>g closure was <strong>in</strong>duced<br />
by a strong base <strong>in</strong> methanol as polar solvent. The reaction protocol offers reliable<br />
access to a variety of different substitution patterns. [1]<br />
The box-type ligands were used for the preparation of new heteroleptic ruthenium or<br />
iridium complexes. The complexes were characterized with respect to their structural<br />
and spectroscopic properties. Initial results regard<strong>in</strong>g the reactivity of the ruthenium<br />
and iridium complexes will be presented. [2]<br />
[1] a) I. Butula, G. Karlovic, Liebigs Ann. Chem 1976, 1455; b) D. Sirbu, G. Consiglio, B.<br />
Milani, P. G. A. Kumar, P. S. Pregos<strong>in</strong>, S. Gischig, J. Organomet. Chem. 2005, 690, 2254 2262;<br />
c) R. I. McDonald, P. B. White, A. B. We<strong>in</strong>ste<strong>in</strong>, C. P. Tam, S. S. Stahl, Org. Lett. 2011, 13,<br />
2830.<br />
[2] G. Mestroni, A., Camus, G. Zass<strong>in</strong>ovich, J. Organomet. Chem. 1974, 73, 119.<br />
Poster 066 Thursday 17:40 - 20:10 123
Direct synthesis of dimethyl carbonate from methanol and<br />
carbon dioxide over surface functionalized CexZr1−xO2<br />
catalysts<br />
Patrick Kollmorgen, Iuliia Prymak, Narayana Kalevaru, Andreas Mart<strong>in</strong>,<br />
Sebastian Wohlrab<br />
Leibniz-Institut für Katalyse e.V. – Albert-E<strong>in</strong>ste<strong>in</strong>-Strasse 29a – 18059 Rostock – GER<br />
patrick.kollmorgen@catalysis.de<br />
Dimethyl carbonate (DMC) is a non-toxic, biodegradable solvent and can be used as<br />
alkylation-/acylation agent, phosgene substitute, fuel additive/antiknock agent, <strong>in</strong>termediate<br />
<strong>in</strong> polymer synthesis, electrolyte <strong>in</strong> lithium-ion-batteries and <strong>in</strong> pharmacy. [1]<br />
In an <strong>in</strong>dustrial scale DMC is ma<strong>in</strong>ly produced via oxidative carbonylation of methanol<br />
us<strong>in</strong>g copper conta<strong>in</strong><strong>in</strong>g species. An <strong>in</strong>terest<strong>in</strong>g alternative susta<strong>in</strong>able route to l<strong>in</strong>ear<br />
carbonates is the direct carboxylation of alcohols which is topic of our current<br />
research. The reaction itself uses CO2 as renewable zero cost feedstock and possess<br />
high atom efficiency. A second aspect of CO2 utilization is the capture of CO2 as<br />
greenhouse gas. Nevertheless for this reaction elementary problems have to be solved.<br />
Due to the thermodynamic stability of the CO2 molecule the activation of the C-Obond<br />
is quite difficult and complex. In addition the reaction is thermodynamically<br />
unfavoured (G=+26 KJ/mol) and consequently the position of the equilibrium leads<br />
to low DMC yields. This work focuses on the CexZr1−xO2 system which has both<br />
acidic and basic sites. [2] These sites play the dom<strong>in</strong>ant role on the catalytic performance.<br />
Our aim is the modification of those acidic and basic properties via chang<strong>in</strong>g<br />
the Ce/Zr ratios or surface functionalization of the CexZr1−xO2 to enhance DMC<br />
yield. In comparison to the monometallic archetypes mixed metal oxides show better<br />
stabilities and higher catalytic activities. CexZr1−xO2 catalysts with vary<strong>in</strong>g molar<br />
metal ratios with x from 0 to 1 were prepared via an oxalate-gel-method. [3] All<br />
synthesized catalysts were catalytically tested <strong>in</strong> a 25 ml autoclave. Reactions were<br />
carried out for 1 h at 443 K, 65 bar of CO2 and typically 10 ml of methanol and 50 mg<br />
of catalyst were used. DMC concentration was determ<strong>in</strong>ed by gas chromatography.<br />
Catalysts where x is 0.6 and 0.8 showed the highest catalytic activity and were further<br />
surface functionalized by different species. The catalysts were characterized by<br />
BET-surface analysis and X-ray diffraction. BET surface areas range between 30 and<br />
90 m 2 /g and XRD-pattern showed that CeO2 exists <strong>in</strong> cubic phase and the ZrO2 exists<br />
<strong>in</strong> monocl<strong>in</strong>ic and tetragonal phase. Our synthesized CexZr1−xO2 solid catalysts<br />
showed comparable activities known from literature. [3] Acid Base surface modifications<br />
on CexZr1−x O2 led to changed catalytic performances. In this context DMC<br />
yield could be <strong>in</strong>creased from 0.4 to 1.1 mol% for Ce0.6Zr0.4O2 and from 0.3 to 1.7<br />
mol% for Ce0.8Zr0.2O2. Results reveal that the Ce content as well as the surface<br />
modification has a significant effect on acid base properties and plays an important<br />
role on the catalytic performance.<br />
[1]<br />
M. Aresta, A. Dibenedetto, C. Pastore, C. Cuocci, B. Aresta, S. Cometa, E. De Giglio, Catalysis<br />
Today 2008, 137, 125-131.<br />
[2]<br />
W. Khaodee, B. Jongsomjit, S. Assabumrungrat, P. Praserthdam, S. Goto, Catalysis Communications<br />
2007, 8, 548-556.<br />
[3]<br />
H. J. Hofmann, A. Brandner, P. Claus, Chemie Ingenieur Technik 2011, 83, 1711-1719.<br />
124 Thursday 17:40 - 20:10 Poster 067
Photochemically Generated S<strong>in</strong>glet Oxygen as Mechanistic<br />
Probe for the Interaction of Bisanthracenes<br />
Matthias Klaper, Torsten L<strong>in</strong>ker<br />
Institut für Chemie – Universität Potsdam – Karl-Liebknecht-Str. 24-25 –<br />
14467 Potsdam OT Golm – GER<br />
mklaper@uni-potsdam.de<br />
The understand<strong>in</strong>g of the <strong>in</strong>teraction of Bisanthracenes via π-π <strong>in</strong>teraction is important<br />
for applications <strong>in</strong> semiconductor techniques. [1] Accord<strong>in</strong>gly, <strong>in</strong>vestigations<br />
on the correlation between π-π stack<strong>in</strong>g ability and photovoltaic performance were<br />
made. [2] Furthermore, it is known that strong <strong>in</strong>teraction will lead preferably to a<br />
high degree of excitonic self quench<strong>in</strong>g or other radiationless deactivation processes<br />
result<strong>in</strong>g <strong>in</strong> poor quantum yields. [3] In literature there is noth<strong>in</strong>g known about endoperoxides<br />
<strong>in</strong>teractions with anthracenes yet.<br />
Here we report about our <strong>in</strong>vestigation on photochemically generated s<strong>in</strong>glet oxygen<br />
as a probe for the <strong>in</strong>teraction of α,ω-dianthrylalkanes and their monoendoperoxides.<br />
Therefore, a number of l<strong>in</strong>ked anthracenes were synthesized by various procedures,<br />
vary<strong>in</strong>g the cha<strong>in</strong>-length from zero to eight.<br />
With these distanced bisanthracenes <strong>in</strong> hand, the k 1 and k 2 values of the two photooxidation<br />
steps to the correspond<strong>in</strong>g mono- and bisendoperoxides were detected.<br />
Interest<strong>in</strong>gly, the k 2 value does not simply rise with prolonged distance, due to less<br />
steric h<strong>in</strong>drance like k 1, but <strong>in</strong>stead reaches a maximum at a certa<strong>in</strong> cha<strong>in</strong> length.<br />
This can be ascribed to the strongest <strong>in</strong>teraction of the anthracene – monoendoperoxid<br />
at this particular distance. This is also assured by experiments of the photo<strong>in</strong>duced<br />
<strong>in</strong>tramolecular [4+4]-cycloaddition at 366 nm, which is only observed for C1- up to<br />
C4-cha<strong>in</strong>es and also by UV and fluorescence spectroscopy. Our f<strong>in</strong>d<strong>in</strong>gs allow conclud<strong>in</strong>g<br />
the formation of a ferrocene-like anthracen - s<strong>in</strong>glet oxygen - anthracen sandwich<br />
complex at this particular distance.<br />
[1]<br />
L. R. MacGillivray et al., J. Am. Chem. Soc. 2006, 128, 2806.<br />
[2]<br />
H. Hoppe et al., Macromolecules 2010, 43, 126.<br />
[3]<br />
a) D. A. M. Egbe et al., Macromolecules 2010, 43, 306; b) P. Günther et al., J. Phys. Chem.<br />
1996, 100, 18931.<br />
Poster 068 Thursday 17:40 - 20:10 125
Development of novel bifunctional chiral thiourea derivative<br />
as organocathalyst<br />
Ana Escamilla, Ana C. Cuñat, Juan F. Sanz<br />
Department of Organic Chemistry – University of Valencia –<br />
c/ Doctor Mol<strong>in</strong>er N o 50 46100 – Valencia – ESP<br />
ana.escamilla@uv.es<br />
In this communication, we are describ<strong>in</strong>g the design of chiral bifunctional thioureas<br />
bear<strong>in</strong>g an imidazol<strong>in</strong>e r<strong>in</strong>g <strong>in</strong> expectation of their dual activation of both electrophiles<br />
and nucleophiles to promote a wide range of nucleophilic addition reactions. We have<br />
modified the r<strong>in</strong>g A substitution <strong>in</strong> order to enhance the acidity of NH protons, thus<br />
<strong>in</strong>creas<strong>in</strong>g the substrate’s nucleophilicity (see scheme below).<br />
The most important moiety of this structure is the imidazol<strong>in</strong>e r<strong>in</strong>g, which is synthesized<br />
from a chiral diam<strong>in</strong>e and an aldehyde. Diam<strong>in</strong>e 2 was obta<strong>in</strong>ed through<br />
amidation and reduction of phenyglyc<strong>in</strong>e methyl esther. In order to prepare the desired<br />
organocathalyst, a thiourea functionality was <strong>in</strong>troduced by means of reaction<br />
between an isothiocyanate and a primary am<strong>in</strong>e.<br />
The new organocathalysts will be tested <strong>in</strong> several transformations, such as Henry or<br />
aza-Henry [1] , Michael [2] and Mannich [3] additions.<br />
[1] X. Xu, T. Furukawa, T. Ok<strong>in</strong>o, H. Miyabe, Y. Takemoto, Chem. Eur.J. 2005, 12, 466-476.<br />
[2] C. Chun-Li, Y. Meng-Chun, S. Xiu-Li, T. Yong Org. Lett. 2006, 8, 2901-2904.<br />
[3] Z.Hui, C. Yongm<strong>in</strong>g, L. Zhengyu, P. Yungui Adv. Synth. Catal. 2009, 351, 2288-2294.<br />
126 Thursday 17:40 - 20:10 Poster 069
Asymmetric Total Synthesis of Smyr<strong>in</strong>diol Employ<strong>in</strong>g an<br />
Organocatalytic Aldol Key Step<br />
Jeanne Fronert, Tom Bisschops, Florian Boeck, Dieter Enders<br />
Institute of Organic Chemistry – Landoltweg 1 – Aachen – GER<br />
jeanne.fronert@rwth-aachen.de<br />
The natural product smyr<strong>in</strong>diol, also called (+)-(2’S,3’R)-3-hydroxymarmes<strong>in</strong>, is a<br />
l<strong>in</strong>ear dihydrofurocoumar<strong>in</strong> which was isolated from the roots of Smyrniopsis aucheri<br />
by Dzhafarov et al. <strong>in</strong> 1992 and from the roots of Brosimum gaudichaudii by Vilegas<br />
et al. <strong>in</strong> 1993. [1] Smyr<strong>in</strong>diol has shown antifungal and antibacterial activity and can<br />
be used to cure Vitiligo, a sk<strong>in</strong> disease, or as a vasodilator. [1a,2]<br />
The first organocatalytic asymmetric synthesis of smyr<strong>in</strong>diol us<strong>in</strong>g a (S)-prol<strong>in</strong>e catalyzed<br />
5-enolexo aldol reaction as key step is described. The diastereo- and enantioselectivity<br />
is virtually complete (de 99%, ee 99%) and the title compound was<br />
obta<strong>in</strong>ed <strong>in</strong> 15 steps <strong>in</strong> an overall yield of 6.3%. [3]<br />
In addition to the aldol reaction the total synthesis also <strong>in</strong>cludes a new type of<br />
coumar<strong>in</strong> assembly via a Sonogashira reaction to a propiolic acid derivative, followed<br />
by a L<strong>in</strong>dlar reduction / lactonization sequence, which opens a new efficient and<br />
flexible entry to the coumar<strong>in</strong> core of other natural products.<br />
[1] a) Z. R. Dzhafarov, Z. A. Kuliev, A. D. Vdov<strong>in</strong>, A. A. Kuliev, V. M. Malikov, N. M. Ismailov,<br />
Chem. Nat. Compd. 1992, 28, 27; b) W. Vilegas, G. L. Pozetti, J. Harumi Yariwake Vilegas, J.<br />
Nat. Prod. 1993, 56, 416.<br />
[2] B. Ngameni, V. Kuete, I. K. Simo, A. T. Mbaveng, P. K. Awoussong, R. Patnam, R. Roy, B.<br />
T. Ngadjui, S. Afr. J. Bot. 2009, 75, 256.<br />
[3] D. Enders, J. Fronert, T. Bisschops, F. Boeck, Beilste<strong>in</strong> J. Org. Chem. 2012, 8, 1112.<br />
Poster 070 Thursday 17:40 - 20:10 127
Investigation of organocatalytic reaction mechnisms us<strong>in</strong>g<br />
ESI-MS<br />
Mart<strong>in</strong> Schmidt, Marianne Engeser<br />
Kekule-Institut für Organische Chemie und Biochemie – Universität Bonn –<br />
Gerhard-Domagk-Str. 1 – Bonn – GER<br />
mlschm@uni-bonn.de<br />
SOMO catalysis has obta<strong>in</strong>ed large <strong>in</strong>terest as a new and powerful version of enantioselective<br />
organocatalysis which <strong>in</strong>cludes radical steps <strong>in</strong>itiated by a one-electron<br />
oxidation. [1] The key <strong>in</strong>termediate enam<strong>in</strong>e radical cation has been postulated but<br />
had not been observed directly until it we could detect it by ESI mass spectrometry<br />
comb<strong>in</strong>ed with an onl<strong>in</strong>e microreactor technique. [2] This Comb<strong>in</strong>ation has proven to<br />
be an excellent tool to <strong>in</strong>vestigate reaction mechanisms <strong>in</strong> solution as it allows the<br />
detection of short-lived, reactive molecules such as radical species.<br />
We have identified enam<strong>in</strong>e radical cation species <strong>in</strong> the case of four commonly used<br />
imidazolid<strong>in</strong>-4-one organocatalysts so far. Subsequent reactions of the enam<strong>in</strong>e radicals<br />
with e.g. styrene (Fig.1) could be observed <strong>in</strong> our experiments as well. [2] Currently,<br />
the project is extended towards establish<strong>in</strong>g electrochemical oxidation onl<strong>in</strong>e<br />
coupled to the MS to replace the chemical oxidant.<br />
A second project aims on mechanism elucidation of enam<strong>in</strong>e mediated, prol<strong>in</strong>e catalysed<br />
reactions which has been a strongly <strong>in</strong>vestigated field of organocatalysis <strong>in</strong> the<br />
last years. Therefore a charge labeled, prol<strong>in</strong>e based organocatalysts was synthesized.<br />
The catalyst carries a fixed charge far away from the catalytic center which enables<br />
us to detect <strong>in</strong>termediate species <strong>in</strong> low concentrations via MS without <strong>in</strong>fluenc<strong>in</strong>g<br />
the properties of the catalytic center.<br />
Figure 1. In situ formation of an <strong>in</strong>termediate enam<strong>in</strong>e radical (red) cation and follow<strong>in</strong>g<br />
reaction with styrene under SOMO catalysis conditions.<br />
[1] T. D. Beeson, A. Mastracchio, J. Hong, K. Ashton, D. W. C. MacMillan, Science, 2007, 316,<br />
582. [2] R. Beel, S. Kobialka, M.L. Schmidt, M. Engeser, Chem.Comm. 2011, 47, 3293.<br />
128 Thursday 17:40 - 20:10 Poster 071
The <strong>in</strong>fluence of calc<strong>in</strong>ation parameters on Cu catalysts<br />
derived from mixed Cu,Zn hydroxy-carbonate precursors<br />
Julia Schumann, Andrey Tarasov, Nygil Thomas, Robert Schlögl, Malte Behrens<br />
Department of Inorganic Chemistry – Fritz-Haber-Institut der Max-Planck-Gesellschaft –<br />
Faradayweg 4-6 – Berl<strong>in</strong> – GER<br />
schumann@fhi-berl<strong>in</strong>.mpg.de<br />
Methanol is one of the most important bulk chemicals. Its synthesis is performed<br />
over Cu/ZnO/Al2O3 catalysts. The well-established catalyst preparation by coprecipitation<br />
leads to a precursor system with a complex phase mixture [1] , conta<strong>in</strong><strong>in</strong>g<br />
different hydroxy-carbonates. Thermogravimetric (TG) measurements show, that the<br />
decomposition of Cu,Zn hydroxy-carbonates dur<strong>in</strong>g calc<strong>in</strong>ation proceeds <strong>in</strong> two ma<strong>in</strong><br />
steps: After the desorption of surface water, firstly, H2O and CO2 are released simultaneously<br />
and <strong>in</strong> a second step only CO2 is released. The <strong>in</strong>termediate is therefore<br />
termed “high temperature carbonate” (HT-CO3). [2] Accord<strong>in</strong>g to the TG data, the<br />
typical calc<strong>in</strong>ation temperatures around 350 ◦ C would favor the formation of HT-<br />
CO3, but its role for the catalytic activity is unclear. The aim of this study is to<br />
<strong>in</strong>vestigate the <strong>in</strong>fluence of the calc<strong>in</strong>ation parameters on the properties and catalytic<br />
performance of catalysts derived from z<strong>in</strong>cian malachite and aurichalcite precursors.<br />
We prepared two series of catalysts by variation of the calc<strong>in</strong>ation conditions. The<br />
first series starts from a phase pure aurichalcite, (Zn,Cu)5(CO3)2(OH)6, with a molar<br />
metal ratio Cu/Zn of 40:60. The second series starts from a z<strong>in</strong>cian malachite,<br />
(Cu,Zn)(CO3)(OH)2 (Cu/Zn 80:20) precursor. All samples were calc<strong>in</strong>ed <strong>in</strong> a rotat<strong>in</strong>g<br />
furnace at 330 ◦ C for 3 h with a flow of 100 ml/m<strong>in</strong>. The heat<strong>in</strong>g rates were varied<br />
between 0.1 and 2 K/m<strong>in</strong>. The result<strong>in</strong>g catalysts have been characterized <strong>in</strong> depth<br />
by XRD, TG analysis and IR spectroscopy and the catalytic activities <strong>in</strong> methanol<br />
synthesis have been tested.<br />
TG <strong>in</strong>vestigations of the calc<strong>in</strong>ed sample series revealed, that catalysts heated with<br />
different heat<strong>in</strong>g rates conta<strong>in</strong> different amounts of HT-CO3 after calc<strong>in</strong>ation. By <strong>in</strong>creas<strong>in</strong>g<br />
the heat<strong>in</strong>g rate, more water accumulates <strong>in</strong> the atmosphere above the sample<br />
and cannot be purged out fast enough. The amount of water <strong>in</strong> the atmosphere dur<strong>in</strong>g<br />
calc<strong>in</strong>ation crucially <strong>in</strong>fluences the decomposition k<strong>in</strong>etics of the hydroxy-carbonate<br />
by promot<strong>in</strong>g the decomposition of the HT-CO3 and the crystallization of the metal<br />
oxides CuO and ZnO. [3] This is confimed by XRD measurements. The samples with<br />
the highest heat<strong>in</strong>g rates are most crystall<strong>in</strong>e <strong>in</strong> both series, the samples of the exaurichalcite<br />
series with lower heat<strong>in</strong>g rates are nearly amorphous, with some weak<br />
features that cannot be ascribed to either ZnO or CuO. IR spectra of the calc<strong>in</strong>ed<br />
samples show bands <strong>in</strong> the carbonate region, similar to the ones <strong>in</strong> the precursors.<br />
Here aga<strong>in</strong>, the samples with the highest heat<strong>in</strong>g rate differ from the other samples by<br />
show<strong>in</strong>g weaker and much broader features. Copper metal surface areas varied <strong>in</strong> a<br />
range of 19-25 m 2 /g and 13-19 m 2 /g for the ex-aurichalcite and ex-z<strong>in</strong>cian malachite<br />
series, respectively. Activity <strong>in</strong> methanol synthesis was measured, but only differences<br />
smaller 10 % were found. There is an apparent trend <strong>in</strong> the activity data (normalized<br />
per weighed portion), but this trend is reversed when normaliz<strong>in</strong>g the activity to the<br />
actual reduced mass of catalyst. Therefore, no beneficial effect of a large amount of<br />
HT-CO3 for the catalytic activity <strong>in</strong> methanol synthesis was observed.<br />
[1] C. Baltes, S. Vukojevic, F. Schüth, J. Catal. 2008, 258, 334.<br />
[2] M. Behrens, F. Girgsdies, A. Trunschke, R. Schlögl, Eur. J. Inorg. Chem. 2009, 1347.<br />
[3] S. Fujita, S. Moribe, Y. Kanamori, R. Takezawa, React. K<strong>in</strong>et. Catal. Lett. 2000, 11.<br />
Poster 072 Thursday 17:40 - 20:10 129
Gold-catalyzed Cycloisomerization of Fluor<strong>in</strong>ated Allenes:<br />
Application <strong>in</strong> BODIPY-Synthesis<br />
L<strong>in</strong>da Lempke ∗ , Norbert Krause ∗ , Tobias Fischer † , Knut Rurack †<br />
∗ Organic Chemistry – TU Dortmund – Otto-Hahn-Straße 6 – 44227 Dortmund – GER<br />
† Bundesanstalt für Materialforschung und -prüfung – Fachbereich 1.9 –<br />
Richard-Willstätter-Straße 11 – 12489 Berl<strong>in</strong> – GER<br />
L<strong>in</strong>da.Lempke@tu-dortmund.de<br />
The gold-catalyzed cycloisomerization of α-functionalized allenes is a well-known<br />
reaction. [1] Us<strong>in</strong>g this selective formation to prepare functionalized cycloisomerization<br />
products is of particular value for different applications or the total synthesis of<br />
natural products and their derivatives.<br />
In this project, the gold-catalyzed cycloisomerization of fluor<strong>in</strong>ated α-am<strong>in</strong>oallenes is<br />
applied for the synthesis of new BODIPY (boron-dipyrromethene) fluorescent dyes. [2]<br />
Furthermore the use of ionic liquids as reaction medium for gold-catalyzed cyclisation<br />
reactions [3] offers the possibility of recycl<strong>in</strong>g the catalyst, thus enhanc<strong>in</strong>g susta<strong>in</strong>ability<br />
and <strong>in</strong>dustrial practicability.<br />
BODIPY’s have particular spectroscopic properties like small stoke shifts and high<br />
quantum yields which open new avenues for their application. The high fluor<strong>in</strong>e content<br />
facilitates XPS-measurements beside the possibility of conventional fluorescent<br />
detection.<br />
Abb.1. Au-catalyzed cycloisomerisation as a key-step <strong>in</strong> BODOPY synthesis.<br />
[1] C. W<strong>in</strong>ter, N. Krause, Chem. Rev. 2011, 111, 1994-2009.<br />
[2] G. Ulrich, R. Ziessel, A. Harriman, Angew. Chem. Int. Ed. 2008, 47, 1184-1201.<br />
[3] Ö. Aksın, N. Krause, Adv. Synth. Catal. 2008, 350, 1106-1112.<br />
130 Thursday 17:40 - 20:10 Poster 073
One-pot organocatalytic asymmetric synthesis of<br />
nitrogenated tricyclic compounds<br />
David Sadaba ∗ , Ignacio Delso † , Tomas Tejero ∗ , Pedro Mer<strong>in</strong>o ∗<br />
∗ Departamento de Síntesis y Estructura de Biomoléculas –<br />
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) – C/ Pedro Cerbuna, 12 –<br />
Zaragoza – ESP<br />
† Servicio de Resonancia Magnética Nuclear –<br />
Centro de Química y Materiales de Aragón (CEQMA) – C/ Pedro Cerbuna, 12 –<br />
Zaragoza – ESP<br />
dsadaba@unizar.es<br />
Five-membered cyclic nitrones have been demonstrated to be <strong>in</strong>terest<strong>in</strong>g heterocycles<br />
and attractive build<strong>in</strong>g blocks for the synthesis of a variety of nitrogenated compounds<br />
conta<strong>in</strong><strong>in</strong>g a pyrrolid<strong>in</strong>e r<strong>in</strong>g <strong>in</strong> their structure, many of them of biological <strong>in</strong>terest.<br />
Most of the reported syntheses of enantiomerically pure five-membered cyclic nitrones<br />
employ natural sugars as start<strong>in</strong>g materials. A different approach was carried out<br />
<strong>in</strong> order to prepare other cyclic nitrones with different substituents, us<strong>in</strong>g common<br />
reactants such as nitrostyrene.<br />
In this work, a new three-step one-pot methodology was developed. The first step<br />
is a Michael addition reaction of an aldehyde (1) to a nitroalkene (2). This is an<br />
organocatalytic reaction mediated by a prol<strong>in</strong>ol chiral derivative. [1] This reaction generates<br />
two chiral carbons <strong>in</strong> a γ-nitroaldehyde compound. In the follow<strong>in</strong>g step, the<br />
reduction of the nitro group to hydroxylam<strong>in</strong>e group was done and, <strong>in</strong> situ, the condensation<br />
of the latter one with the aldehyde to yield the nitrone (3) took place. The<br />
treatment of the reaction mixture provided alkenyl nitrones (3d) gave spontaneously<br />
an <strong>in</strong>tramolecular 1,3-dipolar cycloaddition lead<strong>in</strong>g to tricyclic derivatives 4. [2]<br />
Figure 1<br />
Acknowledgements:<br />
D. S. thanks the Spanish Council for Scientific Research (CSIC) for his JAE-predoctoral grant.<br />
References:<br />
[1] For a review see: D. Roca-Lopez, D. Sadaba, I. Delso, R. P. Herrera, T. Tejero, P. Mer<strong>in</strong>o,<br />
Tetrahedron: Asymmetry 2010, 21, 2561-2601.<br />
[2] D.Sadaba, I. Delso, T. Tejero, P. Mer<strong>in</strong>o, Tetrahedron: Lett 2011, 52, 5976-5979.<br />
Poster 074 Thursday 17:40 - 20:10 131
The effect of tertiary am<strong>in</strong>es on the structure and selectivity<br />
of dialkylallium alkoxides <strong>in</strong> the polymerization of rac-LA<br />
Anna Maria Dabrowska, Anna Litw<strong>in</strong>ska, Pawel Horeglad<br />
Chemistry – University of Warsaw – Zwirki i Wigury 101 – Warsaw – POL<br />
anna.m.dabrowska@student.uw.edu.pl<br />
Polylactide (PLA), called a “nature’s polyethylene” [1] , is well known for its good<br />
mechanical properties, biodegradability, and biocompatibility. Moreover, it can be<br />
synthesized from renewable resources. These make PLA environmentally friendly<br />
polymer of many potential applications. The latter results from the properties of<br />
polylactide (PLA), which depend significantly on its tacticity. Therefore it is essential<br />
to synthesize PLA <strong>in</strong> the controlled and stereoselective way. One of the most<br />
promis<strong>in</strong>g methods for the synthesis of PLA is the r<strong>in</strong>g-open<strong>in</strong>g polymerization (ROP)<br />
of racemic lactide (rac-LA) us<strong>in</strong>g metal alkoxides as <strong>in</strong>itiators.<br />
Dialkylgallium alkoxides are very <strong>in</strong>terest<strong>in</strong>g catalysts as they can polymerize rac-LA<br />
<strong>in</strong> controlled and stereoselective manner. [2] We showed that heterotactically enriched<br />
polylactide can be obta<strong>in</strong>ed <strong>in</strong> the presence of dialkylgallium alkoxides modified with<br />
Lewis bases, while the heteroselectivity was found to be strongly related to the coord<strong>in</strong>ation<br />
efficiency of a Lewis base to Ga center (Scheme 1). [2] Noteworthy is the<br />
fact that dialkylgallium enabled for the first time the facile switch of stereoselectivity<br />
dur<strong>in</strong>g the process of polymerization as the use of strong Lewis bases, such<br />
as N-heterocyclic carbenes, for the complexation of dialkylgallium alkoxides led to<br />
isoselective gallium catalysts. [3]<br />
It is therefore important to exam<strong>in</strong>e <strong>in</strong> details the effect of various Lewis bases on<br />
the activity and stereoselectivity of obta<strong>in</strong>ed dialkylgallium catalysts. I am go<strong>in</strong>g to<br />
present the results of our studies on the effect of tertiary am<strong>in</strong>es on the structure and<br />
selectivity of dialkylgallium alkoxides, and the structure of obta<strong>in</strong>ed polylactide.<br />
Scheme 1<br />
[1] D.J. Cole-Hamilton, Angewandte Chemie 2010, 49, 8564-8566.<br />
[2] P. Horeglad, P. Kruk, J. Pecaut, Organometallics 2010, 29, 3729-3734.<br />
[3] P. Horeglad, G. Szczepaniak, M. Dranka, J. Zachara, Chemical Communications 2012, 48,<br />
1171-1173.<br />
132 Thursday 17:40 - 20:10 Poster 075
Supported MoV-Mixed Metal Oxide Catalyst for Selective<br />
Oxidation of Propane<br />
Pia Kjaer Nielsen, Kazuhiko Amakawa, Annette Trunschke, Robert Schlögl<br />
Anorganische Chemie – Fritz-Haber-Institut der Max-Planck-Gesellschaft –<br />
Faradayweg 4-6 – 14195 Berl<strong>in</strong> – GER<br />
pia@fhi-berl<strong>in</strong>.mpg.de<br />
Introduction<br />
MoV-mixed metal oxides are frequently applied as catalysts for selective oxidation,<br />
<strong>in</strong> bulk phases as well as supported systems. [1] Support<strong>in</strong>g the metal oxide phases<br />
on a high surface area, mesoporous, and <strong>in</strong>ert SiO2 material, allows the possibility<br />
to study the model catalyst surface isolated from bulk properties. In this study we<br />
report a systematic <strong>in</strong>vestigation of the effects of the V:Mo metal oxide ratio of such<br />
supported model systems.<br />
Experimental<br />
Supported MoV-mixed metal oxides were prepared by anchor<strong>in</strong>g (NH4)6Mo7O24<br />
and NH4VO3 to the surface of functionalized SBA-15 by apply<strong>in</strong>g an ion exchange<br />
methodology. [2] Upon calc<strong>in</strong>ation the metal oxide precursors decomposed to disperse<br />
metal oxide species on the surface of the support. A series of samples of vary<strong>in</strong>g<br />
V:Mo ratio with constant total metal load<strong>in</strong>g was obta<strong>in</strong>ed. Materials were characterized<br />
by N2-physisorption, XRD, XRF, SEM/EDX along with <strong>in</strong> situ Raman and<br />
UV-vis spectroscopy, before their catalytic performance <strong>in</strong> oxidative dehydrogenation<br />
of propane (ODP) was <strong>in</strong>vestigated.<br />
Results<br />
The mesoporous structure of SBA-15 is ma<strong>in</strong>ta<strong>in</strong>ed, while the metal oxide species are<br />
distributed homogeneously throughout the f<strong>in</strong>al catalyst materials. Due to the variation<br />
<strong>in</strong> ratios, the <strong>in</strong>teraction between the V and Mo oxides differs. The <strong>in</strong>teraction<br />
has been analyzed us<strong>in</strong>g <strong>in</strong> situ UV-vis and Raman spectroscopy. A consequence of<br />
this variation is difference <strong>in</strong> the catalytic behavior <strong>in</strong> ODP.<br />
[1] H. Dai et al. Journal of Catalysis 2004, 221, 491-499.<br />
[2] Hess et al. J. Phys. Chem. B 2004, 108 (28), 9703-9709.<br />
Poster 076 Thursday 17:40 - 20:10 133
Group 4 Sugar Complexes and Their Application <strong>in</strong> Catalysis<br />
Anne Sachs, Jürgen Heck<br />
Chemistry – Hamburg – Mart<strong>in</strong>-Luther-K<strong>in</strong>g-Platz 6 – Hamburg – GER<br />
sachs@chemie.uni-hamburg.de<br />
In the last decade, we were successful to synthesise various organometallic complexes<br />
of early transition metals with monosaccharide ligands. The obta<strong>in</strong>ed structures are<br />
anionic or neutral d<strong>in</strong>uclear complexes which are bridged via one or two pyranosidato<br />
ligands. [1-3]<br />
Our first complex of this class of compounds was achieved by reaction of CpZrCl3(thf)2<br />
with methyl-4,6-O-benzylidene-β-D-glucopyranoside <strong>in</strong> presence of triethylam<strong>in</strong>e. [1]<br />
Thereby, the complex conta<strong>in</strong><strong>in</strong>g benzylidene protected glucopyranosidato ligands<br />
forms a U-shaped chiral cavity with C 2-symmetry. The anionic zirconate complex 1<br />
<strong>in</strong>corporates a triethylammmonium cation form<strong>in</strong>g a host-guest couple. Add<strong>in</strong>g other<br />
am<strong>in</strong>es the <strong>in</strong>corporated cation is substituted. By us<strong>in</strong>g a racemic mixture the chiral<br />
cavity is able to discrim<strong>in</strong>ate between R- and S-enantiomers. [4]<br />
We obta<strong>in</strong>ed a similar complex conta<strong>in</strong><strong>in</strong>g two titanium centres by us<strong>in</strong>g Cp* <strong>in</strong>stead<br />
of Cp. Molecule 2 conta<strong>in</strong>s only two chlorido ligands and for this reason it is neutral<br />
and cannot <strong>in</strong>corporate other anions. 2 is used as precatalyst for hydroam<strong>in</strong>ation<br />
reactions. [5]<br />
Next to d<strong>in</strong>uclear compounds we are also try<strong>in</strong>g to synthesise mononuclear titanium<br />
and zirconium sugar complexes to use them also as catalysts <strong>in</strong> different reactions.<br />
Figure D<strong>in</strong>uclear anionic zirconate complex 1 and neutral titanium complex 2<br />
[1] L. Jessen, E. T. K. Haupt, J. Heck, Chem. Eur. J. 2001, 7, 3791-3797.<br />
[2] C. Bolm, F. E. Hahn, Activat<strong>in</strong>g Unreactive Substrates, Wiley-VCH Verlag GmbH & Co.<br />
KGaA, We<strong>in</strong>heim, 2009, 147-164.<br />
[3] S. Tschersich, M. Böge, D. Schwidom, J. Heck, Rev. Inorg. Chem. 2011, 31, 27-55.<br />
[4] P. Kitaev, Dissertation, University of Hamburg, 2009.<br />
[5] D. Küntzer, L. Jessen, J. Heck, Chem. Commun. 2005, 5653-5655.<br />
134 Thursday 17:40 - 20:10 Poster 077
Structure and reactivity of supported VOx and MoOx<br />
selective oxidation catalysts<br />
Juliane Scholz , Thorsten Ressler<br />
Institut für Chemie – Technische Universität Berl<strong>in</strong> –<br />
Sekr. C2 / Straße des 17. Juni 135 – 10623 Berl<strong>in</strong> – GER<br />
juliane.scholz@tu-berl<strong>in</strong>.de<br />
Heterogeneous catalysis is an important tool to convert resources to valuable chemicals.<br />
One of the most important reactions to generate functionalized hydrocarbons<br />
is selective oxidation of alkanes and alkenes with molybdenum and vanadium based<br />
oxide catalysts. Industrially used catalysts exhibit a highly complex chemical composition.<br />
To understand pr<strong>in</strong>ciple reaction processes <strong>in</strong> catalytic oxidation it is essential<br />
to study model systems under simplified conditions. Nanostructured oxide materials<br />
are often used as support, to create suitable model systems for detailed simultaneous<br />
<strong>in</strong>vestigations of catalysts structure and performance. The structure of the surface oxide<br />
catalysts is significantly affected by the properties of the support material. Thus,<br />
it is possible to generate a variety of molecular model catalyst structures.<br />
Here, we <strong>in</strong>vestigated the <strong>in</strong>fluence of MgO-coated SBA-15 (MgO/SBA-15 ) with alkal<strong>in</strong>e<br />
surface properties on the structure of vanadium and molybdenum oxide catalysts.<br />
To ga<strong>in</strong> deeper <strong>in</strong>sight <strong>in</strong>to structure activity correlation, we used a comb<strong>in</strong>ation of<br />
spectroscopic techniques and simultaneous determ<strong>in</strong>ation of catalytic activity under<br />
selective propene oxidiz<strong>in</strong>g conditions. The alkal<strong>in</strong>e character of the MgO-based<br />
support led to the formation of highly simplified catalysts units. X-ray absorption<br />
spectroscopy (XAS) and diffuse reflectance UV-Vis (DR-UV-Vis) spectroscopy measurements<br />
showed that a similar structural motif was obta<strong>in</strong>ed for VOx and MoOx<br />
supported on MgO/SBA-15 with a tetrahedral arrangement of oxygen atoms around<br />
the metal centers. In situ XAS <strong>in</strong>vestigations under propene oxidiz<strong>in</strong>g conditions<br />
revealed a correlation between structural changes and the onset of catalytic activity.<br />
Selectivity towards the selective oxidation of propene to acrole<strong>in</strong> was directly correlated<br />
to the number of bridg<strong>in</strong>g M–O–M bonds (Fig. 1). Thus, the presence of<br />
nucleophilic oxygen <strong>in</strong> the M–O–M bond proved to be crucial for selective oxidation.<br />
Fig. 1: Selectivity towards acrole<strong>in</strong> of supported vanadium oxides at different V load<strong>in</strong>gs<br />
compared to a supported molybdenum oxide under propene oxidiz<strong>in</strong>g conditions.<br />
We acknowledge HASYLAB, Hamburg and the Deutsche Forschungsgeme<strong>in</strong>schaft (DFG) for provid<strong>in</strong>g<br />
beamtime and f<strong>in</strong>ancial support, respectively.<br />
Poster 078 Thursday 17:40 - 20:10 135
New method for assessment of the photocatalytic<br />
degradation of VOCs based on FTIR technique<br />
Patrycja Lyczkowska, Małgorzata Cieślak, Grzegorz Celichowski<br />
Department of Materials Technology and Chemistry – University of Lodz –<br />
Pomorska 163 – Lodz – POL<br />
plyczkowska@uni.lodz.pl<br />
These studies were carried out <strong>in</strong> cooperation with Scientific Department of Unconventional<br />
Technologies and Textiles, Textile Research Institute, Brzez<strong>in</strong>ska 5/15, 92-103<br />
Lodz, Poland (Head of work: PhD Eng. Małgorzata Cieślak)<br />
Indoor air quality (IAQ) is one of the most significant factors affect<strong>in</strong>g the health and<br />
well-be<strong>in</strong>g of people who spend a lot of time <strong>in</strong> their lives <strong>in</strong>doors. Volatile organic<br />
compounds (VOCs) <strong>in</strong>clude a variety of chemicals, which adversely affect on human<br />
health. Among the different treatment methods developed for the degradation of<br />
VOCs, photocatalytic oxidation process with us<strong>in</strong>g titanium dioxide as photocatalyst<br />
can be considered as an <strong>in</strong>novative and promis<strong>in</strong>g solution. Currently, research is<br />
carried out on the modification of textile materials with titanium dioxide. The evaluation<br />
of the photocatalytic activity of different forms of titanium dioxide and textile<br />
materials modified by them requires search<strong>in</strong>g a suitable techniques.<br />
The aim of this study was the development of a new measurement method for the<br />
photocatalytic effectiveness assessment based on Fourier Transform Infrared Spectroscopy<br />
(FTIR) technique. FTIR Spectrometer Bruker Vertex 70 equipped with the<br />
gas cuvette was used and the specially photoreactor (with quartz cover) connected to<br />
FTIR was built. The Xenon lamp Optel (150 W) to the photocatalytic process was<br />
used. The photocatalytic activity of titanium oxide (IV) (TiO2) and titanium oxide<br />
(IV) modified by silver (TiO2/Ag) was tested. As a model of VOCs the toluene was<br />
selected.<br />
It was found that, the assessment of the photocatalytic activity of titanium dioxide<br />
towards VOCs us<strong>in</strong>g developed method based on FTIR spectroscopy technique is<br />
possible.<br />
136 Thursday 17:40 - 20:10 Poster 079
Mechanistic Investigations of the Palladium-Catalysed<br />
Arylation of Pyrid<strong>in</strong>e N-Oxides<br />
Emma Svensson, Sasa Duric, S<strong>in</strong>a Zucker, C. Christoph Tzschucke<br />
Chemie und Biochemie – Freie Universität Berl<strong>in</strong> – Takustr. 3 – Berl<strong>in</strong> – GER<br />
emma-svensson@hotmail.com<br />
Direct arylation of pyrid<strong>in</strong>e N-oxides via palladium-catalysed C-H-activation has<br />
shown to be a convenient synthesis of substituted bipyrid<strong>in</strong>e N-oxides. [1,2] The limitation<br />
of the coupl<strong>in</strong>g reaction lies with<strong>in</strong> the electronic properties of the pyrid<strong>in</strong>e Noxide.<br />
Direct arylation of electron-deficient substrates such as 4-ethoxycarbonylpyrid<strong>in</strong>e<br />
N-oxide gives product <strong>in</strong> good yields (eq. 1). [1] On the contrary, arylation of unsubstituted<br />
pyrid<strong>in</strong>e N-oxides is highly dependent on the nature of aryl halide. Reaction<br />
with 4-bromotoluene gives the product <strong>in</strong> high yields (eq. 2), [2] whereas arylation<br />
with 2-bromopyrid<strong>in</strong>e is limited and gives bipyrid<strong>in</strong>e N-oxide <strong>in</strong> low yields (eq. 3).<br />
Initial k<strong>in</strong>etic measurements <strong>in</strong>dicate that the rate-limit<strong>in</strong>g step for pyrid<strong>in</strong>e N-oxides<br />
with electron-withdraw<strong>in</strong>g groups is the C-H-activation, regardless of aryl halide.<br />
Prelim<strong>in</strong>ary data of the coupl<strong>in</strong>g of electron-rich pyrid<strong>in</strong>e N-oxides with bromobenzene<br />
displays a l<strong>in</strong>ear consumption of aryl halide, whereas decay of bromopyrid<strong>in</strong>e does<br />
not show the same l<strong>in</strong>earity. However, k<strong>in</strong>etic measurements of bromopyrid<strong>in</strong>e are<br />
h<strong>in</strong>dered due to a decomposition pathway where nucleophilic attack of pyrid<strong>in</strong>e Noxide<br />
on bromopyrid<strong>in</strong>e forms the N-(2-pyridyl)-2-pyridone product.<br />
Here<strong>in</strong>, we present k<strong>in</strong>etic measurements of the direct arylation of electron-deficient<br />
and electron-rich substrates. Further mechanistic <strong>in</strong>vestigations with different electrophiles<br />
will be performed to elucidate the <strong>in</strong>fluence of aryl halide <strong>in</strong> the coupl<strong>in</strong>g<br />
reaction.<br />
[1] S. Duric, C. C. Tzschucke, Org. Lett. 2011, 13, 2310.<br />
[2] L. C. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem. Soc. 2005, 127, 18020.<br />
Poster 080 Thursday 17:40 - 20:10 137
Catalyst degradation <strong>in</strong> direct methanol fuel cells<br />
Alexander Schökel ∗ , Claudia Brieger † , Christ<strong>in</strong>a Roth †<br />
∗ Materials Science – TU Darmstadt – Petersenstr. 23 – Darmstadt – GER<br />
† Institute of Chemistry and Biochemistry – FU Berl<strong>in</strong> – Takustr. 3 – Berl<strong>in</strong> – GER<br />
schoekel@energy.tu-darmstadt.de<br />
Introduction<br />
One of the major degradation mechanisms <strong>in</strong> direct methanol fuel cells utiliz<strong>in</strong>g a<br />
carbon-supported plat<strong>in</strong>um-ruthenium alloy catalyst (PtRu/C) (see [1] ) is the dissolution<br />
of ruthenium from the anode catalyst and consecutive migration and deposition<br />
of Ru species onto the cathode catalyst and other parts of the fuel cell. While there<br />
are various reports about Ru dissolution from unsupported (e.g. [2] ) and supported<br />
catalysts (e.g. [3] ), none of these focusses on elucidat<strong>in</strong>g the mechanisms <strong>in</strong>volved on<br />
an early timescale of operation (0 − 100 h).<br />
Experimental<br />
Two different techniques (wet spray<strong>in</strong>g and hot press<strong>in</strong>g) for preparation of the<br />
membrane-electrode assemblies (MEA) were chosen to study the <strong>in</strong>fluence of the electrode<br />
preparation process. MEAs from both preparation routes were subjected to<br />
specific operation conditions <strong>in</strong> a methanol fuel cell. This way, a set of samples with<br />
different histories (i.e. cell potential, runtime, fuel) was created and analyzed us<strong>in</strong>g<br />
different techniques. While the particle size was determ<strong>in</strong>ed by X-ray diffraction<br />
(XRD), the Ru content was measured by quantitative synchrotron X-ray fluorescence<br />
spectroscopy (synXRF) and cyclic voltammetry (CV). X-ray absorption spectroscopy<br />
(XAS) was used as a f<strong>in</strong>gerpr<strong>in</strong>t technique to identify the chemical nature of the<br />
ruthenium by comparison of the near edge features. The most important drawback is<br />
the low concentration of Ru species, which is high enough to severly impact the performance,<br />
but almost too low to be detected by standard characterization techniques.<br />
Results<br />
It is observed that already dur<strong>in</strong>g preparation of the MEA a crossover of ruthenium<br />
from the anode to the cathode occurs. As there is no cell potential <strong>in</strong>volved, this has<br />
to be attributed to soluble Ru species permeat<strong>in</strong>g through the membrane. A process<br />
that most def<strong>in</strong>itely cont<strong>in</strong>ues dur<strong>in</strong>g further operation of the fuel cell.<br />
It was possible to obta<strong>in</strong> XAS spectra of catalyst samples conta<strong>in</strong><strong>in</strong>g ruthenium <strong>in</strong><br />
the 10 - 100 ppm range. The quality of the cathode samples’ spectra is good enough<br />
to compare the absorption edge shape to known ruthenium references and identify<br />
the ruthenium’s oxidation state.<br />
Tak<strong>in</strong>g <strong>in</strong>to account the different histories of the samples, we see the expected correlation<br />
between runtime and amount of Ru migration (i.e. longer runtime means more<br />
Ru be<strong>in</strong>g transferred). The correlation between cell potential and Ru migration on<br />
the other hand is not that obvious and will be discussed <strong>in</strong> further detail.<br />
Acknowledgements<br />
The authors gratefully acknowledge the f<strong>in</strong>ancial support from the Federal M<strong>in</strong>istry<br />
of Economics and Technology, Germany (Grant no. 0327853-C).<br />
[1] E. J. Antol<strong>in</strong>i, Solid State Electrochem. 2011, 15, 455.<br />
[2] P. Piela, C. Eickes, E. Brosha, F. Garzon, P. J. Zelenay Electrochem. Soc. 2004, 151, A2053.<br />
[3] FZ Juelich, IEF-3 Report 2007<br />
138 Thursday 17:40 - 20:10 Poster 081
Sulfoxim<strong>in</strong>es as Ligands <strong>in</strong> Copper-Catalysed Asymmetric<br />
Friedel-Crafts Reactions<br />
Anne-Dorothee Ste<strong>in</strong>kamp, Marcus Fr<strong>in</strong>gs, Carsten Bolm<br />
Institut für Organische Chemie – RWTH Aachen University – Landoltweg 1 –<br />
52074 Aachen – GER<br />
Anne.Dorothee.Ste<strong>in</strong>kamp@rwth-aachen.de<br />
Indole-conta<strong>in</strong><strong>in</strong>g compounds are ubiquitous, and many of them exhibit <strong>in</strong>terest<strong>in</strong>g<br />
biological activity. One strategy commonly employed to further functionalise <strong>in</strong>doles is<br />
a Friedel-Crafts reaction, one of the most important methods to form bonds between<br />
two carbon atoms. S<strong>in</strong>ce Jørgensen published the metal-catalysed enantioselective<br />
alkylation of <strong>in</strong>doles <strong>in</strong> 2001, [1] additional research projects have been accomplished<br />
<strong>in</strong> this field. [2]<br />
Sulfoxim<strong>in</strong>es have been verified as powerful ligands <strong>in</strong> asymmetric metal catalysis.<br />
C2-symmetric bissulfoxim<strong>in</strong>es, for example, have been sucessfully employed <strong>in</strong> allylic<br />
alkylations [3] and (hetero)-Diels-Alder reactions. [4]<br />
Here, we present our prelim<strong>in</strong>ary results of an asymmetric Friedel-Crafts reaction between<br />
<strong>in</strong>dole (1) and diethyl-2-benzylidenemalonate (2) catalysed by a chiral sulfoxim<strong>in</strong>ecopper-complex<br />
to achieve the desired product 3 <strong>in</strong> high enantioselectivity.<br />
[1] a) W. Zhuang, T. Hansen, K. A. Jørgensen, Chem. Commun. 2001, 347-348; b) K. B. Jensen,<br />
J. Thorhauge, R. G. Hazell, K. A. Jørgensen, Angew. Chem. 2001, 113, 164-167; Angew. Chem.<br />
Int. Ed. 2001, 40, 160-163.<br />
[2] For selected examples, see: a) J. Zhou, Y. Tang, J. Am. Chem. Soc. 2002, 124, 9030-9031;<br />
b) G. Huang, H. Sun, X. Qiu, Y. Shen, J. Jiang, L. Wang, J. Org. Chem. 2011, 696, 2949-2957;<br />
c) H. J. Lee, D. Y. Kim, Synlett 2012, 23, 1629-1632.<br />
[3] C. Bolm, O. Simić, M. Mart<strong>in</strong>, Synlett 2001, 1878-1880.<br />
[4] a) C. Bolm, O. Simić, J. Am. Chem. Soc. 2001, 123, 3830-3831; b) C. Bolm, M. Mart<strong>in</strong>, O.<br />
Simić, M. Verrucci, Org. Lett. 2003, 5, 427-429.<br />
Poster 082 Thursday 17:40 - 20:10 139
A simple model of a copolymer cha<strong>in</strong>: the <strong>in</strong>fluence of the<br />
conf<strong>in</strong>ement on the structure<br />
Tomasz Piskorz , Andrzej Sikorski<br />
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
tomasz.k.piskorz@gmail.com<br />
A coarse-gra<strong>in</strong>ed model of polymer cha<strong>in</strong>s on a three-dimensional lattice was built.<br />
The cha<strong>in</strong>s were represented by sequences if beads a [310] hybrid lattice. The l<strong>in</strong>ear<br />
and star-branched cha<strong>in</strong>s were under consideration. The Monte Carlo simulations<br />
employ<strong>in</strong>g the algorithm with micromodifications of cha<strong>in</strong>’s conformation was performed.<br />
The size, structure and order<strong>in</strong>g <strong>in</strong> model macromolecules were <strong>in</strong>vestigated.<br />
[1] I. Carmes<strong>in</strong>, K. Kremer, Macromolecules 1988, 21 (9), 2819-2823<br />
140 Thursday 17:40 - 20:10 Poster 083
Stereoselective Intramolecular Cyclopropanation through<br />
Catalytic Olef<strong>in</strong> Activation<br />
Sebastian Klimczyk ∗ , Xueliang Huang ∗ , Luis F. Veiros † , Nuno Maulide ∗<br />
∗ Max-Planck-Institut für Kohlenforschung – Kaiser-Wilhelm-Platz 1 –<br />
45470 Mülheim an der Ruhr – GER<br />
† Departamento de Engenharia Química – Universidade Técnica de Lisboa –<br />
Av. Rovisco Pais – 1049-001 Lisboa – POR<br />
klimczyk@mpi-muelheim.mpg.de<br />
The direct cyclopropanation of olef<strong>in</strong>s is an important and valuable transformation<br />
<strong>in</strong> organic synthesis from a laboratory scale all the way to <strong>in</strong>dustrial production, as<br />
cyclopropanes are common structural features of both naturally occur<strong>in</strong>g and nonnatural<br />
bioactive substances. [1] Olef<strong>in</strong> cyclopropanation is dom<strong>in</strong>ated by the powerful<br />
chemistry of diazo compounds, which can be decomposed by specific transition<br />
metals (commonly rhodium, ruthenium, palladium, iridium or copper) to produce<br />
metallocarbene complexes <strong>in</strong> situ. [2] These metallocarbenes are mild and selective<br />
cyclopropanat<strong>in</strong>g agents and perform best with electron-rich or -neutral olef<strong>in</strong>ic partners.<br />
Dur<strong>in</strong>g our recent studies on the gold-catalysed rearrangement of sulfonium ylides<br />
bear<strong>in</strong>g an allyloxycarbonyl moiety, [3] we serendipitously discovered a direct <strong>in</strong>tramolecular<br />
cyclopropanation of sulfonium ylides onto olef<strong>in</strong>s. In this presentation, we shall<br />
report on the development of a gold-catalysed <strong>in</strong>tramolecular cyclopropanation of<br />
electron-neutral alkenes by stabilised sulfonium ylides, mechanistic and computational<br />
<strong>in</strong>vestigations <strong>in</strong>to this process and prelim<strong>in</strong>ary results on an asymmetric version. [4]<br />
Gold-catalysed <strong>in</strong>tramolecular cyclopropanation of sulfonium ylides.<br />
[1]<br />
a) Brackmann, F.; de Meijere, A. Chem. Rev. 2007, 107, 4493; (b) Brackmann, F.; de Meijere,<br />
A. Chem. Rev. 2007, 107, 4538.<br />
[2]<br />
a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis<br />
with Diazo compounds; Wiley Interscience: New York, 1998; b) Lebel, H.; Marcoux, J.-F.;<br />
Mol<strong>in</strong>aro, C.; Charette, A. B. Chem. Rev. 2003, 103, 977; c) Reissig, H.-U.; Zimmer, R. Chem.<br />
Rev. 2003, 103, 1151; d) Maas, G. Chem. Soc. Rev. 2004, 33, 183.<br />
[3]<br />
Huang, X.; Peng, B.; Luparia, M.; Gomes, L. F. R.; Veiros, L. F.; Maulide, N. Angew. Chem.<br />
Int. Ed. 2012, 51, 8886.<br />
[4]<br />
Huang X.; Klimczyk, S.; Veiros, L. S.; Maulide, N. Chem. Sci. <strong>2013</strong> doi: 10.1039/C2SC21914J.<br />
Poster 084 Thursday 17:40 - 20:10 141
Influence of calc<strong>in</strong>ation conditions on supported Cu particles<br />
as a catalyst for methanol steam reform<strong>in</strong>g<br />
Lena Schmidt, Gregor Koch, Thorsten Ressler<br />
Institut für Anorganische und Analytische Chemie – Technische Universität Berl<strong>in</strong> –<br />
Straße des 17. Juni 135 – 10623 Berl<strong>in</strong> – GER<br />
lena.schmidt@mailbox.tu-berl<strong>in</strong>.de<br />
Hydrogen is frequently discussed as energy carrier of the future. Complications <strong>in</strong><br />
handl<strong>in</strong>g due to its gaseous aggregate state can be avoided by chemically b<strong>in</strong>d<strong>in</strong>g hydrogen,<br />
e.g. as methanol. Methanol synthesis and its reverse reaction (i.e. methanol<br />
steam reform<strong>in</strong>g to release hydrogen) are <strong>in</strong>dustrially catalyzed by a Cu/ZnO/Al2<br />
O3 catalyst. [1,2] For a more efficient use of valuable resources catalysts need to be<br />
improved <strong>in</strong> both activity and selectivity. reliable structure-activity relations are required.<br />
In order to exclude contributions from other components, here Cu particles<br />
<strong>in</strong> the size range of few nm and stabilized on a nanostructured silica support were<br />
<strong>in</strong>vestigated as model systems.<br />
Four samples of Cu particles on a SBA-15 support were prepared by <strong>in</strong>cipient wetness<br />
with Cu-citrate solutions with different concentrations. Afterwards samples of<br />
vary<strong>in</strong>g layer thickness and concentration were calc<strong>in</strong>ed under controlled conditions.<br />
Reducibility of the prepared CuO particles and activity of the result<strong>in</strong>g Cu phase<br />
were studied by temperature programmed reduction (TPR) and catalytic measurements<br />
(Fig. 1), respectively. It was shown, that activity <strong>in</strong> methanol steam reform<strong>in</strong>g<br />
and structure of the active Cu phase were <strong>in</strong>fluenced by the calc<strong>in</strong>ation conditions.<br />
Correspond<strong>in</strong>g structure activity correlations are presented.<br />
Fig. 1: Comparison of the relative H2 ion currents under methanol steam reform<strong>in</strong>g<br />
conditions of Cu particles supported on SBA-15 calc<strong>in</strong>ed under different conditions and<br />
with vary<strong>in</strong>g Cu load<strong>in</strong>gs.<br />
[1] S. Sá, H. Silva, Applied Catalysis B 2010, 99, 43.<br />
[2] M. M. Günter, T. Ressler, Catalysis Letters 2001, 71, 37.<br />
142 Thursday 17:40 - 20:10 Poster 085
Cont<strong>in</strong>uous-flow photoreactor packed with magnesium(II)<br />
2,3-bis(1-adamantylsulfanyl)phthalocyan<strong>in</strong>e immobilized on<br />
silica<br />
Michal Kryjewski ∗ , Michal Nowak † , Tomasz Gosl<strong>in</strong>ski † , Jadwiga Mielcarek ∗<br />
∗ Department of Inorganic and Analytical Chemistry –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
† Department of Chemical Technology of Drugs –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
mkryjewski@wp.eu<br />
S<strong>in</strong>glet oxygen ( 1 O2) constitutes a versatile reagent <strong>in</strong> many synthetic approaches,<br />
able to oxidize substrates that are unaffected by oxygen <strong>in</strong> its normal, triplet state. Organic<br />
chemists have found utility of 1 O2 as synthetic reagent, characterized its versatility,<br />
availability, low costs, and negligible environmental impact. 1 O2 reacts rapidly<br />
with unsaturated carbon-carbon bonds <strong>in</strong> ene reactions, [4+2] and [2+2] cycloadditions,<br />
heteroatom oxidations. [1] Phthalocyan<strong>in</strong>es (Pcs) are synthetic aza-analogues of<br />
porphyr<strong>in</strong>s, which upon illum<strong>in</strong>ation with light of an appropriate wavelength generate<br />
1 O2.<br />
We synthesized magnesium(II) 2,3-bis(1-adamantylsulfanyl)phthalocyan<strong>in</strong>e and reported<br />
its photochemical properties. [2] This new macrocycle exhibited high s<strong>in</strong>glet<br />
oxygen quantum yield value Φ∆ = 0.49 <strong>in</strong> both dimethylformamide and dimethylsulfoxide.<br />
Therefore, it was chosen as an active agent <strong>in</strong> design of cont<strong>in</strong>uous-flow<br />
photoreactor for s<strong>in</strong>glet oxygen generation. The phthalocyan<strong>in</strong>e was deposited on<br />
silica gel and next used to pack glass chromatography column. LED array emitt<strong>in</strong>g<br />
light of wavelength λ = 690 nm, correspond<strong>in</strong>g to the absorbance maximum of the<br />
compound, was used.<br />
1,3-Diphenylisobenzfuran (DPBF) is a chemical quencher of s<strong>in</strong>glet oxygen which was<br />
used <strong>in</strong> a hexane solution pass<strong>in</strong>g via column dur<strong>in</strong>g the measurements. Illum<strong>in</strong>ation<br />
of silica gel modified with Pc resulted immediately <strong>in</strong> decrease of DPBF concentration<br />
<strong>in</strong> eluate, while silica gel without immobilized Pc showed no 1 O2 production.<br />
Fig. 1 Scheme of the photoreactor, change of absorbance at λ = 411 nm dur<strong>in</strong>g constant<br />
flow of DPBF solution <strong>in</strong> dark and light conditions.<br />
[1] M. C. DeRosa et al., Coord. Chem. Rev. 2002, 233-234, 351-371.<br />
[2] M. Kryjewski et al., Inorg Chem Commun <strong>2013</strong>, 27, 56-59.<br />
This study was supported by grant from the Polish M<strong>in</strong>istry of Science and Higher Education –<br />
National Science Centre (N N404 069440).<br />
Poster 086 Thursday 17:40 - 20:10 143
Stable ruthenium <strong>in</strong>denylidene complexes with a sterically<br />
reduced NHC ligand<br />
Adam Ziel<strong>in</strong>ski, Grzegorz Szczepaniak, Karol Grela<br />
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
aziel<strong>in</strong>ski2407@gmail.com<br />
Over the past decade olef<strong>in</strong> metathesis became a powerful tool <strong>in</strong> organic synthesis. [1]<br />
New ruthenium complexes that comb<strong>in</strong>e high catalytic activity with excellent tolerance<br />
to multiplicitous functional groups have been developed. [2] Despite the fact that<br />
many modifications of olef<strong>in</strong> metathesis catalysts have been <strong>in</strong>troduced dur<strong>in</strong>g the<br />
past years, obta<strong>in</strong><strong>in</strong>g a new complex that allows good yields with demand<strong>in</strong>g partners<br />
is still a challenge.<br />
S<strong>in</strong>ce the <strong>in</strong>troduction of the ‘first generation’ Ru-based catalysts the basic structure<br />
has been modified lead<strong>in</strong>g to different catalyst families [3] , <strong>in</strong>clud<strong>in</strong>g the most prom<strong>in</strong>ent<br />
mixed N-heterocyclic carb<strong>in</strong>e (NHC)–phosph<strong>in</strong>e metathesis catalysts, described<br />
as ‘second generation’. The replacement of one labile phosph<strong>in</strong>e ligand with a nonlabile<br />
NHC led to an <strong>in</strong>creased longevity of the active species and therefore better<br />
catalyst performance.<br />
A new <strong>in</strong>denylidene complex conta<strong>in</strong><strong>in</strong>g o-tolyl NHC ligand has been synthetized. [4]<br />
The catalytic activity of the complex was <strong>in</strong>vestigated <strong>in</strong> model reactions. Notably,<br />
for the RCM of sterically demand<strong>in</strong>g olef<strong>in</strong>s it is one of the most efficient catalysts<br />
reported so far.<br />
Fig. 1. New o-tolyl Ru catalyst<br />
[1]<br />
T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18-29.<br />
[2]<br />
K. Grela, S. Harutyunyan, A. Michrowska, Angew. Chem., Int. Ed. 2002, 41, 4038.<br />
[3]<br />
G. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 2010, 110, 1746.<br />
[4]<br />
C. Torborg, G. Szczepaniak, A. Zieliński, M. Malińska, K. Woźniak, K. Grela, “Stable Ruthenium<br />
Indenylidene Complexes with a Sterically Reduced NHC Ligand” Chem. Commun. <strong>2013</strong>,<br />
<strong>in</strong> press<br />
144 Thursday 17:40 - 20:10 Poster 087
New Susta<strong>in</strong>able Decarboxylative Allylations of Benzoic acid<br />
Derivatives<br />
Kai Pfister, Lukas J. Gooßen<br />
FB Organische Chemie – Technische Universität Kaiserslautern –<br />
Erw<strong>in</strong>-Schröd<strong>in</strong>ger-Straße Build<strong>in</strong>g 54 – Kaiserslautern – GER<br />
kpfister@chemie.uni-kl.de<br />
With<strong>in</strong> recent years, the field of decarboxylative allylation reactions has undergone<br />
tremendous development. [1] However, most of the known catalytic protocols are versions<br />
of the Carroll rearrangement and extend only to allyl esters of carboxylic acids<br />
that – upon extrusion of CO2 – form stabilized carbanions. [1] Even fewer methods<br />
for the decarboxylative allylation of benzoic acids have been developed and they still<br />
suffer from limited substrate scope, for example the restriction to electron-rich benzoic<br />
acids. [2] Furthermore the requirement of an excess of silver(I) salts and toxic allyl<br />
halides makes this approach less attractive.<br />
We have recently overcome these drawbacks by develop<strong>in</strong>g a waste free method for the<br />
decarboxylative allylation of benzoic acid derivatives without the need of stoichiometric<br />
amount of additives. The developed method gives the correspond<strong>in</strong>g allylbenzenes<br />
<strong>in</strong> good to excellent yields, proceeds at moderate temperatures and produces only CO2<br />
as byproduct.<br />
The new catalyst also allows the conversion of benzoic esters that are generated <strong>in</strong><br />
situ. For example, benzoic acids can be allylated with diallyl carbonate and directly<br />
be converted to the correspond<strong>in</strong>g allylarenes. In this process, CO2 and allyl alcohol<br />
rema<strong>in</strong> the only side products.<br />
Decarboxylative Allylations<br />
[1] J. D. Weaver, A. Recio, A. J. Grenn<strong>in</strong>g, J. A. Tunge, Chem. Rev. 2011, 111, 1846–1913.<br />
[2] J. Wang, Z. Cui, Y. Zhang, H. Li, L.-M. Wu, Z. Liu, Org. Biomol. Chem. 2011, 9, 663–666.<br />
Poster 088 Thursday 17:40 - 20:10 145
Development new convenient palladium-catalyzed<br />
trifluorov<strong>in</strong>ylations of arene halides<br />
S<strong>in</strong>a P. Zucker, Sasa Duric, Bernd M. Schmidt, N<strong>in</strong>a M. N<strong>in</strong>nemann, Dieter Lentz,<br />
C. Christoph Tzschucke<br />
Institut für Chemie und Biochemie – Freie Universität Berl<strong>in</strong> – Takustraße 3 –<br />
14195 Berl<strong>in</strong> – GER<br />
honey@zedat.fu-berl<strong>in</strong>.de<br />
Trifluorostyrenes are <strong>in</strong>terest<strong>in</strong>g and important compounds <strong>in</strong> material sciences and<br />
drug development, yet, only few convenient reactions for their preparation have<br />
been reported. [1] Most of them require the formation of highly reactive and unstable,<br />
organometallic <strong>in</strong>termediates or are multistep sequences. Recently we developed<br />
the synthesis of trifluorostyrenes by coupl<strong>in</strong>g of aryl bromides with stable<br />
trimethoxy(trifluorov<strong>in</strong>yl)borate 1 derived from the bulk compound HFC-134a. [2] To<br />
further simplify the procedure and to broaden the substrate scope, we are develop<strong>in</strong>g a<br />
one-step/one-pot procedure for a convenient palladium-catalyzed coupl<strong>in</strong>g reaction of<br />
aryl halides with <strong>in</strong> situ generated trifluorov<strong>in</strong>ylanion synthons. This method requires<br />
highly active catalysts, which operate at very low temperatures as well as a better<br />
understand<strong>in</strong>g of the elemental steps <strong>in</strong>volved. The synthesis of differnt precatalysts<br />
and prelim<strong>in</strong>ary results of coupl<strong>in</strong>g reactions will be discussed.<br />
[1] R. Anilkumar, D. J. Burton, Tetrahedron Letters 2002, 43, 2731-2733; A. Raghavanpillai, D.<br />
J. Burton, J. Org. Chem. 2004, 69, 7083-7091; M. Ohashi, T. Kambara, T. Hatanaka, H. Saijo,<br />
R. Doi, S. Ogoshi, J. Am. Chem. Soc. 2011, 133, 3256-3259; M. Ohashi, H. Saijo, M. Shibata,<br />
S. Ogoshi, Eur. J. Org. Chem. 2012, 3454-5457; Eur. J. Org. Chem. <strong>2013</strong>, 3, 443-447; T.<br />
Yamamoto, T. Yamakawa, Org. Lett. 2012, 14, 3454-3457; C. Xu, S. Chen, L. Lu, Q. Shen, J.<br />
Org. Chem. 2012, 77, 10314-10320.<br />
[2] S. Duric, B. M. Schmidt, N. M. N<strong>in</strong>nemann, D. Lentz, C. C. Tzschucke, Chem. Eur. J. 2012,<br />
18, 437-441.<br />
146 Thursday 17:40 - 20:10 Poster 089
Search<strong>in</strong>g for the Transmetalation Intermediate <strong>in</strong><br />
Copper-Catalyzed 1,4-Addition Reactions via NMR<br />
Spectroscopy<br />
Felicitas von Rekowski, Katr<strong>in</strong> Schober, Ruth M. Gschw<strong>in</strong>d<br />
Department of Organic Chemistry – University of Regensburg – Universitätsstr. 31 –<br />
Regensburg – GER<br />
Felicitas.Von-Rekowski@chemie.uni-regensburg.de<br />
For the formation of C-C bonds, with a new chiral center, one of the most powerful<br />
methods is the enantioselective catalytic 1,4-addition reaction to α,β-unsaturated<br />
systems. With a catalytic system consist<strong>in</strong>g of chiral phosphoramidite ligands and<br />
copper(I) salts it is possible to reach high chemo- and regioselectivity and quantitative<br />
yields. A further advantage are the relatively low costs compared to other<br />
applied catalytic systems. [1−4] In order to elucidate the structure of the formed Cu(I)<br />
complexes as well as their temperature dependent geometry we comb<strong>in</strong>e experimental<br />
as well as simulated 31 P NMR spectra and 1 H diffusion experiments of various<br />
mixtures. For this purpose the Cu(I) source, the ligand to salt ratio and the solvent<br />
were varied. With these data we were able to identify a b<strong>in</strong>uclear precatalytic complex<br />
structure with a mixed trigonal/tetrahedral coord<strong>in</strong>ation on copper. [5−8] This<br />
complex structure provides a free coord<strong>in</strong>ation site for the transmetalation reagent.<br />
The transmetalation of the organic moiety from the organometallic reagent to the<br />
precatalytic copper complex represents the first step <strong>in</strong> the proposed mechanism.<br />
However, up to now no experimental proof for such a transmetalated species was<br />
found. Thus we elucidate several systems comb<strong>in</strong><strong>in</strong>g the precatalytic copper complex<br />
with diaryl/dialky z<strong>in</strong>c or trialkyl alum<strong>in</strong>um reagents by various NMR spectroscopic<br />
techniques. Recently we were able to detect for the first time a transmetalation <strong>in</strong>termediate<br />
by 1 H 31 P HMBC experiments, but the structure of the transmetalated<br />
species is until now not completely elucidated.<br />
Schematic presentation of the 1,4-addition of a trialkylalum<strong>in</strong>um reagent with the<br />
<strong>in</strong>vestigated precatalytic copper complex.<br />
[1]<br />
A. Alexakis et al., Chem. Rev. 2008, 108, 2796.<br />
[2]<br />
T. Jerphagnon et al., Chem. Soc. Rev. 2009, 38, 1039.<br />
[3]<br />
N. Krause et al., Synthesis 2001, 2, 171.<br />
[4]<br />
J. F. Teichert et al., Angew. Chem. Int. Ed. 2010, 41, 2486.<br />
[5]<br />
H. Zhang et al., Angew. Chem. Int. Ed. 2006, 45, 6391.<br />
[6]<br />
H. Zhang et al., Chem. Eur. J. 2007, 13, 6691.<br />
[7]<br />
K. Schober et al., J. Am. Chem. Soc. 2008, 130, 12310.<br />
[8]<br />
K. Schober et al., Angew. Chem. Int. Ed. 2010, 49, 2794.<br />
Poster 090 Thursday 17:40 - 20:10 147
Secondary Phosp<strong>in</strong>e Oxides: A Stable Approach for Gold<br />
Catalysis<br />
Felix Schröder ∗ , Jean Philippe Goddard † , Virg<strong>in</strong>ie Mansuy † , Louis Fensterbank †<br />
∗ Chemistry Department – Technische Universität Berl<strong>in</strong> – Straße des 17. Juni 115 –<br />
Berl<strong>in</strong> – GER<br />
† Chimie Organique de Synthèse – Université Pierre et Marie Curie Paris 6 –<br />
4 Place Jussieu – Paris – FRA<br />
schroederfelix@onl<strong>in</strong>e.de<br />
The use of Secondary Phosph<strong>in</strong>e Oxide Gold(I) Complexes (SPO-Au) <strong>in</strong> enyne cycloisomerizations<br />
was exam<strong>in</strong>ed. The SPO-Au complex is affordable and easy to synthesize,<br />
and it is not as <strong>in</strong>stable under no protect<strong>in</strong>g atmospheric conditions as other<br />
transition metal-ligand complexes are. A large variety of different enynes (Scheme<br />
1) were synthesized <strong>in</strong> order to determ<strong>in</strong>e the activity and selectivity of the catalytic<br />
system. The ma<strong>in</strong> focus was put on 1,6-enynes with a tosyl or ortho-tosyl protected<br />
nitrogen l<strong>in</strong>ker <strong>in</strong> position four on the enyne with a vary<strong>in</strong>g substitution pattern at<br />
the triple and double bond. Other enynes bear<strong>in</strong>g malonic acid dimethyl ester <strong>in</strong> position<br />
four or an acetyl group <strong>in</strong> position three also gave very <strong>in</strong>terest<strong>in</strong>g results. The<br />
catalytic conversion mostly followed the general procedure given <strong>in</strong> the literature. [1,2]<br />
Three different ma<strong>in</strong> product classes could be identified. Two of them are formal<br />
metatheses products bear<strong>in</strong>g highly substituted 1,3-dienes and the third is an <strong>in</strong>terest<strong>in</strong>g<br />
class of cyclopropane derivatives (Scheme 2). The class of enynes bear<strong>in</strong>g an<br />
acetyl group showed furthermore a 1,2-migration of the acetyl which was presented<br />
earlier by Fensterbank et al. [3] The chiral background of the SPO-Au complex was<br />
also used for enantioselective cycloisomerizations of 1,6-enynes. The enantiomeric<br />
excess could be raised <strong>in</strong> the beg<strong>in</strong>n<strong>in</strong>g from 0% to 11% by chang<strong>in</strong>g the reaction<br />
conditions. It was shown that the used SPO-Au complex has the potential for substitut<strong>in</strong>g<br />
other more expensive and fragile catalytic systems and our results encourage<br />
further <strong>in</strong>vestigation.<br />
[1] L. Zhang, J Sun, S. A. Kozm<strong>in</strong>, Adv. Synth. Catal. 2006, 348, 2271-2296.<br />
[2] C. H. M. Amijs, V. López-Carrillo, M. Raducan, P. Pérez-Galán, C. Ferrer, A. M. Echevarren,<br />
J. Org. Chem. 2008, 73, 7721-7730.<br />
[3] X. Moreau, J.-P. Goddard, Matthieu Bernard, G. Lemière, J. M. López-Romero, E. Ma<strong>in</strong>etti,<br />
N. Marion, V. Mouriès, S. Thorimbert, L. Fensterbank, M. Malacria, Adv. Synth. Catal. 2008,<br />
350, 43-48.<br />
148 Thursday 17:40 - 20:10 Poster 091
Synthesis of biphenolic natural products through<br />
Suzuki-Miyaura-reaction us<strong>in</strong>g Pd/C <strong>in</strong> water<br />
Mart<strong>in</strong> Riemer ∗ , Bernd Schmidt †<br />
∗ Institut für Chemie – Universität Potsdam –<br />
Karl Liebknechtstraße 24-25 Haus 25 D1.12 – Golm – GER<br />
† Institut für Chemie – Universität Potsdam –<br />
Karl Liebknechtstraße 24-25 Haus 25 D1.16 – Golm – GER<br />
mariemer@uni-potsdam.de<br />
Biphenols and their derivatives are lead structures <strong>in</strong> many natural products, drugs<br />
(e.g. vancomyc<strong>in</strong>) and precursor of many ligands. [1] Biphenyls are phytoalex<strong>in</strong>s of<br />
Pyr<strong>in</strong>ae (apples, pears) and therefore economically attractive. [2]<br />
A good method to synthesise biaryls is the Pd-mediated SUZUKI-MIYAURA-reaction.<br />
The reaction is hampered by the phenolic structure of these phytoalex<strong>in</strong>s, because<br />
electron-rich arylhalides are less reactive. It is challeng<strong>in</strong>g to avoid the protect<strong>in</strong>g/deprotect<strong>in</strong>g<br />
steps and actually only a few examples of a direct coupl<strong>in</strong>g are<br />
known. [3]<br />
We report an efficient method for the synthesis of biphenols and the total synthesis<br />
of biphenolic phytoalex<strong>in</strong>s which features a ligandless SUZUKI-MIYAURA-reaction<br />
us<strong>in</strong>g simple Pd on charcoal (heterogenous, easy to remove) <strong>in</strong> water. [4]<br />
[1] G. Br<strong>in</strong>gmann, T. Gulder, T. A. M. Gulder, M. Breun<strong>in</strong>g, Chem. Rev. 2011, 111, 563.<br />
[2] C. Chizzali, L. Beerhues, Beilste<strong>in</strong> J. Org. Chem. 2012, 613.<br />
[3] J. S. Freundlich, H. E. Landis, Tetrahedron Lett. 2006, 47, 4275.<br />
[4] T. Hirao, H. Sakurai, J. Org. Chem. 2002, 67, 2721.<br />
Poster 092 Thursday 17:40 - 20:10 149
Synthesis and characterization of long-term s<strong>in</strong>ter<strong>in</strong>g-stable<br />
Ni catalysts for dry reform<strong>in</strong>g of CO2<br />
Kathar<strong>in</strong>a Mette ∗ , Stefanie Kühl ∗ , Robert Schlögl ∗ , Malte Behrens ∗ , Hendrik Düdder † ,<br />
Kev<strong>in</strong> Kähler † , Mart<strong>in</strong> Muhler †<br />
∗ Abteilung Anorganische Chemie – Fritz-Haber-Institut der Max-Planck-Gesellschaft –<br />
Faradayweg 4-6 – 14195 Berl<strong>in</strong> – GER<br />
† Laboratory of Industrial Chemistry – Ruhr-University Bochum – Universitätsstr. 150 –<br />
44801 Bochum – GER<br />
mette@fhi-berl<strong>in</strong>.mpg.de<br />
Fossil power generations emit large amounts of the greenhouse gas CO2. Thus, the<br />
efficient conversion of CO2 <strong>in</strong>to useful chemical <strong>in</strong>termediates is an important component<br />
for prospective resource-sav<strong>in</strong>g and susta<strong>in</strong>able energy economics.<br />
This work ma<strong>in</strong>ly focuses on the use of CO2 and methane as raw materials to obta<strong>in</strong><br />
syngas by dry reform<strong>in</strong>g (DRM: CO2 + CH4 −→ 2CO + 2H2). S<strong>in</strong>ce dry reform<strong>in</strong>g<br />
is a highly endothermic reaction, several carbon produc<strong>in</strong>g side reactions can<br />
occur lead<strong>in</strong>g to deactivation of the catalysts. [1] To suppress side reactions, high reaction<br />
temperatures are needed. For the catalyst development the ma<strong>in</strong> challenge is the<br />
preparation of a noble metal-free material, which prevents cok<strong>in</strong>g and is stable at high<br />
temperatures. Here, we show that Ni/MgAlOx catalysts derived from hydrotalcitelike<br />
(htl) precursors fulfill these requirements.<br />
Ni/MgAl2O4 catalysts have been prepared from hydrotalcite-like (htl) compounds as<br />
precursors by a constant pH co-precipitation method. The precursors and catalysts<br />
were extensively characterized <strong>in</strong> their calc<strong>in</strong>ed and reduced states as well as after<br />
DRM, us<strong>in</strong>g a variety of methods.<br />
XANES spectroscopy reveals the presence of two different Ni oxide species <strong>in</strong> the<br />
mostly amorphous calc<strong>in</strong>ed materials; NiO and NiAl2O4. The reduced catalysts exhibit<br />
a homogeneous metal distribution with high BET and specific Ni surface areas<br />
(up to 40 m 2 /gNi) and small Ni particles (∼10 nm), which are embedded <strong>in</strong> an<br />
MgAlOx matrix (Fig. 1). The ex-htl catalysts show high activities and outstand<strong>in</strong>g<br />
stabilities <strong>in</strong> DRM at 900 ◦ C over 100 hours. The specific activities are found to correlate<br />
l<strong>in</strong>early with the specific metal surface area. TEM analysis of the spent catalysts<br />
reveals a good stability of the microstructure and only m<strong>in</strong>or carbon deposition. In<br />
summary, we developed a noble metal free Ni/MgAlOx catalyst, which is stable at<br />
high temperatures even with high Ni load<strong>in</strong>gs. With these materials cok<strong>in</strong>g dur<strong>in</strong>g<br />
DRM can be suppressed to a certa<strong>in</strong> extent by an <strong>in</strong>crease of the reaction temperature<br />
allow<strong>in</strong>g stable operation over 100 hours.<br />
Fig. 1: TEM micrographs of the Ni/MgAlOx catalysts reduced at 1000 ◦ C; 50 mol%<br />
(left), 25 mol% (center) and 5 mol% Ni (right).<br />
[1] S. Wang, G. Q. (Max) Lu, Energy & Fuels 1996, 10, 896-904.<br />
150 Thursday 17:40 - 20:10 Poster 093
Postsynthesis, Characterization, and Catalytic Properties <strong>in</strong><br />
Alkene Epoxidation of Hydrothermally Stable Mesoporous<br />
Ti-SBA-15<br />
Edyta Makuch, Agnieszka Wróblewska<br />
Department of Chemical Organic Technology –<br />
Institute of Organic Chemical Technology, West Pomeranian University of Technology Szczec<strong>in</strong> –<br />
Pulaskiego 10 – Poland – POL<br />
editamakuch@wp.pl<br />
The microporous TS-1 catalyst (with the structure of MFI type) used <strong>in</strong> the process<br />
of allylic compounds epoxidation was obta<strong>in</strong>ed <strong>in</strong> 1983 by Taramasso at al. [1] A few<br />
years later, <strong>in</strong> 1990, the microporous titanium-silicalite catalyst TS-2 with the MEL<br />
structure was obta<strong>in</strong>ed by Reddy at al. [2] Despite of the differences <strong>in</strong> the structures<br />
of TS-1 and TS-2, these catalysts have close and small pore size (0.5 nm) and a similar<br />
catalytic activity. Because of small pore size these materials can be used only for the<br />
epoxidation of unsaturated compounds with the small molecules.<br />
In 1992 Camblor at al. [3] obta<strong>in</strong>ed the titanium silicalite catalyst Ti-Beta (with pore<br />
size of 0.8 nm) hav<strong>in</strong>g the structure of BEA. Ti-Beta due to the <strong>in</strong>corporation of<br />
alum<strong>in</strong>um <strong>in</strong> the crystal lattice, is considered as a catalyst show<strong>in</strong>g oxidiz<strong>in</strong>g and<br />
acidic properties. This properties of the Ti-Beta catalyst cause that epoxides formed<br />
dun<strong>in</strong>g the epoxidation of allylic compounds can easily undergo hydration. The research<br />
published by Mobil R & D Corporation <strong>in</strong> 1992 confirmed the discovery of<br />
mesoporous materials of M41S type. These materials are characterized by narrow<br />
distribution of pores (from 2 to 30 nm) and large specific surface (from 800 to 1600<br />
m2/g). [4] The literature data show that all titanium silicalite catalysts (TS-1, TS-2,<br />
Ti-Beta, Ti-MCM-41, Ti-MCM-48) undergo deactivation <strong>in</strong> the process of allyl alcohol<br />
epoxidation. One of the reasons is the leach<strong>in</strong>g of titanium from the structure of<br />
the catalyst. In the case of mesoporous titanium silicalite catalysts (Ti-MCM-41, Ti-<br />
MCM-48) deactivation is also connected with the <strong>in</strong>stability of the structure <strong>in</strong> water<br />
solution. Much greater thermal stability (compared to the other titanium silicalite<br />
catalysts) and high arrangement of the structure has the mesoporous Ti-SBA-15 catalyst.<br />
This material, which belong to newest titanium silicalite catalysts, is obta<strong>in</strong>ed<br />
with the use of a biodegradable polymer Pluronic P123 as a structure-direct<strong>in</strong>g agent.<br />
[1] M. Taramasso, G. Perygo, B. Notari, “Preparation of porous crystall<strong>in</strong>e synthetic material<br />
comprised of silicon and titanium oxides”, Pat. USA 4 410 501, 1983.<br />
[2] J. S. Reddy, R. Kumar, P. Ratnasam, “Titanium silicalite-2: synthesis, characterization and<br />
catalytic properties”, Appl. Catal. A: General 1990, 58, L1-L4.<br />
[3] M. A. Camblor, A. Corma, J. Perez-Pariente, “Zeolites, A new highly efficient method for the<br />
synthesis of Ti-Beta zeolite oxidation catalyst”, Appl. Catal. A: General 1995, 133, L185-L189.<br />
[4] G. Oye, J. Stocker, “Sythesis, characterization and potential applications of new marerials <strong>in</strong><br />
the mesoporous range”, Adv. Colloid Interfac. 2001, 89-90, 439-466.<br />
Poster 094 Thursday 17:40 - 20:10 151
Synthesis and immobilisation of Pd-bipyrid<strong>in</strong>e catalysts for<br />
aerobic alcohol oxidation<br />
Anja Sokolowski, C. Christoph Tzschucke<br />
Chemie und Biochemie – Freie Universität Berl<strong>in</strong> – Takustraße 3 – Berl<strong>in</strong> – GER<br />
anjasoko@zedat.fu-berl<strong>in</strong>.de<br />
Palladium-catalysed oxidations typically require a stoichiometric secondary oxidant<br />
such as benzoqu<strong>in</strong>one or CuCl2 . This <strong>in</strong>creases the complexity of the reaction and<br />
complicates product isolation and reduces the atom efficiency. [1] A major <strong>in</strong>terest <strong>in</strong><br />
palladium-catalysed reactions is the stabilisation of the catalyst and the reoxidation of<br />
the Pd(0) <strong>in</strong>termediate to prevent Pd-black formation. To address these limitations,<br />
recent developments utilise coord<strong>in</strong>at<strong>in</strong>g solvents or ligands to stabilise the Pd(0)<br />
<strong>in</strong>termediates and molecular oxygen as stochiometric oxidant. [2,3]<br />
Our work <strong>in</strong>vestigates the viability of immobilisation of Pd bipyrid<strong>in</strong>e-complexes on<br />
gold electrode. This methodology could both provide fast reoxidation of Pd(0) on the<br />
electrode surface and prevent Pd black formation. A variety of substituted bipyrid<strong>in</strong>es<br />
were synthesized and attached to a sulfur functionalised l<strong>in</strong>ker that can be immobilised<br />
on gold surfaces. The synthesis of the functionalized l<strong>in</strong>kers and characterisation of<br />
the immobilized complexes will be presented.<br />
[1] B. A. Ste<strong>in</strong>hoff, I. A. Guzei, S. S. Stahl, J. Am. Chem. Soc. 2004, 126, 11268-11278.<br />
[2] D. M. Pearson, N. R. Conley, R. M. Waymouth, Organometallics 2011, 30, 1445-1453.<br />
[3] G.-J. ten Br<strong>in</strong>k, I. W. C. E. Arends, M. Hoogenraad, G. Verspui, R. A. Sheldon, Adv. Synth.<br />
Catal. 2003, 345, 1341-1352.<br />
152 Thursday 17:40 - 20:10 Poster 095
Ultrasound-Assisted Rapid Synthesis of Ferrocene<br />
Conta<strong>in</strong><strong>in</strong>g Beta-Am<strong>in</strong>o Ketone with Direct-Type Catalytic<br />
Mannich Reaction ans Investigat<strong>in</strong>g its Physical Properties<br />
Bahadir Kesk<strong>in</strong> ∗ , S. Arda Ozturkcan ∗ , Ahmet Alt<strong>in</strong>dal ‡<br />
∗ Chemistry – Yildiz Technical University – 34210 – Istanbul – TUR<br />
‡ Physics – Yildiz Technical University – 34210 – Istanbul – TUR<br />
bahadirkesk<strong>in</strong>@gmail.com<br />
The scientific endeavor on the <strong>in</strong>vestigation of ferrocene conta<strong>in</strong><strong>in</strong>g molecules keeps<br />
<strong>in</strong>creas<strong>in</strong>g although 60 years has passed over its discovery by Pauson and Kealy. [1] An<br />
important carbon–carbon bond form<strong>in</strong>g reaction <strong>in</strong> organic synthesis for the preparation<br />
of beta-am<strong>in</strong>o carbonyl compounds [2] is Mannich reaction. Water is one of<br />
the eco-friendly, ease of access, <strong>in</strong>expensive solvent and can certa<strong>in</strong>ly be considered<br />
as the cleanest solvent available for chemists. [3] Sonochemistry as a green <strong>in</strong>novation<br />
powerful technique can be extremely efficient and is applicable to a wide variety of<br />
practical syntheses has <strong>in</strong>creas<strong>in</strong>g <strong>in</strong>terest <strong>in</strong> accelerate organic reactions. [4] The concept<br />
of green <strong>in</strong>novations <strong>in</strong> synthetic chemistry have emerged as a major solution<br />
for the development of cleaner and more benign chemical processes. [5] As part of<br />
this green concept, “water” and “ultrasound” have become so popular and received<br />
substantial <strong>in</strong>terest.<br />
A green <strong>in</strong>novative, quite rapid, powerful novel and efficient method was developed<br />
to synthesize various beta-am<strong>in</strong>oketone derivative (4) from cyclohexanone (3), substituted<br />
4-am<strong>in</strong>obenzyl cyanide (2) and, ferrocenecarboxaldehyde (1) via ultrasoundassisted<br />
direct-type catalytic Mannich reaction us<strong>in</strong>g bismuth (III) triflate <strong>in</strong> water.<br />
Good yields of the desired product (4) were obta<strong>in</strong>ed from available substrates, such<br />
as beta-am<strong>in</strong>oketones, at room temperature <strong>in</strong> 2 hours by ultrasound. The prom<strong>in</strong>ent<br />
advantages of the proposed method are simple conditions, easy work-up, low toxicity,<br />
shorter reaction time, anti-selectivity and higher yields over to traditional methods.<br />
The product clarified by spectroscopic methods (FTIR, 1 H NMR, UV-Vis, MS) after<br />
the purification processes and <strong>in</strong>vestigated its physical properties.<br />
Scheme 1. Synthesis of beta-am<strong>in</strong>oketone us<strong>in</strong>g Mannich reaction.<br />
[1]<br />
D. A. Boyd, R.J. Crutchley, P.E. Fanwick, T. Ren, Inorg. Chem. 2009, 49, 1322-1324.<br />
[2]<br />
S. Kobayashi, H. Ishitani, Chem. Rev. 1999, 99, 1069-1094.<br />
[3]<br />
J. Noei, A. R Khosropour, Ultras. Sonochem. 2009, 16, 711-717.<br />
[4]<br />
Y. Q. Liu, L. H. Li, L. Yang, H. Y. Li, Chemical Papers 2010, 64, 533-536.<br />
[5]<br />
S. K. Hota, A. Chatterjee, P. K. Bhattacharya, P. Chattopadhyay, Green Chem. 2009, 11,<br />
169-176.<br />
Poster 096 Thursday 17:40 - 20:10 153
Synthesis of complex Phosphonates via Fe-catalyzed Allylic<br />
Substitution<br />
Susanne Rommel, André P. Dieskau, Bernd Plietker<br />
Institut für Organische Chemie – Universität Stuttgart – Pfaffenwaldr<strong>in</strong>g 55 –<br />
70569 Stuttgart – GER<br />
susanne.rommel@oc.uni-stuttgart.de<br />
Organo-phosphonates are useful build<strong>in</strong>g blocks <strong>in</strong> organic synthesis. They are used<br />
<strong>in</strong> a broad spectrum of reactions, e.g. the Horner-Wadsworth-Emmons-reaction. So<br />
far the access to complex organo-phosphonates is mostly limited to high temperature<br />
procedures. Even more challeng<strong>in</strong>g are phosphonates with two adjacent quaternary<br />
carbon centers due to unfavorable steric <strong>in</strong>teractions.<br />
Previously, our group succeeded <strong>in</strong> develop<strong>in</strong>g a Fe-catalyzed regioselective alkoxyallylation<br />
of activated double bonds. Here we present the extension of this method to<br />
the snythesis of diversely functionalised organo-phosphonates via a tandem phospha-<br />
Michael-addition-allylic substitution-reaction.<br />
[1] S. Rommel, A. P. Dieskau, B. Plietker, Eur. J. Org. Chem., accepted.<br />
[2] A.P. Dieskau, M.S. Holzwarth, B. Plietker, Chem. Eur. J. 2012, 18, 2423.<br />
[3] W.S. Wadsworth, W.D. Emmons, J. Am. Chem. Soc., 1961, 83, 1733.<br />
154 Thursday 17:40 - 20:10 Poster 097
Small molecules adsorbed on fuel cell catalysts studied by a<br />
comb<strong>in</strong>ed XAS/<strong>in</strong>-situ DRIFTS approach<br />
Claudia Brieger ∗ , Alexander Schökel ∗ , André Wolz ∗ , Christ<strong>in</strong>a Roth ∗<br />
∗ Institute of Chemistry and Biochemistry – FU Berl<strong>in</strong> – Takustr. 3 – Berl<strong>in</strong> – GER<br />
† Institute of Material Science – TU Darmstadt – Petersenstr. 23 – Darmstadt – GER<br />
claudia.brieger@fu-berl<strong>in</strong>.de<br />
One problem <strong>in</strong> fuel cell technology is the Pt-catalyzed carbon corrosion at the cathode,<br />
lead<strong>in</strong>g to a severe degradation of the performance <strong>in</strong> long-term operation. Consequently,<br />
new support concepts are required. One approach is to replace the carbon<br />
support by electron conduct<strong>in</strong>g (doped) oxides. But while oxide supports are very<br />
common <strong>in</strong> heterogeneous catalysis, only little is known about their structure, work<strong>in</strong>g<br />
pr<strong>in</strong>ciples, degradation behavior and their application <strong>in</strong> electrocatalysis. Thus<br />
to follow structural changes of the novel catalyst systems, and <strong>in</strong> particular changes<br />
of the novel oxide support materials, will be of great importance <strong>in</strong> the future.<br />
Here we report on our approach to comb<strong>in</strong>e XAS (<strong>in</strong> particular delta µ XANES)<br />
and <strong>in</strong>-situ DRIFTS for future <strong>in</strong>vestigation of the <strong>in</strong>teraction between the support<br />
material and the adsorption of small molecules relevant to fuel cell catalysis. In-situ<br />
measurements shall be used to differentiate between reactive <strong>in</strong>termediates and “spectator”<br />
adsorbates and account for metal-support-<strong>in</strong>teractions. Due to the catalysts’<br />
small particle size and low metal load<strong>in</strong>gs, XAS is the optimum choice for our studies,<br />
s<strong>in</strong>ce it provides <strong>in</strong>formation on structure (EXAFS) and adsorbates (delta µ XANES)<br />
at the same time. In particular, EXAFS yields results about cluster size and morphology<br />
whereas delta µ XANES gives additional <strong>in</strong>formation about b<strong>in</strong>d<strong>in</strong>g sites<br />
and adsorbate coverage. With <strong>in</strong>-situ DRIFTS <strong>in</strong>teractions between the adsorbates<br />
and the oxide support can be studied. A comb<strong>in</strong>ation of both techniques, for <strong>in</strong>stance<br />
XAS-IR, has been shown by Newton. [1] To further establish the novel delta µ XANES<br />
technique, <strong>in</strong>-situ DRIFTS measurements will be carried out simultaneously to complement<br />
the delta µ XANES <strong>in</strong>formation. Therefore, CO oxidation has been picked as<br />
a model reaction to analyze the metal-support <strong>in</strong>teractions of oxide-supported Pt-M<br />
catalysts, s<strong>in</strong>ce numerous studies for comparison can be found <strong>in</strong> the literature. Additionally,<br />
it exhibits a good spectral signature, which allows for comparison between<br />
delta µ XANES and DRIFTS.<br />
For the planned experiments, we will exam<strong>in</strong>e the adsorption of CO on Pt-M (M=Pt,<br />
Ru) on different support materials (carbon, oxides) as a model system which is relevant<br />
to fuel cell catalysis. Us<strong>in</strong>g a temperature controlled, comb<strong>in</strong>ed reactor cell, delta<br />
µ XANES and <strong>in</strong>-situ DRIFTS measurements will be done simultaneously. This cell<br />
is constructed right now and based on a DRIFTS cell design by Drochner. [2] Different<br />
requirements have to be taken <strong>in</strong>to account, such as implementation of X-ray w<strong>in</strong>dows<br />
and m<strong>in</strong>imization of the dead volume. This design allows for the first time to<br />
take XAS and <strong>in</strong>-situ DRIFTS spectra of the sample and the reference <strong>in</strong> one s<strong>in</strong>gle<br />
cell, thus under the same conditions. The new <strong>in</strong>sight will be used to develop tailormade<br />
and more stable catalysts, whose structure will be adapted to the prevail<strong>in</strong>g<br />
conditions <strong>in</strong> order to reduce costs, which is of particular <strong>in</strong>terest for commercial applications.<br />
Furthermore, new <strong>in</strong>formation will be ga<strong>in</strong>ed about reaction and poison<strong>in</strong>g<br />
mechanisms of catalysts <strong>in</strong> fuel cells.<br />
[1] M. A. Newton, A. J. Dent, S. G. Fiddy, B. Jyoti, J. Evans Catalysis Today 2007, 126, 64-72.<br />
[2] S. Kohl, A. Drochner, H. Vogel Catalysis Today 2010, 150, 67-70.<br />
Poster 098 Thursday 17:40 - 20:10 155
Regio- and Enantioselective Cyclobutene Allylations<br />
Supaporn Niyomchon, Davide Audisio, Marco Luparia, Nuno Maulide<br />
Max-Planck-Institut für Kohlenforschung – Kaiser-Wilhelm-Platz 1 –<br />
45470 Mülheim an der Ruhr – GER<br />
niyomchon@kofo.mpg.de<br />
Palladium catalysed asymmetric allylic alkylation (AAA) is a powerful synthetic<br />
method for the preparation of optically active compounds. [1] Recently, our laboratory<br />
has focused on the palladium-catalysed reactions of bicyclic lactone 1 with stabilized<br />
(“soft”) nucleophiles to generate highly functionalised cyclobutenes with impressive<br />
diastero- and enantioselectivities. [2,3]<br />
We have now <strong>in</strong>vestigated the behaviour of this system <strong>in</strong> the presence of nonstabilized<br />
(“hard”) nucleophiles. In this presentation, we report our prelim<strong>in</strong>ary results<br />
on the catalytic, asymmetric regioselective allylation of lactone 1 with allyl boronates<br />
2 as well as exploratory mechanistic studies. [4]<br />
[1] B. M. Trost, M. L. Crawley, Chem. Rev. 2003, 103, 2921-2943.<br />
[2] a) F. Frébault, M. Luparia, M. T. Oliveira, R. Goddard, N. Maulide, Angew.Chem. Int. Ed.<br />
2010, 49, 5672-5676; b) M. Luparia, D. Audisio, N. Maulide, Synlett. 2011, 735-740.<br />
[3] a) M. Luparia, M. T. Oliveira, D. Audisio, F. Frébault, R. Goddard, N. Maulide, Angew.<br />
Chem. Int. Ed. 2011, 50, 12631-12635; b) D. Audisio, M. Luparia, M. T. Oliveira, D. Klütt, N.<br />
Maulide, Angew. Chem. Int. Ed. 2012, 51, 7314-7317.<br />
[4] S. Niyomchon, M. Luparia, D. Audisio, submitted.<br />
156 Thursday 17:40 - 20:10 Poster 099
Effect of the preparation conditions on the photoactivity of<br />
TiO2 prepared by hydrolysis of titanium isopropoxide<br />
Magdalena Grześkowiak, Jacek Przepiórski, Antoni W. Morawski<br />
Institute of Chemical and Environmental Eng<strong>in</strong>eer<strong>in</strong>g –<br />
West Pomeranian University of Technology – Pułaskiego 10 – Szczec<strong>in</strong> – POL<br />
mgrzeskowiak@zut.edu.pl<br />
Titanium dioxide also called as titania is very well-known photocatalyst. [1]<br />
Received TiO2 powders were obta<strong>in</strong>ed through the hydrolysis of precursor solution<br />
consist<strong>in</strong>g of a mixture of organometallic compound, titanium isopropoxide (TTIP),<br />
and 2-propanol <strong>in</strong> a volume ratio of 1:3. Subsequently, precursor solution was dissolved<br />
by slowly add<strong>in</strong>g <strong>in</strong>to water under magnetic stirr<strong>in</strong>g at ambient temperature<br />
<strong>in</strong> various pH. Obta<strong>in</strong>ed a colloidal white suspension was dried overnight at 110 o C.<br />
F<strong>in</strong>ally, portions of the hydrated amorphous titanium dioxide was calc<strong>in</strong>ed at 500 o C<br />
for various times <strong>in</strong> an argon atmosphere.<br />
The aim of the present work is to focus on the <strong>in</strong>fluence of the water volume used<br />
to hydrolysis process and calc<strong>in</strong>ation time on the chamical and physical properties<br />
of obta<strong>in</strong>ed TiO2 photocatalysts. Moreover, titanias obta<strong>in</strong>ed through hydrolysis<br />
process carried out <strong>in</strong> 250 ml of water <strong>in</strong> an environment of both acidic and alkal<strong>in</strong>e<br />
conditions were compared.<br />
The obta<strong>in</strong>ed powders were characterized by N2 adsorption-desorption (BET) and<br />
X-ray powder diffraction. Also the photocatalytic activity of obta<strong>in</strong>ed TiO2 powders<br />
and its photodecomposition of azo-dye as a model compound (New Cocc<strong>in</strong>e) was<br />
<strong>in</strong>vestigated (Fig. 1).<br />
Figure 1. Concentration changes of New Cocc<strong>in</strong>e dur<strong>in</strong>g the photodecomposition process<br />
under UV irradation us<strong>in</strong>g test materials obta<strong>in</strong>ed by: a) hydrolysis <strong>in</strong> various water<br />
volume and calc<strong>in</strong>ed at 500 o C for 180 m<strong>in</strong>, b) hydrolysis <strong>in</strong> 250 ml of water and calc<strong>in</strong>ed<br />
at 500 o C for various times<br />
[1] D. P. Macwan, P. N. Dave, S. Chaturvedi, “A review on nano-TiO2 sol-gel type synthesis and<br />
its applications”, The Journal of Materials Science 2011, 46, 3669-3686.<br />
Poster 100 Thursday 17:40 - 20:10 157
Microwave Assisted Synthesis of Chitosan & Prote<strong>in</strong><br />
Conjugates<br />
Zafer Omer Ozdemir<br />
Chemistry – Kırklareli University – Kirklareli – TUR<br />
ozdemirz@gmail.com<br />
Chitosan is a biodegradable natural polyelectrolyte bear<strong>in</strong>g -NH2 groups. These<br />
characteristics of chitosan make it convenient for conjugation reactions. [1-3]<br />
Microwave assisted synthesis of vary<strong>in</strong>g ratios of conjugates of chitosan with prote<strong>in</strong>s<br />
(BSA and HSA) and polyacrylic acid us<strong>in</strong>g various activators (carbodiimide<br />
and HBTU/HOBt) and characterization of these molecules are aimed <strong>in</strong> this project.<br />
In addition, chitosan will be modified with bromoacetic acid to make it water-soluble.<br />
Microwave usage <strong>in</strong> conjugation reactions is a new approach and usage of microwave<br />
energy <strong>in</strong> chemical reactions is rapidly <strong>in</strong>creas<strong>in</strong>g.<br />
Synthesized bioconjugates will be characterized with various chromatographic and<br />
spectroscopic methods and <strong>in</strong>terpreted. The bioconjugates synthesized <strong>in</strong> the project<br />
will have usage potential <strong>in</strong> many fields (enhanc<strong>in</strong>g immunogenicity, drug delivery,<br />
molecular imag<strong>in</strong>g, gene transfer, artificial tissues, etc.) by modify<strong>in</strong>g them with<br />
various methods.<br />
[1] H. Zhang, R. Li, W. Liu, International Journal of Molecular Sciences 2011, 12, 917-934.<br />
[2] I. Aranaz, R. Haris, A. Heras, Current Organic Chemistry, 14, 308-330, 2010.<br />
[3] S. C. Yadav, A. Kumari, R. Yadav, Peptides, 32, 173-187, 2011.<br />
This work was supported by Yildiz Technical University Project No 29-07-04-GEP01<br />
158 Thursday 17:40 - 20:10 Poster 101
Efficiently Quenched Fluorescent NIR Probe for Detection of<br />
Enzyme Activity<br />
Jagoda Sloniec, Ute Resch-Genger, Andreas Hennig<br />
Analytical Chemistry; Reference Materials –<br />
Federal Institute for Materials Research and Test<strong>in</strong>g – Richard-Willstätter-Straße 11 –<br />
Berl<strong>in</strong> – GER<br />
jagoda.sloniec@bam.de<br />
Fluorescence technologies are powerful research tools <strong>in</strong> the detection of enzyme<br />
activity. [1] The use of activatable optical probes, which are targeted aga<strong>in</strong>st diseaserelated<br />
enzymes, allows imag<strong>in</strong>g of enzymatic activity, monitor<strong>in</strong>g of enzyme reaction<br />
and determ<strong>in</strong>ation of k<strong>in</strong>etic properties of an enzyme. [2] Here<strong>in</strong> we <strong>in</strong>troduce an efficiently<br />
quenched fluorescent probe for activity detection of a model enzyme (PGA).<br />
Ow<strong>in</strong>g to position<strong>in</strong>g dye and quencher at the same side of the enzyme recognition<br />
moiety we secure a close spatial proximity and thereby an optimal dye-quencher <strong>in</strong>teraction<br />
<strong>in</strong> our fluorescent probe. Hence, our approach ensures efficient fluorescence<br />
quench<strong>in</strong>g for NIR dyes by exploit<strong>in</strong>g contact-based quench<strong>in</strong>g mechanisms. The enzymatic<br />
cleavage of our fluorescent probe leads to a fragmentation <strong>in</strong>to <strong>in</strong>dividual<br />
molecular build<strong>in</strong>g blocks via a well-established qu<strong>in</strong>one-methide elim<strong>in</strong>ation and to<br />
a release of previously quenched dyes. We report the successful multistep synthesis,<br />
a dye screen<strong>in</strong>g with a set of NIR dyes, relative quantum yields of synthesized fluorescent<br />
probes, fluorescence quench<strong>in</strong>g mechanism and enzyme k<strong>in</strong>etic parameters.<br />
Fig.1. Design pr<strong>in</strong>ciple of our efficient quenched fluorescent probe.<br />
[1] a) A. Hennig, D. Roth, T. Enderle et al., ChemBioChem 2006, 7, 733; b) H. Sahoo, A. Hennig,<br />
M. Florea et al., J. Am. Chem. Soc. 2007, 129, 15927; c) A. Hennig, H. Bakirci, W. M. Nau,<br />
Nat. Meth. 2007, 4, 629; d) A. Hennig, M. Florea, D. Roth et al., Anal. Biochem. 2007, 360,<br />
255; e) R. N. Dsouza, A. Hennig, W. M. Nau, Chem. Eur. J. 2012, 18, 3444.<br />
[2] W. Pham, Y. Choi, R. Weissleder et al., Bioconjugate Chem. 2004, 15, 1403.<br />
Poster 102 Thursday 17:40 - 20:10 159
Fluorescent Lipids as FRET-Probes<br />
– Sh<strong>in</strong><strong>in</strong>g Light on Sph<strong>in</strong>golipid Metabolism –<br />
Thomas P<strong>in</strong>kert, Christoph Arenz<br />
Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 –<br />
12489 Berl<strong>in</strong> – GER<br />
thomas.p<strong>in</strong>kert@chemie.hu-berl<strong>in</strong>.de<br />
Lipid signal<strong>in</strong>g processes have been shown to be related to major cellular events<br />
e.g. proliferation, cell death (apoptosis, necroptosis), autoimmune and <strong>in</strong>flammatory<br />
processes. [1] Related diseases comprise acute lung <strong>in</strong>jury, diabetes and cancer [2]<br />
as well as bacterial <strong>in</strong>fections (e.g. Neisseria gonorrhoea). [3] Therefore, the realtime-visualization<br />
and <strong>in</strong>-situ-quantification of these processes <strong>in</strong> liv<strong>in</strong>g tissues are<br />
of key importance <strong>in</strong> lipid chemistry. Recently, this was accomplished for the acid<br />
ceramidase [4] and different phospholipases [5] by the synthesis of doubly labeled fluorescent<br />
lipid analogues which allow the determ<strong>in</strong>ation of enzyme activity with<strong>in</strong> the<br />
liv<strong>in</strong>g cell by means of Förster resonance energy transfer (FRET).<br />
These biochemical tools could not only supersede laborious and expensive radioactive<br />
assays, but could also sh<strong>in</strong>e light on transport k<strong>in</strong>etics and topology, essential <strong>in</strong>formation<br />
that is still elusive s<strong>in</strong>ce established analytical methods (mass spectrometry<br />
of purified fragments) fail <strong>in</strong> this regard.<br />
Hav<strong>in</strong>g synthesized a probe for the acid ceramidase [4] we now aim at establish<strong>in</strong>g<br />
probes for the sph<strong>in</strong>gomyel<strong>in</strong>-synthase and acid sph<strong>in</strong>gomyel<strong>in</strong>ase (aSMase). The latter<br />
enzyme is responsible for the degradation of membrane constituent sph<strong>in</strong>gomyel<strong>in</strong><br />
and <strong>in</strong>volved cell cycle regulation and development of Niemann-Pick lysosomal storage<br />
disease. [3] In order to design a FRET-probe for the aSMase we want to synthesize a<br />
fluorescently labeled artificial substrate, which upon action of the enzyme shows different<br />
photospectral properties. This should allow the determ<strong>in</strong>ation of the enzyme<br />
activity <strong>in</strong> situ.<br />
Structure and mode of operation of the envisioned aSMase-FRET-probe.<br />
[1] R. W. Jenk<strong>in</strong>s, D. Canals, Y. A. Hannun, Cell Signal 2009, 21, 836-846.<br />
[2] E. L. Smith, E. H. Schuchman, FASEB J 2008, 22, 3419-3431.<br />
[3] T. Kolter, K. Sandhoff, Angew. Chem. Int. Ed. 1999, 38, 1532-1568.<br />
[4] K. P. Bhabak, A. Hauser, S. Redmer, S. Banhart, D. Heuer, C. Arenz, <strong>2013</strong>, <strong>in</strong> revision.<br />
[5] O. Wichmann, J. Wittbrodt, C. Schultz, Angew. Chem. Int. Ed. 2006, 45, 508-512.<br />
160 Thursday 17:40 - 20:10 Poster 103
LC-MS of <strong>in</strong>tact prote<strong>in</strong>s - a tool for fast venom mass<br />
profil<strong>in</strong>g. Application to death adder (Acanthophis laevis)<br />
venom.<br />
Daniel Petras ∗ , Stefan H. Hüttenha<strong>in</strong> † , Roderich D. Süssmuth ∗ , Juan J. Calvete ‡<br />
∗ Institut für Chemie – TU Berl<strong>in</strong> – GER<br />
† Fachbereich Chemie- und Biotechnologie – Hochschule Darmstadt – GER<br />
‡ Laboratorio de Venómica y Prote<strong>in</strong>ómica Estructural –<br />
Instituto de Biomedic<strong>in</strong>a de Valencia, CSIC – ESP<br />
daniel.petras@chem.tu-berl<strong>in</strong>.de<br />
Snake venoms are complex mixtures of bioactive polypeptides. A deep understand<strong>in</strong>g<br />
of the composition of venoms is of applied importance not only for explor<strong>in</strong>g their<br />
enormous potential as sources of pharmacological novelty, but also to fight the dire<br />
consequences of snakebite envenom<strong>in</strong>gs. [1] Unravel<strong>in</strong>g complex molecular venom phenotypes<br />
is now with<strong>in</strong> the reach of “omic” tecnologies. In particular, the last decade<br />
has witnessed the development of bottom-up proteomic strategies to explore venom<br />
proteomes. [2] Proteomics-based protocols to quantify the extent of cross-reaction of<br />
IgG or (Fab’)2 antivenoms aga<strong>in</strong>st homologous and heterologous venoms, have been<br />
also recently <strong>in</strong>troduced. [3-5] Drawbacks of bottom up venomics <strong>in</strong>clude the co-elution<br />
(HPLC), low mass resolution (SDS-PAGE), or impaired quantification ability (2DE),<br />
of the venom components. In addition, HPLC peak identification is restricted to the<br />
detection limit (LOD) of UV detectors, which is up to 100 times higher than LODs<br />
of mass analysers. [6] Further, off-l<strong>in</strong>e mass determ<strong>in</strong>ation is time-consum<strong>in</strong>g and not<br />
amenable for high-throughput screen<strong>in</strong>g. To overcome these difficulties, LC-MS can<br />
be applied for the rapid venom analysis. [7] In this work, we applied a LC-MS method<br />
us<strong>in</strong>g high resolution mass spectrometry for the rapid mass profil<strong>in</strong>g of death adder,<br />
Acanthophis laevis, venoms from three different geographic regions of Papua-New<br />
Gu<strong>in</strong>ea. Quantification of detected masses was achieved by comb<strong>in</strong><strong>in</strong>g UV chromatographic<br />
areas and the summed extracted ion chromatogram signals. Our results show<br />
that A. laevis venom consists of PLA2s (50-75%), 3FTxs (10-35%), Kunitz-type <strong>in</strong>hibitors<br />
(2-15 %), peptides (< 1%), and non-assigned m/z < 2000 (5-7 %) and >23<br />
kDa (∼4%) components. These data provide a valuable <strong>in</strong>sight <strong>in</strong>to A. laevis venom<br />
composition and geographic variability, and found the scaffold for the further venomic<br />
characterization of this medically relevant snake.<br />
[1]<br />
R. J. McCleary , R. M. K<strong>in</strong>i, Toxicon <strong>2013</strong>, 62, 56-74.<br />
[2]<br />
J. J. Calvete, Expert Rev. Proteomics 2011, 8, 39-58.<br />
[3]<br />
B. Lomonte, J. Escolano, J. Fernández, L. Sanz, Y. Angulo, J. M. Gutiérrez, J. J. Calvete, J.<br />
Proteome Res. 2008, 7, 2445-2457.<br />
[4]<br />
D. Petras, L. Sanz, A. Segura, M. Herrera, M. Villalta, D. Solano, M. Vargas, G. León, D. A.<br />
Warrell, R. D. Theakston, R. A. Harrison, N. Durfa, A. Nasidi, J. M. Gutiérrez, J. J. Calvete, J.<br />
Proteome Res. 2011, 10, 1266-1280.<br />
[5]<br />
D. Pla, J. M. Gutiérrez, J. J. Calvete, Toxicon 2012, 15, 688-699.<br />
[6]<br />
R. J. He<strong>in</strong>, Proquest, Umi Dissertation Publish<strong>in</strong>g 2011.<br />
[7]<br />
B. G. Fry, J. C. Wickramaratna, W. C. Hodgson, P. F. Alewood, R. M. K<strong>in</strong>i, H. Ho, W. Wüster,<br />
Rapid Commun Mass Spectrom. 2002, 1, 600-608.<br />
Poster 104 Thursday 17:40 - 20:10 161
Mutual Lewis Acid–Base Interactions of Cations and Anions<br />
<strong>in</strong> Ionic Liquids<br />
Markus Holzweber ∗ , Ralf Lungwitz † , Denise Doerfler ‡ , Stefan Spange † , Mihkel Koel ⋄ ,<br />
Herbert Hutter ‡ , Wolfgang L<strong>in</strong>ert ‡<br />
∗ Division 6.8 - Surface Analysis and Interfacial Chemistry –<br />
BAM - Federal Institute for Material Science and Test<strong>in</strong>g – Unter den Eichen 44 –<br />
Berl<strong>in</strong> – GER<br />
† Institute of Chemistry – Chemnitz University of Technology – Strasse der Nationen 62 –<br />
Chemnitz – GER<br />
‡ Institute of Applied Synthetic Chemistry – Vienna University Of Technology –<br />
Getreidemarkt 9/ – Vienna – AUT<br />
⋄ Institute of Chemistry – Tall<strong>in</strong>n Technical University – Akadeemia Tee 15 –<br />
Tall<strong>in</strong>n – EST<br />
markus.holzweber@bam.de<br />
Solute properties are known to be strongly <strong>in</strong>fluenced by solvent molecules due to<br />
solvation. This is due to mutual <strong>in</strong>teraction as both the properties of the solute<br />
and of the solvent strongly depend on each other. The presented work is based<br />
on the idea that ionic liquids are cations solvated by anions and anions solvated<br />
by cations. To show this (<strong>in</strong> this system strongly pronounced) <strong>in</strong>teraction the long<br />
time established donor–acceptor concept for solvents and ions <strong>in</strong> solution by Viktor<br />
Gutmann is extended to ionic liquids. A number of solvent parameters, such as the<br />
Kamlet–Abboud–Taft and the Dimroth–Reichardt ET scale for ionic liquids neglect<br />
this mutual <strong>in</strong>fluence, which, however, seems to be <strong>in</strong> fact necessary to get a proper<br />
description of ionic liquid properties. It is shown how strong such parameters vary<br />
when the <strong>in</strong>fluence of the counter ion is taken <strong>in</strong>to account. Furthermore, acceptor<br />
and donor numbers for ionic liquids are presented.<br />
162 Thursday 17:40 - 20:10 Poster 105
Synthesis and study of antioxidant properties of fullerene C60<br />
derivatives.<br />
Robert Czochara, Michał Symonowicz, Grzegorz Litw<strong>in</strong>ienko<br />
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
rczochara@chem.uw.edu.pl<br />
Oxidative damage of organic materials is caused by free radicals and Reactive Oxygen<br />
Species (ROS). Antioxidants can <strong>in</strong>hibit oxidation reaction by removal of free<br />
radicals. Activity of antioxidants depends on structure and chemical nature, thus,<br />
nanoparticles are new promis<strong>in</strong>g objects for free radical research. Fullerenes [1] can<br />
f<strong>in</strong>d many potential applications <strong>in</strong> science, <strong>in</strong>dustry and medic<strong>in</strong>e. [2,3] Carbon core<br />
makes fullerene an <strong>in</strong>terest<strong>in</strong>g <strong>in</strong>itial structure <strong>in</strong> the development of novel radicalscaveng<strong>in</strong>g<br />
compounds with specific functionalities. Recently, it has been shown that<br />
fullerenes and their derivatives can trap several radicals per molecule [4] and can potentially<br />
be used as a protective substance aga<strong>in</strong>st ROS.<br />
The aim of our studies is to synthesize [5] organic derivatives of fullerene C60(X)n<br />
(where X= C10HqqNO2; (NHC6H4OH)6; C9H9NO). The structures are shown <strong>in</strong><br />
Figure 1.<br />
By means of the differential scann<strong>in</strong>g calorimetry (DSC) and Clark electrode [6,7] we<br />
also carried out the <strong>in</strong>vestigations on the potential antioxidant properties dur<strong>in</strong>g the<br />
oxidation of stearic (ST) and l<strong>in</strong>olenic (LNA) acids as models of oxidizable organic<br />
materials. Our results showed that at high temperature <strong>in</strong> bulk lipid phase the C60<br />
and its derivatives are stable and can break radical oxidation cha<strong>in</strong>s. This feature<br />
is useful because new derivatives can be applied as antioxidants work<strong>in</strong>g <strong>in</strong> extreme<br />
conditions.<br />
This work was supported by Faculty of Chemistry, University of Warsaw, grant BST<br />
501/86-DSM-102400.<br />
Figure 1. Obta<strong>in</strong>ed fullerene C60 derivatives.<br />
[1]<br />
H. W. Kroto, J. R. Heath, S. C. O’Brien, R. F. Curl, R. E. Smalley, Nature 1985, 318, 162.<br />
[2]<br />
B.C. Yadav, R. Kumar, International Journal of Nanotechnology and Applications 2008,<br />
2, 15.<br />
[3]<br />
R. Bakry, R. Vallant, International Journal of Nanomedic<strong>in</strong>e 2007, 2, 639.<br />
[4]<br />
S. S. Huang, S. K. Tsai, C.L. Chih, L.Y. Chiang, Free Radical Biol. Med. 2001, 30, 643.<br />
[5]<br />
M. Prato, M. Magg<strong>in</strong>i, Acc. Chem. Res. 1998, 31, 519.<br />
[6]<br />
P. Ziaja, K. Jodko-Piorecka, R. Kuzmicz, G. Litw<strong>in</strong>ienko, Polym. Chem. 2012, 3, 93.<br />
[7]<br />
R. Czochara, P. Ziaja, P. Piotrowski, R. Pokrop, G. Litw<strong>in</strong>ienko, Carbon 2012, 50, 3943.<br />
Poster 106 Thursday 17:40 - 20:10 163
Homogeneous immunoassay based on biolum<strong>in</strong>escence<br />
resonance energy transfer from Luciola m<strong>in</strong>grelica luciferase<br />
Daria V. Smirnova, Janna V. Samsonova, Alexander P. Osipov, Natalia N. Ugarova<br />
Chemistry Department – M.V. Lomonosov Moscow State University –<br />
Len<strong>in</strong>skiye Gory 1-3 – Moscow – RUS<br />
S_mir_nova@mail.ru<br />
Homogeneous immunoassay is one of the perspective, but <strong>in</strong>sufficiently explored direction<br />
of biolum<strong>in</strong>escence resonance energy transfer (BRET) applications. Here we<br />
propose a rapid and potentially sensitive homogeneous immunoassay of low molecular<br />
weight antigen based on the BRET. In this work we studied possibility of luciferase L.<br />
m<strong>in</strong>grelica application <strong>in</strong> homogeneous immunoassay for determ<strong>in</strong>ation of low molecular<br />
weight antigens. Progesterone was chosen as a model antigen. System <strong>in</strong>cludes<br />
thermostable mutant form of luciferase (4TS), conjugated with progesterone (donor)<br />
and fluoro-labeled antibody (acceptor of biolum<strong>in</strong>escence). As an acceptor we used<br />
Alexa fluor 610-x dye, because it has an optimal spectral overlap of the lum<strong>in</strong>escent<br />
and dye excitation spectra and a larger quantum yield as compared with Cy3 or Cy3.5,<br />
described at [1] . The method could f<strong>in</strong>d a wide range of applications by exchang<strong>in</strong>g<br />
antigens and correspond<strong>in</strong>g antibodies.<br />
In this work, we optimized conditions of synthesis of luciferase-progesterone conjugates.<br />
Via heterogeneous ELISA we demonstrated, ability of progesterone-luciferase<br />
conjugate form a complex with antibody. The strict dependence of Biolum<strong>in</strong>escent<br />
activity on the ratio luciferase/progesterone <strong>in</strong> reaction mixture was observed: <strong>in</strong>creased<br />
from 12 to 63 percent, while this ratio was reduced from 1: 50 to 1: 5. We<br />
obta<strong>in</strong>ed conjugates of dye-labeled antibody (BRET-acceptor), with an F/P ratio of<br />
3 to 10, and tested them for the lum<strong>in</strong>escence energy transfer measurement.<br />
Then biolum<strong>in</strong>escent progesterone-tagged luciferase spectra <strong>in</strong> absence and presence<br />
of fluoro-labeled antibody were registrated at different concentrations of components.<br />
In absence of fluoro-labeled antibody only one maximum (590 nm), correspond to<br />
the luciferase emission was obserwed. When fluoro-labeled antibody was added, a<br />
reduction <strong>in</strong> the light emission at around 590 nm, and <strong>in</strong>crease around 630 nm were<br />
observed, suggest<strong>in</strong>g a transfer of energy from the progesterone-tagged luciferase to<br />
the fluoro-labeled anti-progesterone antibody.<br />
BRET-<strong>in</strong>dices were taken as the ratios of the light emissions at 630 and 590 nm.<br />
L<strong>in</strong>ear relationship was observed between BRET <strong>in</strong>dices and the amount of dye <strong>in</strong>corporated<br />
<strong>in</strong>to a prote<strong>in</strong>. Then the relationships between the BRET <strong>in</strong>dices and labeled<br />
antibodies concentration were plotted. A reduction of BRET <strong>in</strong>dex <strong>in</strong> presence of progesterone<br />
was observed. This show possibility of application Luc4TS conjugate for<br />
the determ<strong>in</strong>ation of low molecular weight antigen via homogeneous ELISA <strong>in</strong> short<br />
time.<br />
[1] Y. Yamakawa, H. Veda et al., Journal of Bioscience and Bioeng<strong>in</strong>eer<strong>in</strong>g, 2002, 93, 537-542.<br />
164 Thursday 17:40 - 20:10 Poster 107
Wheat Bran as Anti-Urolithiasis Crystallization<br />
Khaled Sekkoum ∗ , Nasser Beleboukhari ∗ , Abdelkrim Cheriti † , Safia Taleb ‡<br />
∗ Biomolecules & Chiral Separation Laboratory – University of Bechar – POBox 417 –<br />
Bechar – ALG<br />
† Phytochemistry & Organic Syntheesis Laboratory – University of Bechar –<br />
POBox 417 – Bechar – ALG<br />
‡ Material & Catalysis Laboratory – Djilali Liabes University – Sidi Bel Abess – ALG<br />
khalidos669@yahoo.fr<br />
Urolithiasis can lead to the loss of renal function <strong>in</strong> some cases. In this study, we<br />
tested the <strong>in</strong>hibit<strong>in</strong>g effect of wheat bran (Triticum aestivum L) extract on calcium<br />
oxalate crystallization <strong>in</strong> a turbidimetric model, by FTIR spectroscopy, and polarized<br />
microscopy. The results show that this plant extract has a major <strong>in</strong>hibitory effect on<br />
calcium oxalate crystallization.<br />
Poster 108 Thursday 17:40 - 20:10 165
Preparation of z<strong>in</strong>c phthalocyan<strong>in</strong>e catalysts by cotton fabric<br />
dye<strong>in</strong>g<br />
Ahmet Lütfi Uğur ∗ , Ali Erdoğmuş † , M. Arif Kaya †<br />
∗ Chemistry – Canakkale 18 March University – Canakkale – TUR<br />
† Chemistry Department – Yildiz Technical University – Istanbul – TUR<br />
alugur3@hotmail.com<br />
Among tetrapyrrole compounds, phthalocyan<strong>in</strong>es (Pc) which are full-aromatic planar<br />
molecules due to their 18-π electron structure can be substituted with a great deal of<br />
functional groups. In addition to their extensive use as pigments and dyes, this versatility<br />
gives rise to many applications, such as catalysts, liquid crystals, electrochromic<br />
and photochromic substances, data storage systems, photodynamic cancer therapy<br />
agents, photoactive units, chemical sensors, and nonl<strong>in</strong>ear optical devices. [1-3] Catalytic<br />
activities of metallo-phthalocyan<strong>in</strong>es derived from their structural similarity to<br />
metallo-porphyr<strong>in</strong> complexes have been widely studied because of their rather cheap<br />
and facile preparation <strong>in</strong> a large scale and of their chemical and thermal stability. [4]<br />
In this study, a novel phthalonitrile derivative was prepared from a s<strong>in</strong>gle step reaction.<br />
By us<strong>in</strong>g phthalonitrile derivative, metallo-phthalocyan<strong>in</strong>es carry<strong>in</strong>g acidic substituents<br />
on the periphery were synthesized. Spectral results such as FT-IR, UV–Vis,<br />
EI-MS and 1H-NMR for the newly synthesized compounds are <strong>in</strong> good agreement<br />
with the proposed structures. Last part of this work dealt with the cotton fabric<br />
which was modified with a cationic auxiliary and converted to cationic cotton fabric<br />
for dye<strong>in</strong>g process.<br />
[1]<br />
N. B. McKeown, Phthalocyan<strong>in</strong>e materials: synthesis, structure and function Cambridge<br />
University Press, Cambridge, 1998.<br />
[2]<br />
F. H. Moser, A. L. Thomas, Properties The phthalocyan<strong>in</strong>es, vol. 1CRC Press, Boca Raton,<br />
FL, 1983.<br />
[3]<br />
C.C. Leznoff, A.B.P. Lever, Phthalocyan<strong>in</strong>es properties and applications, VCH Publishers,<br />
We<strong>in</strong>heim, 1989.<br />
[4]<br />
M. Kimura, Y. Yamaguchi, T. Koyama, K. Hanabusa, H. Shirai, “Catalytic oxidation of 2mercaptoethanol<br />
by cationic water-soluble phthalocyan<strong>in</strong>atocobalt(II) complexes”, J. Porphyr<strong>in</strong><br />
Phthalocyan<strong>in</strong>es 1997, 1 (4), 309-315<br />
166 Thursday 17:40 - 20:10 Poster 109
The structure and biological activity of the fucoidans from<br />
the brown alga Fucus evanescens<br />
Ksenia Porshneva ∗ , Olesya S. Vishchuk † , Tatiana N. Zvyag<strong>in</strong>tseva †<br />
∗ bioorganic chemistry and biotechnology – Far Eastern Federal University –<br />
27, Oktabrskaya Street – Vladivostok – RUS<br />
† PIBOC FEB RAS – prospekt stoletiya Vladivostoka, 159 – Vladivostok – RUS<br />
porszneva@gmail.com<br />
Nowadays the search and isolation of biological active substances from algae are very<br />
actual problems. Polysaccharides from brown algae of the Russian Far Eastern seas<br />
possess unique structure and properties. Thus, brown algae of the Russian Far Eastern<br />
are of great <strong>in</strong>terest because they are renewable and easily cultivated source of<br />
this substances. Fucoidans are high sulfated homo- and heteropolysaccharides from<br />
brown algae. The reason of high <strong>in</strong>terest to these polysaccharides is wide spectrum<br />
of biological activities, such as ant<strong>in</strong>eoplastic, immunomodulat<strong>in</strong>g, antibacterial, antiviral<br />
and antiphlogistic activity. Due to fucoidans are nontoxic for the body they<br />
are widely tested on ability to prevent from development of different types of cancer.<br />
The alga Fucus evanescens was found out to be the richest source of fucoidans. The<br />
aim of this research was to obta<strong>in</strong> highly purified fucoidans from this species of algae<br />
for further determ<strong>in</strong>ation of the structural characteristics of isolated fucoidans. The<br />
next stage of the <strong>in</strong>vestigation is to elucidate correlation between the structure of<br />
fucoidans and their anticancer and ant<strong>in</strong>eoplastic activity.<br />
Poster 110 Thursday 17:40 - 20:10 167
Analysis of the size distribution and the fluorence probe<br />
encapsulation <strong>in</strong> water <strong>in</strong> oil macromeulsion used as cell<br />
model systems<br />
Maria Concetta Dipalo ∗ , Emiliano Altamura ∗ , Pasquale Stano † , Fabio Mavelli ∗<br />
∗ Chemistry Department – University – Via Orabona 4 – Bari – ITA<br />
† Biology Department – University of Roma Tre – Viale Guglielmo Marconi 446 –<br />
Roma – ITA<br />
marichy@t<strong>in</strong>.it<br />
Emulsion droplets and lipid vesicles have been extensively used as compartmentalized<br />
chemical systems to model cells <strong>in</strong> lab experiments [1] , s<strong>in</strong>ce they have an aqueous core<br />
enclosed by a lipid boundary. Their size can range from few nanometers to tens of<br />
micron and they can encapsulate biomolecules, like prote<strong>in</strong>s, DNA and RNA, <strong>in</strong> the<br />
<strong>in</strong>ner aqueous solution. [2] Recently, the phase transfer method has been presented as<br />
a new method for giant vesicle preparation where the macroemulsion formation is the<br />
<strong>in</strong>itial step of the procedure. Moreover, the physics of the biomolecules encapsulation<br />
dur<strong>in</strong>g the lipid compartment preparation is highly relevant both <strong>in</strong> basic and applied<br />
research. In orig<strong>in</strong> of life studies, the entrapment of solutes <strong>in</strong>side liposomes might<br />
expla<strong>in</strong> the onset of metabolic pathways <strong>in</strong> primitive cells. Prelim<strong>in</strong>ary unexpected<br />
observations [3] seem to <strong>in</strong>dicate that the formation of liposomes acts as an attractor<br />
for the solutes <strong>in</strong> solution, br<strong>in</strong>g<strong>in</strong>g about a very high local concentration <strong>in</strong> some of<br />
them.<br />
In this contribution, we present a study of macroemulsion droplets preparation and<br />
fluorescence probes encapsulation. The ternary system studied is m<strong>in</strong>eral oil/1palmitoyl-2-oleoyl-sn-glycero-3-phosphochol<strong>in</strong>e(POPC)/water.<br />
The <strong>in</strong>fluence of the<br />
vortex<strong>in</strong>g time on the droplets size distribution and on the probe encapsulation has<br />
been studied by perform<strong>in</strong>g both a dimensional and a fluorescence <strong>in</strong>tensity analysis<br />
by confocal microscopy. We have also <strong>in</strong>vestigated the correlation between the yield<br />
of encapsulation of various fluorophores and different physical-chemical properties, <strong>in</strong><br />
order to determ<strong>in</strong>e a law of distribution of their local concentration.<br />
Water <strong>in</strong> Oil droplets conta<strong>in</strong><strong>in</strong>g 10 µM Calce<strong>in</strong> <strong>in</strong><br />
[1]<br />
P. Walde, K. Cosent<strong>in</strong>o, H. Engel,P. Stano, ChemBioChem 2010, 11, 848-865.<br />
[2]<br />
P. Stano, P. Carrara, Y. Kuruma, T. de Souza, P. L. Luisi, J. Mat. Chem. 2011, 21, 18887-<br />
18902.<br />
[3]<br />
P. L. Luisi, M. Allegretti, T. de Souza, F. Ste<strong>in</strong>iger, A. Fahr, P. Stano, ChemBioChem 2011,<br />
11, 1989-1992.<br />
168 Thursday 17:40 - 20:10 Poster 111
Thym<strong>in</strong>e and 2,6-diam<strong>in</strong>opur<strong>in</strong>e: a crystal architecture study<br />
<strong>in</strong> the context of crystal eng<strong>in</strong>eer<strong>in</strong>g and nucleic acid base<br />
pair<strong>in</strong>g<br />
Urszula Budniak, Katarzyna N. Jarzembska, Paul<strong>in</strong>a M. Dom<strong>in</strong>iak<br />
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
urszula.budniak@student.uw.edu.pl<br />
Nucleobases, i.e. either pur<strong>in</strong>es or pyrimid<strong>in</strong>es, constitute undoubtedly a crucial group<br />
of compounds <strong>in</strong> the context of nucleic acids. The specific <strong>in</strong>teractions between these<br />
moieties are responsible for ma<strong>in</strong>ta<strong>in</strong><strong>in</strong>g a proper structure of DNA, and thus are<br />
essential for the correct transfer of the genetic <strong>in</strong>formation. Nucleobases may form<br />
hydrogen bond<strong>in</strong>g (<strong>in</strong> general, between the complementary pairs) but also may participate<br />
<strong>in</strong> π-stack<strong>in</strong>g <strong>in</strong>teractions (between the aromatic r<strong>in</strong>g fragments).<br />
Beside the natural nucleic acid bases (NABs), also their analogues are commonly<br />
<strong>in</strong>vestigated. Some of such derivatives are encountered <strong>in</strong> organisms, while others<br />
are obta<strong>in</strong>ed artificially. Nevertheless, the <strong>in</strong>formation ga<strong>in</strong>ed from the studies of<br />
unnatural compounds can contribute to our knowledge about nucleic acid properties<br />
<strong>in</strong> general, and is extremely useful for drug design.<br />
The presented project is focused on two nucleobases, i.e. thym<strong>in</strong>e and 2,6- diam<strong>in</strong>opur<strong>in</strong>e.<br />
The first one occurs naturally <strong>in</strong> biological systems, whereas the second is the<br />
derivative of aden<strong>in</strong>e. The two analysed moieties should b<strong>in</strong>d together via triple hydrogen<br />
bond<strong>in</strong>g, which is <strong>in</strong> contrast to a double Watson-Crick bond<strong>in</strong>g characteristic<br />
for a standard A-T pair. With<strong>in</strong> this project a lot of effort was dedicated to synthesis<strong>in</strong>g<br />
the component crystals and the co-crystal, and to characterise them. For that<br />
purpose X-ray diffraction experiments were carried out. For good quality and well<br />
diffract<strong>in</strong>g crystals the experimental charge density analysis was performed, while for<br />
the rema<strong>in</strong><strong>in</strong>g cases the TAAM procedure (Transferable Aspherical Atom Model) was<br />
applied. [1] Here, we present a comprehensive study of crystal pack<strong>in</strong>g and energetic<br />
features of the analysed systems <strong>in</strong> the context of the related compounds deposited<br />
<strong>in</strong> the Cambridge Structural Database (CSD) and our previous works dedicated to<br />
the NAB derivatives. [2,3] The nature of <strong>in</strong>termolecular <strong>in</strong>teractions, structural motifs<br />
and crystal pack<strong>in</strong>g was analysed via Hirshfeld surfaces and f<strong>in</strong>gerpr<strong>in</strong>t plots, charge<br />
density distribution, and theoretical calculations (CRYSTAL, Gaussian, and PIXEL).<br />
The solvent impact was also considered.<br />
[1] N. K. Hansen, P. Coppens, “Test<strong>in</strong>g aspherical atom ref<strong>in</strong>ements on small-molecule data sets”,<br />
Acta Cryst. 1978, A34, 909-921.<br />
[2] K.N. Jarzembska, M. Kubsik, R. Kamiński, K. Woźniak, P.M. Dom<strong>in</strong>iak, “From a s<strong>in</strong>gle molecule<br />
to molecular crystal architectures - structural and energetic studies of selected uracil derivatives”,<br />
Cryst. Growth Des. 2012, 12, 2508-2524.<br />
[3] K.N. Jarzembska, A.M. Goral, R. Gajda, P.M. Dom<strong>in</strong>iak, “Hoogsteen-Watson-Crick 9-methyladen<strong>in</strong>e:1-methylthym<strong>in</strong>e<br />
complex: charge density study <strong>in</strong> the context of crystal eng<strong>in</strong>eer<strong>in</strong>g and<br />
nucleic acid base pair<strong>in</strong>g”, Cryst. Growth Des. 2012, 13, 239-254.<br />
[4] The authors acknowledge Polish M<strong>in</strong>istry of Science and Higher Education for f<strong>in</strong>ancial support<br />
with<strong>in</strong> the “Diamond Grant” program.<br />
Poster 112 Thursday 17:40 - 20:10 169
Synthesis and evaluation of polycations as <strong>in</strong>hibitors of<br />
human coronavirus NL63<br />
Justyna Ciejka ∗ , Aleksandra Milewska † , Kamil Kam<strong>in</strong>ski ∗ , Anna Karewicz ∗ ,<br />
Dorota Bielska ∗ , Maria Nowakowska ∗ , Jan Potempa † , Krzysztof Pyrc † ,<br />
Krzysztof Szczubialka ∗<br />
∗ Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Krakow – POL<br />
† Faculty of Biochemistry Biophysics and Biotechnology – Jagiellonian University –<br />
Gronostajowa 7 – Krakow – POL<br />
justyna.ciejka@gmail.com<br />
Human coronavirus NL63 (HCoV NL63) is generally classified as a common cold virus<br />
and it may cause severe upper and lower respiratory tract diseases. Thus, there is a<br />
need to develop effective methods of prevent<strong>in</strong>g and treat<strong>in</strong>g these <strong>in</strong>fections.<br />
The aim of this study was to synthesise and explore anticoronaviral activity of polymerbased<br />
compounds. Four polycations, i.e. N(2 hydroxyl)propyl 3 trimethylammonium<br />
chitosan chloride (HTCC), hydrophobically modified HTCC (HM HTCC), O(2<br />
hydroxypropyl) 3 trimethylammonium poly(v<strong>in</strong>yl alcohol) chloride (HTPVA) and<br />
poly(allylam<strong>in</strong>e hydrochloride) (PAH) were <strong>in</strong>vestigated. In order to evaluate the<br />
<strong>in</strong>hibitory activity of the tested polymers <strong>in</strong> vitro study us<strong>in</strong>g LLC MK2 cells and<br />
ex vivo study us<strong>in</strong>g human airway epithelium (HAE) cultures were performed. The<br />
cytopathic effect (CPE) was correlated with a quantitative RT PCR based assay. The<br />
cytotoxicity was exam<strong>in</strong>ed by an XTT assay and a Neutral Red assay.<br />
The results show that cationically modified polymers are effective <strong>in</strong>hibitors of HCoV<br />
NL63 replication. A cationically modified chitosan derivative HTCC seems to be the<br />
best <strong>in</strong>hibitor of replication of HCoV NL63 at nontoxic concentrations. Non modified<br />
polymers (chitosan, polyv<strong>in</strong>yl alcohol) did not show any antiviral properties.<br />
Acknowledgements<br />
This work was supported by the grant from Foundation for Polish Science Team<br />
Programme cof<strong>in</strong>anced by the EU European Regional Development Fund (PolyMed,<br />
TEAM/2008 2/6), the M<strong>in</strong>istry of Scientific Research, Poland (0095/B/P01/2009/37<br />
and N N204 151336), Iuventus Plus grant from the M<strong>in</strong>istry of Science and Higher<br />
Education, Poland (IP 2010 033870) (KP) and Foundation for Polish Science with<strong>in</strong><br />
the Hom<strong>in</strong>g Programme. The Faculty of Biochemistry, Biophysics and Biotechnology<br />
of the Jagiellonian University is a beneficiary of the structural funds from the<br />
European Union (grant No: POIG.02.01.00 12 064/08 “Molecular biotechnology for<br />
health”).<br />
Structures of the polymers show<strong>in</strong>g anticoronaviral properties<br />
170 Thursday 17:40 - 20:10 Poster 113
Polymeric photosensitizer for use <strong>in</strong> antimicrobial<br />
photodynamic therapy<br />
Urszula Kwolek, Ewa Rząd, Mariusz Kępczyński, Maria Nowakowska<br />
Department of Physical Chemistry and Electrochemistry – Jagiellonian University –<br />
Ingardena 3 – Kraków – POL<br />
kwolek@chemia.uj.edu.pl<br />
A porphyr<strong>in</strong>-polycation conjugate, a polymeric photosensitizer was synthesized and<br />
characterized. The conjugate (Fig. 1) was prepared by modification of the method<br />
described previously [1] , based on covalent attachment of the protoporphyr<strong>in</strong> IX (Pp)<br />
to the polycation cha<strong>in</strong> of polyethyleneim<strong>in</strong>e (PEI). Protoporphyr<strong>in</strong> was chosen due<br />
to its good photosensizit<strong>in</strong>g properties [2] , while PEI was previously shown to cross<br />
through bacterial outer membranes. [3,4] Therefore, this conjugate is expected to be<br />
promis<strong>in</strong>g for use <strong>in</strong> antibacterial photodynamic therapy (APDT).<br />
The polymeric photosensitizer was characterized us<strong>in</strong>g spectroscopic methods (fluorescence,<br />
absorption and NMR spectra) and chromatographic analysis. The obta<strong>in</strong>ed<br />
results <strong>in</strong>dicate that Pp-PEI exhibits strongly aggregation <strong>in</strong> aqueous solution at physiological<br />
pH (pH=7.4), whereas absorption and fluorescence spectra of Pp-PEI dissolved<br />
<strong>in</strong> methanol were typical for monomeric form of porphyr<strong>in</strong>s. Chromatographic<br />
analysis (GPC) provided <strong>in</strong>formation that synthesized product is uncrossl<strong>in</strong>ked.<br />
The <strong>in</strong>fluence of Pp-PEI on lipid membranes was studied us<strong>in</strong>g liposomes as a model.<br />
The k<strong>in</strong>etics of the <strong>in</strong>corporation of Pp-PEI <strong>in</strong>to the liposomes, the b<strong>in</strong>d<strong>in</strong>g constant<br />
(Kb) to the lipid membranes and fluorescence quench<strong>in</strong>g of porphyr<strong>in</strong> were evaluated.<br />
The results demonstrate that porphyr<strong>in</strong> chromophores b<strong>in</strong>d to liposomes, but due to<br />
the large size of the attached polymer, the b<strong>in</strong>d<strong>in</strong>g constant is rather low. Incorporation<br />
of Pp-PEI <strong>in</strong>to lipid membranes was confirmed us<strong>in</strong>g laser scann<strong>in</strong>g confocal<br />
microscopy.<br />
Fig. 1. The structure of Pp-PEI.<br />
[1]<br />
L. Huang, T. Zhiyentayev, Y. Xuan, D. Azhibek, G. B. Kharkwal, M. R. Hambl<strong>in</strong>, Lasers <strong>in</strong><br />
Surgery and Medic<strong>in</strong>e 2011, 43, 313-323.<br />
[2]<br />
F. Ricchelli, Journal of Photochemistry and Photobiology B: Biology 1995, 29, 109-118.<br />
[3]<br />
T. Dai, G. P. Tegos, T. Zhiyentayev, E. Mylonakis, M. R. Hambl<strong>in</strong>, Lasers <strong>in</strong> Surgery and<br />
Medic<strong>in</strong>e 2010, 42, 38-44.<br />
[4]<br />
I. M. Helander, K. Latva-Kala, K. Lounatmaa, Microbiology 1998, 144, 385-390.<br />
Poster 114 Thursday 17:40 - 20:10 171
An Novel Acyclic Nucleic Acid Mimic: Preparation,<br />
Properties and Prospection [1]<br />
Meng Su<br />
Fakultät für Chemie und Pharmazie – Ludwig-Maximilians-Universität München –<br />
Butenandtstr. 5-13, Build<strong>in</strong>g F – 81377 Munich – GER<br />
nieseln.su@gmail.com<br />
For decades, nucleic acid mimics have aroused cont<strong>in</strong>ued <strong>in</strong>terest to chemist as well as<br />
biologist and shown impressive applications <strong>in</strong> molecular biology and pharmaceutical<br />
sciences. Here<strong>in</strong>, a novel nucleic acid mimic based on 3-am<strong>in</strong>o-1,2-propanediol was<br />
designed and synthesized. The opened sugar r<strong>in</strong>g allowed more flexibility. Amide<br />
l<strong>in</strong>kage was <strong>in</strong>troduced to avoid nuclease hydrolysis, and the reserved phosphodiester<br />
bond ensured the solubility. F<strong>in</strong>ally, the distance between the base and sugar was<br />
<strong>in</strong>creased, which benefited the repulsion between strands.<br />
After the four monomers were <strong>in</strong> hand, substituted s<strong>in</strong>gle strands and thromb<strong>in</strong> b<strong>in</strong>d<strong>in</strong>g<br />
aptamers (TBA) were synthesized with solid phase synthesizer, confirmed by<br />
MADLI-TOF mass spectrometry. Accord<strong>in</strong>g to the melt<strong>in</strong>g temperatures, all the<br />
15-mer oligomers, substituted at different positions, showed lower duplex stability<br />
compared to dsDNA (-3.7 ∼ -9.0 K). However, when the acyclic monomer placed<br />
<strong>in</strong> positions T3, T7 and T12, the aptamer showed higher thermodynamic stability<br />
than unmodified one (+10.7K ), while substitution at other positions decreased the<br />
stability (-16.4 ∼ -20.2 K). Besides, conformational difference was <strong>in</strong>dicated by CD<br />
spectra. Furthermore, for the s<strong>in</strong>gle strand, the hydrolysis resistance were improved<br />
50 fold <strong>in</strong> SVPDE and 32 fold <strong>in</strong> bov<strong>in</strong>e serum, and for the quadruplex 3.6 fold and<br />
1.7 fold respectively.<br />
In short, the novel acyclic nucleic acid mimic offered greater protection towards exonucleases,<br />
specific substituted aptamers even showed improved thermodynamic stability.<br />
This study provides valuable <strong>in</strong>formation regard<strong>in</strong>g the optimal design of oligonucleotides.<br />
Study of further applications such as RNA <strong>in</strong>terference and molecular<br />
beacon are now underway.<br />
Left: acyclic nucleic acid monomers <strong>in</strong> this study, R = P(OCH2CH2CN)N i Pr2; middle:<br />
melt<strong>in</strong>g temperatures (partially) of modified dsDNA and aptamers, letters <strong>in</strong> bold and<br />
italic stand for modified monomers; right: PAGE show<strong>in</strong>g the cleavage k<strong>in</strong>etics of ssDNA<br />
and aptamers by SVPDE and bov<strong>in</strong>e serum<br />
[1] This work was supported by the National Natural Science Foundation of Ch<strong>in</strong>a. The author<br />
thanks Dr. X<strong>in</strong>j<strong>in</strong>g Tang at Pek<strong>in</strong>g University Health Science Center for helpful discussions.<br />
172 Thursday 17:40 - 20:10 Poster 115
Characterization of a Cisplat<strong>in</strong>-DNA-Antibody and its<br />
Correspond<strong>in</strong>g Antibody-Antigen-Complexes by Mass<br />
Spectrometry Under Native Conditions<br />
Lena Ruhe ∗ , Johanna Hofmann † , Ulrike Hochkirch ∗ , Jürgen Thomale ‡ ,<br />
Michael W. L<strong>in</strong>scheid ∗<br />
∗ Department of Chemistry – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 –<br />
Berl<strong>in</strong> – GER<br />
† Department of Molecual Physics – Fritz-Haber-Institute of Max-Planck-Society –<br />
Faradayweg 4-6 – Berl<strong>in</strong> – GER<br />
‡ Institute of Cell Biology – University Hospital Essen – Hufelandstraße 55 –<br />
Essen – GER<br />
lena.ruhe@chemie.hu-berl<strong>in</strong>.de<br />
S<strong>in</strong>ce antibodies have been <strong>in</strong>creas<strong>in</strong>gly used <strong>in</strong> the diagnostic and therapeutic medic<strong>in</strong>e,<br />
new analytical tools for their detection and characterization are gett<strong>in</strong>g more and<br />
more important. In recent years, especially soft ionization techniques of mass spectrometry<br />
like electrospray ionization (ESI) were improved for the detection of high<br />
masses. This allows the analysis of precise molecular masses of large native prote<strong>in</strong>s<br />
like antibodies without any fragmentation. In order to understand structural aspects<br />
of native non-covalent complexes the analysis of a whole antibody-antigen-complex is<br />
a big challenge and first results are presented <strong>in</strong> this work.<br />
In this study we analyzed the monoclonal rat antibody R-C18 specific for Cisplat<strong>in</strong><br />
<strong>in</strong>duced DNA adducts which was developed by Thomale et al. [1] The detection of<br />
this antibody <strong>in</strong> its native state was successfully performed by a modified nano-ESI<br />
time of flight mass spectrometer (ToF-MS). [2] The antibody was found to be 20 to<br />
50 fold charged - extremely depend<strong>in</strong>g on the parameters used. The correct mass of<br />
the unmodified antibody was determ<strong>in</strong>ed to 144 kDa. As a model for the antigen<br />
we used synthetic oligonucleotides with known base sequences to produce the specific<br />
plat<strong>in</strong>ated DNA antigens. Oligomers conta<strong>in</strong> 50 bases and were analyzed as s<strong>in</strong>gle<br />
and double strands. The sequences of these 50mers was chosen that only one of the<br />
s<strong>in</strong>gle strands conta<strong>in</strong>s two adjacent guan<strong>in</strong>es to give the supposed b<strong>in</strong>d<strong>in</strong>g pattern<br />
G*G*-cisPt(NH3)2 after <strong>in</strong>cubation with Cisplat<strong>in</strong>. As a result we could detect the<br />
unmodified and the plat<strong>in</strong>ated DNA oligomers us<strong>in</strong>g mass spectrometry <strong>in</strong> positive<br />
and negative mode. The whole antibody-antigen-complex us<strong>in</strong>g these synthetic plat<strong>in</strong>ated<br />
oligomers could be successfully measured <strong>in</strong> positive mode. Surpris<strong>in</strong>gly, the<br />
antibody b<strong>in</strong>ds not only to the plat<strong>in</strong>ated synthetic 50mer double strand but also to<br />
each of the correspond<strong>in</strong>g plat<strong>in</strong>ated s<strong>in</strong>gle strands. That means that the b<strong>in</strong>d<strong>in</strong>g<br />
pattern of this special antibody might neither be restricted to DNA double strands,<br />
nor to the until now assumed b<strong>in</strong>d<strong>in</strong>g pattern of G*G* <strong>in</strong>trastrand Cisplat<strong>in</strong> adducts.<br />
In conclusion we show the successful detection of antibodies and their antibodyantigen-complexes<br />
under native conditions via nano-ESI-High Mass-Q-ToF-MS. In<br />
future it could be possible to determ<strong>in</strong>e the precise epitope-b<strong>in</strong>d<strong>in</strong>g structure of DNA<br />
antigens detected by diagnostic relevant antibodies.<br />
[1] Liedert et al., Nucl. Acids Res. 2006, 34 (6), e47.<br />
[2] van den Heuvel et al., Anal. Chem. 2006, 78, 7473-7483.<br />
Poster 116 Thursday 17:40 - 20:10 173
K<strong>in</strong>etic studies on the antiradical activity of sulforaphane.<br />
Jakub Cędrowski, Grzegorz Litw<strong>in</strong>ienko<br />
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
jcedrowski@chem.uw.edu.pl<br />
Sulforaphane (1-isothiocyanato-4-(methylsulf<strong>in</strong>yl)butane, SFN, Figure 1) is a product<br />
of glucoraphan<strong>in</strong> hydrolysis, a compound naturally found <strong>in</strong> cruciferous vegetables<br />
such as broccoli. SFN belongs to the group of isothiocyanates and it is considered as<br />
a potential anticancer agent with antioxidant activity. [1]<br />
The antiradical molecular mechanism of SFN has not been clearly recognized yet.<br />
Yuan et al. [2] suggested that methylene sulfoxide group (CH3-SO-CH2-) is responsible<br />
for SFN activity and proposed a mechanism <strong>in</strong>volv<strong>in</strong>g H-atom transfer from<br />
methylene group (CH3-SO-CH2-) to an alkyl radical. This <strong>in</strong>terpretation is surpris<strong>in</strong>g<br />
because of high BDE value (Bond Dissociation Energy) for C-H bond of methylene<br />
sulfoxide group (eg. BDE for C-H bond <strong>in</strong> dimethyl sulfoxide is 94 kcal/mol). [3] It<br />
is also suggested that isothiocyanate group of SFN (–N=C=S) is not essential for<br />
antioxidant properties, because after reaction of benzyl isothiocyanate with hydroxyl<br />
radical, the –N=C=S group is unchanged. [2]<br />
The aim of this study was to answer which moiety is responsible for SFN antioxidant<br />
activity. In our work we studied SFN and its analogues (n-hexyl isothiocyanate<br />
(HITC) and dibuthyl sulfoxide (DBSO)) with model DPPH radical <strong>in</strong> methanol. The<br />
progress of the reaction was measured by stopped-flow measurements at 517nm.<br />
Obta<strong>in</strong>ed bimolecular rate constants show that DBSO is almost <strong>in</strong>active toward<br />
DPPH radical. On the other hand HITC reacts with DPPH but much slower than<br />
SFN. Equimolar mixture of DBSO with HITC does not change the rate of reaction<br />
as compared to HITC used alone.<br />
We have proved that isothiocyanate group (-NCS) slowly reacts with radicals and this<br />
observation is <strong>in</strong> agreement with reports on k<strong>in</strong>etics of reactions of other compounds<br />
with -NCS group and radicals. [4,5] We account that the presence of both the methylene<br />
sulfoxide group and isothiocyanate group <strong>in</strong> SFN is necessary for its antiradical<br />
properties.<br />
This work was supported by Faculty of Chemistry, University of Warsaw, grant BST<br />
501/86-DSM-102400.<br />
Figure 1. The structure of sulforaphane.<br />
[1]<br />
Zhang Y.S., Talalay P., Cancer Res.(Suppl.) 1994 54, 1976-1981.<br />
[2]<br />
Yuan H. et al.,<br />
Ch<strong>in</strong>.J.Chem.Eng. 2010 18, 312-321.<br />
[3]<br />
Luo Y.R., Handbook of bond dissociation energies<br />
<strong>in</strong> organic compounds, CRC Press LLC 2003.<br />
[4]<br />
Leard<strong>in</strong>i R. et al., J.Org.Chem. 1997<br />
62, 8394-8399. [5] Benati L. et al., J.Org.Chem. 2000 65, 8669-8674.<br />
174 Thursday 17:40 - 20:10 Poster 117
Towards new fungal enzyme <strong>in</strong>hibitors via five and six<br />
membered nitrones<br />
Mattia Ghirardello, Fernando Gomollon-Bel, David Sadaba, Tomas Tejero, Pedro Mer<strong>in</strong>o<br />
Departamento de Síntesis y Estructura de Biomoléculas –<br />
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) –<br />
Universidad de Zaragoza - CSIC - C/ Pedro Cerbuna 12 – Zaragoza – ESP<br />
mattiag@unizar.es<br />
Even though they are not the most understood molecules <strong>in</strong> biology, it is well known<br />
that glycans are a primary class of biomolecules, as important as DNA, RNA, prote<strong>in</strong>s<br />
or lipids. [1] For <strong>in</strong>stance, carbohydrates decorate the surface of most cells direct<strong>in</strong>g<br />
the <strong>in</strong>teractions between them. Therefore, study<strong>in</strong>g the enzymes that synthesize and<br />
modify membrane-attached glycans may lead to the understand<strong>in</strong>g of very important<br />
biological pathways. Also, by prepar<strong>in</strong>g and study<strong>in</strong>g modified sugars to <strong>in</strong>hibit this<br />
enzymes we can achieve potencial antibiotics, fungicides or antitumoral agents.<br />
In our laboratory, thanks to the vast experience we have <strong>in</strong> the chemistry of nitrones, [2]<br />
we are develop<strong>in</strong>g several methods for the preparation of five and six membered nitrones<br />
that can be functionalized and then reduced to give pirrolid<strong>in</strong>es and piperid<strong>in</strong>es,<br />
classic <strong>in</strong>hibitors of glycosidases and transglycosidades (Figure 1). The products<br />
obta<strong>in</strong>ed are currently be<strong>in</strong>g tested <strong>in</strong> molecular dock<strong>in</strong>g, molecular dynamics and<br />
<strong>in</strong>hibition assays.<br />
Figure 1<br />
Aknowledgements:<br />
M. G. thanks the Spanish M<strong>in</strong>istry of Education, Culture and Sports for a FPU Predoctoral grant.<br />
F. G.-B. and D. S. are grateful to the Spanish Council for Scientific Research (CSIC) for their JAE<br />
Predoctoral grants.<br />
References:<br />
[1] R. F. Service, Science 2012, 18, 321-323.<br />
[2] P. Mer<strong>in</strong>o, S. Franco, F. Merchán, T. Tejero, Synlett. 2000, 442-454; I. Delso, T. Tejero, A.<br />
Goti, P. Mer<strong>in</strong>o, J. Org. Chem. 2011, 76, 4139-4143.<br />
Poster 118 Thursday 17:40 - 20:10 175
A mechanistic study of the <strong>in</strong>teraction between nitrite and<br />
oxy myoglob<strong>in</strong> us<strong>in</strong>g ultra fast techniques<br />
Gabriela Denisa Hathazi, Sonia Mahut, Radu Silaghi-Dumitrescu<br />
Faculty of Chemistry and Chemical Eng<strong>in</strong>eer<strong>in</strong>g – Babes-Bolyai University –<br />
Arany Janos Str. no. 11 RO-400028, Cluj Napoca – Cluj-Napoca – ROU<br />
denisahathazi@yahoo.com<br />
The nitrite anion NO −<br />
2 has recently received much biochemical attention as an endogenous<br />
source of nitric oxide that has the potential to be supplemented for therapeutic<br />
effects [1] , as well as for its <strong>in</strong>volvement <strong>in</strong> the Blue Baby Syndrome [2] , or its use as a<br />
preservative <strong>in</strong> meat products. [3] S<strong>in</strong>ce the reaction can proceed <strong>in</strong> two directions due<br />
to the equilibrium between the oxy and the deoxy form of the glob<strong>in</strong>s, we set out to<br />
establish which is the route taken and which are the very first species formed at the<br />
start of the process. This reaction is known to have complex autocatalytic k<strong>in</strong>etics,<br />
mediated by prote<strong>in</strong> free-radicals, start<strong>in</strong>g with a slow (lag) phase, after which proceeds<br />
onto a fast autocatalytic phase, lead<strong>in</strong>g to the oxidation of the oxy form to the<br />
met form, nitrite to nitrate; <strong>in</strong> the presence of a higher concentration of NO −<br />
2 nitritemet<br />
adducts are formed. [4] UV-vis spectra were collected upon stopped-flow mix<strong>in</strong>g<br />
of glob<strong>in</strong>s with a supraphysiological excess of nitrite and various k<strong>in</strong>etic simulations<br />
were performed, deconstruct<strong>in</strong>g the result<strong>in</strong>g spectra <strong>in</strong>to <strong>in</strong>dividual components, we<br />
have found a match, that suggests that the <strong>in</strong>itial pathway <strong>in</strong>volves the formation<br />
of an iron(II)-peroxonitrate adduct which releases nitrate and the high-valent radical<br />
species, ferryl. This is the first study where a reaction <strong>in</strong>termediate is directly<br />
detected <strong>in</strong> the oxy+nitrite reaction.<br />
[1] A. Keszler, B. Piknova, A. N. Schechter, N. Hogg “The reaction between nitrite and oxyhemoglob<strong>in</strong>:<br />
a mechanisti study”, J. Biol. Chem. 2008, 281(1), 9615-1922.<br />
[2] R. H. Ste<strong>in</strong>horn, “Therapeutic approaches us<strong>in</strong>g nitric oxide <strong>in</strong> <strong>in</strong>fants and children”, Free<br />
Radic. Biol. Med. 2011, 51(5), 1027-1034.<br />
[3] A. Dejam, C.J. Hunter, C. Tremonti, R. M. Pluta, Y. Y. Hon, G. Grimes, K. Partovi, M.M.<br />
Pelletier, E. H. Oldfield, R. O. Cannon, A. N. Schechter, M. T. Gladw<strong>in</strong>, “Nitrite <strong>in</strong>fusion <strong>in</strong><br />
humans and nonhumans primates: endocr<strong>in</strong>e effects, pharmacok<strong>in</strong>etics and tolerance formation”,<br />
Circulation 2007, 116(16), 1821-1831.<br />
[4] R. Grub<strong>in</strong>a, Z. Huang, S. Shiva, M. S. Joshi, I. Azarov, S. Basu, L. A. R<strong>in</strong>gwood, A. Jiang,<br />
N. Hogg, D. B. Kim-Shampiro, M. T. Gladw<strong>in</strong>, “Concerted nitric oxide formation and the release<br />
from simultaneous reactions of nitrite with deoxy and oxy hemoglob<strong>in</strong>”, J. Biol. Chem. 2007,<br />
282, 12916-12927.<br />
176 Thursday 17:40 - 20:10 Poster 119
Structural modification of thiazol<strong>in</strong>-4-ones as potent<br />
5-lipoxygenase <strong>in</strong>hibitors<br />
Andreas Lill, Sebastian Barzen, Carmen B. Rödl, Dieter Ste<strong>in</strong>hilber, Bett<strong>in</strong>a Hofmann,<br />
Holger Stark<br />
Institute of Pharmaceutical Chemistry – Goethe University – Max-von-Laue-Straße 9 –<br />
Frankfurt am Ma<strong>in</strong> – GER<br />
lill@pharmchem.uni-frankfurt.de<br />
Arachidonic acid released from cytoplasmic membrane upon external stimuli is the<br />
source of one important group of <strong>in</strong>flammatory mediators: the leukotrienes (LTs). The<br />
key enzyme of their biosynthesis is the iron-conta<strong>in</strong><strong>in</strong>g, heme-free 5-lipoxygenase (5-<br />
LO). LTs play a pivotal role <strong>in</strong> <strong>in</strong>flammation, allergic disorders, asthma, cardiovascular<br />
diseases and cancer. Up to now, only two LT-<strong>in</strong>terfer<strong>in</strong>g drugs are marketed with<br />
limited success: the LT-receptor antagonist Montelukast (S<strong>in</strong>gulair R○) and the iron<br />
chelat<strong>in</strong>g 5-LO <strong>in</strong>hibitor Zileuton (Zyflo R○). The need to discover new active ligands<br />
for anti-leukotriene therapy is still urgent. [1,2]<br />
Based on early virtual screen<strong>in</strong>g [3] and medium-throughput screen<strong>in</strong>g we previously<br />
identified the 5-arylidene-2-aryl-thiazol<strong>in</strong>-4-one as a lead structure (Fig. 1). [4]<br />
Our previous studies on structure activity-relationships (SAR) po<strong>in</strong>ted out that this<br />
lead shows a cont<strong>in</strong>uous SAR for 5-LO. [4] Now we were focused on further evaluation,<br />
characterization and cytotoxicity of the thiazol<strong>in</strong>ones. Therefore we designed<br />
and synthesized novel 5-arylidene-2-aryl-thiazol<strong>in</strong>-4-one derivatives as direct 5-LO <strong>in</strong>hibitors,<br />
modify<strong>in</strong>g lipophilicity, the exocyclic double bond and <strong>in</strong>troduc<strong>in</strong>g bicylic or<br />
mono aryl residues (part A to C). The compounds were prepared by one-pot dom<strong>in</strong>o<br />
reaction of thioglycolic acid, the correspond<strong>in</strong>g benzaldehyd and benzonitrile or <strong>in</strong> a<br />
related two-step synthetic procedure.<br />
With the results of 5-LO <strong>in</strong>hibitory assay us<strong>in</strong>g cell-free as well as whole-cell (PMNL<br />
cells) [2][4] conditions we identified a naphthalene derivative with a ten-fold higher<br />
<strong>in</strong>hibitory potency than Zileuton and ga<strong>in</strong>ed further <strong>in</strong>sights <strong>in</strong>to the SAR of the<br />
thiazol<strong>in</strong>one-based 5-LO <strong>in</strong>hibitors. [5]<br />
K<strong>in</strong>dly supported by TRIP, OSF, NeFF, Anwendungsorientierte Arzneimittelforschung<br />
(Fraunhofer IME) and EU COST Actions CM1103, BM1107, BM0806.<br />
Figure 1: 5-Arylidene-2-aryl-thiazol<strong>in</strong>one core scaffold with structural variations<br />
[1] M. Peters-Golden and W. Henderson, N. Engl. J. Med. 2007, 357, 1841.<br />
[2] O. Werz, O and D. Ste<strong>in</strong>hilber, Pharmacol. Ther. 2006, 112, 701.<br />
[3] G. Schneider et al., ChemMedChem 2008, 3, 1535.<br />
[4] B. Hofmann et al., J. Med. Chem. 2011, 54, 1943.<br />
[5] S. Barzen et al., Bioorg. Med. Chem. 2012, 20, 3575.<br />
Poster 120 Thursday 17:40 - 20:10 177
Identification and Characterization Of Secondary<br />
Metabolites Of Paenibacillus larvae<br />
Sebastian Müller ∗ , Eva Garcia-Gonzalez † , Ra<strong>in</strong>er Borriss ‡ , Elke Genersch † ,<br />
Roderich Süßmuth ∗<br />
∗ Department of Organic Chemistry, Biological Chemistry –<br />
Technische Universität Berl<strong>in</strong> – Müller-Breslau Straße 10 – Berl<strong>in</strong> – GER<br />
† Bee Research Institute, Molecular Microbiology and Bee Diseases –<br />
Humboldt-Universität Berl<strong>in</strong> – Friedrich-Engels-Str. 32 – Hohen Neuendorf – GER<br />
‡ Bacterial Genetics – Humboldt-Universität Berl<strong>in</strong> – Chausseestr. 117 – Berl<strong>in</strong> – GER<br />
sebastian.mueller@chem.tu-berl<strong>in</strong>.de<br />
American foulbrood (AFB) is considered the most contagious and destructive <strong>in</strong>fectious<br />
disease <strong>in</strong> honeybees, caused by the Gram-positive, spore-form<strong>in</strong>g bacterium<br />
Paenibacillus larvae. [1] Recently, comparative genome analysis revealed that P. larvae<br />
harbours giant gene clusters that code for polyketide synthases (PKS) and nonribosomal<br />
peptide synthetases (NRPS). [2] These enzymatic complexes are responsible for<br />
the biosynthesis of natural products that are implicated <strong>in</strong> multiple functions such as<br />
antibiotic, immunosuppressive, cytostatic and toxic activity. We hypothesized that<br />
P. larvae requires these substances <strong>in</strong> order to successfully compete aga<strong>in</strong>st bacterial<br />
competitors present <strong>in</strong> the larvae, i.e. that the substances produced by these NRPS<br />
serve as antibiotics. In P. larvae genome, we so far identified, extended, and assembled<br />
three putative NRPS/PKS clusters. Us<strong>in</strong>g bacterial growth <strong>in</strong>hibition assays<br />
we were able to demonstrate that P. larvae stra<strong>in</strong>s <strong>in</strong>deed <strong>in</strong>hibited the growth of<br />
different bacterial species suggest<strong>in</strong>g that at least some of these NRPS/PKS clusters<br />
are functional and lead to non-ribosomal antibiotic production. One of these clusters<br />
expresses a tripeptide that is related to antibiotic activity of P. larvae supernatants.<br />
The structure of the tripeptide D-Phe-D-Ala-L-Trp could be elucidated by means of<br />
LC-ESI-MS and GC-CI-MS. A knock-out mutant for the trimodular NRPS cluster<br />
showed a dramatic decrease <strong>in</strong> bacterial growth <strong>in</strong>hibition. The NRP itself showed<br />
no antibiotic activity. Further experiments, both <strong>in</strong> vitro and <strong>in</strong> vivo, are planned to<br />
prove the role of this substance <strong>in</strong> pathogenesis.<br />
NRPS assembly l<strong>in</strong>e of tripeptide FAW (D-Phe-D-Ala-L-Trp)<br />
[1] E. Genersch, E. Forsgren, J. Pentikä<strong>in</strong>en, A. Ashiralieva, S. Rauch, J. Kilw<strong>in</strong>ski, I. Fries. Int.<br />
J. Syst. Evol. Microbiol. 2006, 56, 501-511.<br />
[2] A. Koumoutsi, X. H. Chen, A. Henne, H. Liesegang, G. Hitzeroth, P. Franke, J. Vater, R.<br />
Borriss, JB. 2004, 186.4, 1084-1096.<br />
178 Thursday 17:40 - 20:10 Poster 121
3,9,17,23-tetraiodo-phthalocyan<strong>in</strong>e magnesium(II) for<br />
applications <strong>in</strong> targeted photodynamic therapy of cancer<br />
Małgorzata Cyza ∗ , Mariusz Kępczyński ∗ , Grzegorz Szewczyk † , Arkadiusz Gut ∗ ,<br />
Łukasz Łapok ∗ , Maria Nowakowska ∗<br />
∗ Department of Physical Chemistry and Electrochemistry – Jagiellonian University –<br />
Ingardena 3 – Cracow – POL<br />
† Department of Biophysics – Jagiellonian University – Gronostajowa 7 – Cracow – POL<br />
malgorzatacyza@gmail.com<br />
Over the past years, metallophthalocyan<strong>in</strong>es (MPc) have been recognized as a very<br />
important compound <strong>in</strong> biomedical studies. MPc derivatives are aromatic macrocycles<br />
based on an 18 π electron system. These compounds are photoactive and tend to<br />
generate s<strong>in</strong>glet oxygen species. Due to this property they can be used as potential<br />
photosensitizers <strong>in</strong> the photodynamic therapy (PDT) of tumors. [1]<br />
Phthalocyan<strong>in</strong>es are known to aggregate <strong>in</strong> aqueous solution. [2] It is expected that<br />
aggregates will have an adverse effect on efficacy of the PDT. One way to overcome<br />
the low solubility of MPc is their encapsulation <strong>in</strong> liposomal vesicles. [1]<br />
3,9,17,23-tetraiodo-phthalocyan<strong>in</strong>e magnesium(II) (PcI4Mg), a MPc derivative, was<br />
obta<strong>in</strong>ed <strong>in</strong> this study and its photochemistry was evaluated. The obta<strong>in</strong>ed compound<br />
is characterized by low value of fluorescence quantum yield. The tendency to generate<br />
s<strong>in</strong>glet oxygen species was measured us<strong>in</strong>g phosphorescence detection. This method<br />
<strong>in</strong>dicated a high value of the s<strong>in</strong>glet oxygen quantum yield. Unfortunately, it was observed<br />
a tendency for aggregation both <strong>in</strong> aqueous environments and methanol. The<br />
aggregation constant <strong>in</strong> methanol was determ<strong>in</strong>ed us<strong>in</strong>g physicochemical techniques<br />
<strong>in</strong>clud<strong>in</strong>g UV-ViS and fluorescence. Next, the <strong>in</strong>teraction between PcI4Mg and liposomes,<br />
a model of biological membrane, was studied. So called b<strong>in</strong>d<strong>in</strong>g constant to<br />
liposomes was determ<strong>in</strong>ed. Studies us<strong>in</strong>g the liposomes were carried out <strong>in</strong> a phosphate<br />
buffer solution (pH 7.4). F<strong>in</strong>ally, photostability of the obta<strong>in</strong>ed phthalocyan<strong>in</strong>e<br />
<strong>in</strong> organic solvents was evaluated.<br />
3,9,17,23-tetraiodo-phthalocyan<strong>in</strong>e magnesium(II) (PcI4Mg)<br />
[1] C. Gol, M. Durmus, Synthetic Metals 2012, 162, 605-613.<br />
[2] A. Ogunisipe, D. Maree, T. Nyokong, Journal of Molecular Structure 2003, 650, 131-140.<br />
[3] K. Nawalany, A. Rus<strong>in</strong>, M. Kępczyński, A. Mikhailov, G. Kramer-Marek, M. Śnietura, J. Połtowicz,<br />
Z. Krawczyk, M. Nowakowska, Journal of Photochemistry and Photobiology B: Biology<br />
2009, 97, 8-17.<br />
Poster 122 Thursday 17:40 - 20:10 179
Vibrational multiconfiguration self-consistent field theory<br />
and a web<strong>in</strong>terface for provid<strong>in</strong>g potential energy surfaces<br />
Florian Pfeiffer, Sandra Heislbetz, Guntram Rauhut<br />
Institute of Theoretical Chemistry – University of Stuttgart – Pfaffenwaldr<strong>in</strong>g 55 –<br />
Stuttgart – GER<br />
pfeiffer@theochem.uni-stuttgart.de<br />
The accurate determ<strong>in</strong>ation of vibrational state energies based on variational approaches<br />
requires the <strong>in</strong>clusion of vibration correlation effects. However, based on<br />
VSCF wavefunctions many states show very small lead<strong>in</strong>g VCI coefficients and show<br />
thus multi-reference character. For that reason we have implemented vibrational multiconfiguration<br />
self-consistent field theory (VMCSCF). [1] With several improvements<br />
we have been able to accelerate our program tremendously. [2] We will present the<br />
theory of the current implementation and illustrate benchmark calculations. Based<br />
on multi-level potential energy surfaces (PES) obta<strong>in</strong>ed from explicitly correlated<br />
coupled-cluster theory, i.e. CCSD(T)-F12/VTZ-F12, mean absolute deviations with<br />
respect to experimental data were found to be as low as 3.0 cm −1 . [3]<br />
To provide these high-level multi-dimensional PES to the scientific community we have<br />
set up a web <strong>in</strong>terface (www.pes-database.theochem.uni-stuttgart.de) which allows to<br />
download potential files free of charge. [4] These can be used for vibrational structure<br />
calculations, molecular dynamics simulations and many other purposes, which require<br />
very accurate representations of the PES. The functionality of the web <strong>in</strong>terface allows<br />
the users to search for certa<strong>in</strong> molecules and even to upload potential files, which have<br />
been generated by Molpro.<br />
[1] S. Heislbetz, G. Rauhut, J. Chem. Phys. 2010, 132, 124102.<br />
[2] S. Heislbetz, F. Pfeiffer, G. Rauhut, J. Chem. Phys. 2011, 134, 204108.<br />
[3] F. Pfeiffer, G. Rauhut, J. Phys. Chem. A 2011, 115, 11050.<br />
[4] F. Pfeiffer, M. Neff, G. Rauhut, to be submitted 2012.<br />
180 Thursday 17:40 - 20:10 Poster 123
Three-dimensional, porous superstructures by self-assembly<br />
of noble metal nanoparticles – <strong>in</strong>vestigation of structural<br />
properties and their application <strong>in</strong> catalysis<br />
Anne-Krist<strong>in</strong> Herrmann, Nikolai Gaponik, Alexander Eychmüller<br />
Physical Chemistry/Electrochemistry – TU Dresden – Bergstraße 66b – Dresden – GER<br />
AK.Herrmann@chemie.tu-dresden.de<br />
New challenges <strong>in</strong> nanotechnology arise <strong>in</strong> the assembly of nanocrystals <strong>in</strong>to threedimensional<br />
and complex superstructures which may carry synergistic properties and<br />
opens up new k<strong>in</strong>d of application fields. A new approach lead<strong>in</strong>g to highly porous,<br />
non-ordered nanostructured solids makes use of a sol-gel process where noble metal<br />
nanoparticles act as build<strong>in</strong>g blocks for nanowires which are <strong>in</strong>terconnected and <strong>in</strong>terpenetrat<strong>in</strong>g<br />
and therefore form<strong>in</strong>g a self support<strong>in</strong>g network with macroscopic<br />
dimensions. [1,2] In this case no l<strong>in</strong>ker systems or templates are used <strong>in</strong> order to realize<br />
the network formation. Instead of this controlled destabilization of the colloidal solution<br />
act as key step for <strong>in</strong>itialization of the process. Subsequent supercritical dry<strong>in</strong>g<br />
<strong>in</strong> CO2 is used <strong>in</strong> order to remove the solvent from the pores and transfer the material<br />
<strong>in</strong>to so called aerogels. Details concern<strong>in</strong>g the mechanism and the particle <strong>in</strong>teraction<br />
are still under <strong>in</strong>vestigation. In order to characterize the aerogels concern<strong>in</strong>g their<br />
composition and structure on the nano- and micro-scale different techniques are used<br />
as for example optical spectroscopy (HR)TEM, SEM, XRD, EDX, N2 and H2 adsorption.<br />
It was shown that their primary structural units match the size range of<br />
the <strong>in</strong>itial nanoparticles (5-15 nm) and they provide a very high surface area, extreme<br />
low density (1/1000 compared to the correspond<strong>in</strong>g bulk metals) but also macroscopic<br />
dimensions whilst ma<strong>in</strong>ta<strong>in</strong><strong>in</strong>g most of the nanoscale properties. Therefore<br />
metallic aerogels provide promis<strong>in</strong>g candidates for many different application fields as<br />
for example: heterogeneous- and electrocatalysis, energy harvest<strong>in</strong>g systems, optical<br />
sensors, surface enhanced Raman scatter<strong>in</strong>g (SERS) substrates, broad band optical<br />
limiters, and conduct<strong>in</strong>g transparent substrates. [3] As an example of an application<br />
<strong>in</strong> the field of catalysis the electrocatalytical activity towards the oxidation of ethanol<br />
of a freestand<strong>in</strong>g α-, β-, or γ- cyclodextr<strong>in</strong> modified palladium nanoparticle aerogel<br />
with extremely high electrocatalytic current density and good durability was recently<br />
reported. [4] Further possibilities and results for application <strong>in</strong> catalysis will be discussed<br />
with<strong>in</strong> the presentation.<br />
[1] Bigall, Herrmann, Vogel, Rose, Simon, Carrillo-Cabrera, Dorfs, Kaskel, Gaponik, Eychmüller,<br />
“Hydrogels and Aerogels from Noble Metal Nanoparticles”, Angew. Chem. Int. Ed. 2009, 48,<br />
9731.<br />
[2] Herrmann, Bigall, Lu, Eychmüller, “Ordered and nonordered porous superstructures from metal<br />
nanoparticles”, <strong>in</strong>: Complex-Shaped Metal Nanoparticles, ed. Sau, Rogach, Wiley-VCH, 2012.<br />
[3] Gaponik, Herrmann, Eychmüller, “Colloidal Nanocrystal-Based Gels and Aerogels: Material<br />
Aspects and Application Perspectives”, J. Phys. Chem. Lett. 2012, 3, 8-17.<br />
[4] Liu, Herrmann, Geiger, Borchardt, Simon, Kaskel, Gaponik, Eychmüller, Angew. Chem. Int.<br />
Ed. 2012, 51, 5743-5747.<br />
Poster 124 Thursday 17:40 - 20:10 181
Towards large scale vibrational structure calculations<br />
Dom<strong>in</strong>ik Oschetzki, Michael Neff, Guntram Rauhut<br />
Institut für Theoretische Chemie – Universität Stuttgart – Pfaffenwaldr<strong>in</strong>g 55 –<br />
D-70569 Stuttgart – GER<br />
osch@theochem.uni-stuttgart.de<br />
The calculation of accurate anharmonic frequencies for large molecules or clusters is<br />
still very demand<strong>in</strong>g. The reason for that are the calculation of high-level potential energy<br />
surfaces (PES) <strong>in</strong> comb<strong>in</strong>ation with accurate vibrational correlation calculations<br />
as provided by vibrational configuration <strong>in</strong>teraction methods (VCI). For the efficient<br />
calculation of the PES several techniques can be used for acceleration, like an automated<br />
iterative <strong>in</strong>terpolation or a gridcomput<strong>in</strong>g <strong>in</strong>terface. The gridcomput<strong>in</strong>g <strong>in</strong>terface<br />
allows for the use of massive parallel architectures and distributed systems, like<br />
the Cray XE6 at the HLRS <strong>in</strong> Stuttgart. Together with the SEGL Client the generation<br />
of the PES can be completely automated on these massive parallel architectures.<br />
In addition to this bottleneck the subsequent VCI calculation becomes expensive,<br />
s<strong>in</strong>ce the configuration space grows rapidly with the system size. To reduce the computational<br />
demands of the VCI calculation, a configuration selection technique is used<br />
to limit the calculation to those configurations, which have a large contribution to the<br />
energy. The observation is that only a very small fraction of the configuration space<br />
is needed to get wavenumber accuracy compared to the experiment. The selection<br />
is based on a VPT2 like energy criterion. To reduce the computational demands of<br />
the VCI calculations further, contractions <strong>in</strong> the calculation of matrix elements and a<br />
more rigorous use of Slater-Condon analogous rules are used. We <strong>in</strong>vestigated a set of<br />
lithium fluoride cluster (up to Li10F10). The equilibrium structures and PES of these<br />
clusters have been calculated at the DF-LCCSD(T)-F12a level of theory us<strong>in</strong>g a reasonable<br />
basis set. For these systems the LCCSD(T)-F12a method gives an accurate<br />
discription of the electronic structure, while the PES calculation on several thousand<br />
cores benefits from the DF implementation. As the bottleneck of the PES calculation<br />
is reduced dramatically by us<strong>in</strong>g the Cray XE6 the subsequent VCI calculations get<br />
more and more the bottleneck. Thereby improv<strong>in</strong>g the VCI calculations will be aga<strong>in</strong><br />
<strong>in</strong> focus.<br />
182 Thursday 17:40 - 20:10 Poster 125
The application of X-rays fluorescence spectroscopy to<br />
determ<strong>in</strong>ation of fluorides <strong>in</strong> solid materials<br />
Zuzanna Kowalkiewicz , Sylwia Lipiecka, Katarzyna Makowska, Włodzimierz Urbaniak<br />
Faculty of Chemistry – Adam Mickiewicz University <strong>in</strong> Poznań –<br />
Umultowska Street 89b – Poznań – POL<br />
zuzanna.kowalkiewicz@amu.edu.pl<br />
X-rays fluorescence spectroscopy is a method based on the fluorescence phenomenon.<br />
Fluorescence is an emission of characteristic X-rays from sample after radiation of a<br />
high energy (X-rays or Gamma rays). Fluorescent radiation of a certa<strong>in</strong> <strong>in</strong>gredient is<br />
result of the transition of electrons dur<strong>in</strong>g release of absorbed energy. Characteristic<br />
emitted radiation can be measure as wavelength of photons (wavelength dispersive<br />
spectrometer- XRF WDS) or energy of photons (energy dispersive spectrometer- XRF<br />
EDS). The majority of X-rays fluorescence spectrometers are limited to determ<strong>in</strong>ation<br />
elements from sodium to uranium, therefore determ<strong>in</strong>ation of fluor<strong>in</strong>e by XRF<br />
spectroscopy is impossible. Moreover, hydrofluoric acid reacts with silicon dioxide<br />
(a component of glass), thus ICP-MS technique is not allowed to measure samples<br />
consist of even small amounts of fluorides.<br />
The aim of this study is to design the new method of determ<strong>in</strong>ation of fluorides <strong>in</strong><br />
solid samples us<strong>in</strong>g X-rays fluorescence spectroscopy. This method <strong>in</strong>cludes two steps<br />
of preparation of sample-lixiviation calcium compounds by acetic acid and sample<br />
filtration. The residue on the filter constitutes the most <strong>in</strong>soluble <strong>in</strong> water fluoride<br />
salt-calcium fluoride (CaF2, fluorspar). Fluorides from a filtrate are determ<strong>in</strong>ed by<br />
ion-selective electrode measurement and simultaneously fluorides from a residue are<br />
determ<strong>in</strong>ed us<strong>in</strong>g XRF apparatus. Own<strong>in</strong>g to mentioned reason fluor<strong>in</strong>e could not be<br />
directly measured by XRF spectroscopy. Hence, a concentration of the anions is calculated<br />
by measurement of a content of calcium <strong>in</strong> the residue. Thus, the concentration<br />
of fluorides are computed by stoichiometric composition of CaF2.<br />
Poster 126 Thursday 17:40 - 20:10 183
A sesquiterpenes acids content of the sedative properties of<br />
lavender flowers (Lavandula angustifolia)<br />
Michal<strong>in</strong>a Adaszyńska, Maria Swarcewicz, Małgorzata Śmist<br />
Department of Organic Synthesis and Drug Technology –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – Piastow Avenue 42 – Szczec<strong>in</strong> –<br />
POL<br />
madaszynska@zut.edu.pl<br />
Lavender is a valuable resource for a wide therapeutic biological activity. In a series<br />
of publications, new varieties of lavender are still generat<strong>in</strong>g <strong>in</strong>terest <strong>in</strong> research,<br />
result<strong>in</strong>g <strong>in</strong> the possibility of us<strong>in</strong>g this herb, such as an antibacterial agent, antifungal,<br />
antioxidant, anti-<strong>in</strong>flammatory as well as act<strong>in</strong>g as a natural antidiabetic medication<br />
and sedative. [1-3] Count<strong>in</strong>g a group of sedative drugs and sleep aids, almost completely<br />
devoid of adverse side effects at normal dosages, preparations are made based on plant<br />
extracts. The aim of this study was to determ<strong>in</strong>e the content of sesquiterpenes acids:<br />
valeric and acetoxyvalerenic acids with flowers of different varieties of lavender.<br />
The determ<strong>in</strong>ation was performed by the method described <strong>in</strong> the European Pharmacopoeia.<br />
[4] Samples of lavender flowers were subjected by gr<strong>in</strong>d<strong>in</strong>g. Extraction of<br />
sesquiterpenes acid were made <strong>in</strong> methanol. The result<strong>in</strong>g extract was analyzed by<br />
HPLC chromatography and chromatographic analysis were carried out <strong>in</strong> parallel with<br />
the addition of the <strong>in</strong>ternal standard (1,8-dihydroxyantrah<strong>in</strong>one). Studies have shown<br />
that different varieties of lavender sesquiterpenes acids content. Most valeric acid was<br />
determ<strong>in</strong>ed <strong>in</strong> the variety ’Ellegance Purple’ (1.52 mg/100 g), and the least <strong>in</strong> the<br />
variety ’Blue River’ (0.75 mg/100 g). However, the flowers of ’Blue River’ conta<strong>in</strong>ed<br />
10-fold more acetoxyvalerenic acid (65.8 mg/100 g) than those of ’Ellegance Purple’<br />
(6.5 mg/100 g).<br />
[1] L. Hui, L. He, L. Huxan, L. XiaoLan, Afri. J. Microbiol. Res., 2010, 4, 309-313.<br />
[2] A. Issa, M. Mohammad, M. Hudaib, K. Tawah, J. Med. Plants. Res. 2011, 5 (16), 3876-3882.<br />
[3] W. Soyowan, V. Siripornpanich, T. Piriyapunyaporn, J. Med. Assoc. Thai. 2012, 9 (4), 2-9.<br />
[4] European Pharmacopoeia 5.0.<br />
184 Thursday 17:40 - 20:10 Poster 127
Gas chromatographic-mass spectrometric identification and<br />
quantitation of volatile cognac spirit components<br />
Peter Nalivayko<br />
Analitycal Chemistry – Belarussian State University – ul. Len<strong>in</strong>gradskaya 14 – M<strong>in</strong>sk –<br />
BLR<br />
NalivaykoPeter@gmail.com<br />
Cognac is a heavy object of analysis because of the complexity of production technology<br />
that requires sophisticated analytical equipment, specialized methodological<br />
materials, skilled labor and certa<strong>in</strong> material costs. This fact comb<strong>in</strong>ed with the lack<br />
of fund<strong>in</strong>g and high cost of production generated a flow of counterfeit that occupied<br />
significant market share. The purpose of this study is to develop a methodology of<br />
f<strong>in</strong>d<strong>in</strong>g of most common ways of cognac adulteration <strong>in</strong> Eastern Europe. The study<br />
is based on an assessment of the organoleptic characteristics of cognac, and gas GC-<br />
MS analysis that allows to def<strong>in</strong>e the composition and ratio of volatile cognac spirit<br />
components as well as components of the decomposition of oak.<br />
Poster 128 Thursday 17:40 - 20:10 185
A DFT Study on The Coord<strong>in</strong>ation of N,<br />
N-dimethyl-N’-(2-chloro)benzoylthiourea with Ni 2+ and<br />
Co 3+ Metal Ions<br />
Celal Özpınar ∗ , Gül Altınbaş Özpınar † , Fatih Mehmet Emen ‡ , Nevzat Külcü ⋄<br />
∗ Department of Chemistry – Kirklareli University – Kavakli – Kırklareli – TUR<br />
† Department of Chemistry – Bursa Technical University – Mer<strong>in</strong>os – Bursa – TUR<br />
‡ Department of Chemistry – Mehmet Akif Ersoy University – Burdur – TUR<br />
⋄ Department of Chemistry – Mers<strong>in</strong> University – Mers<strong>in</strong> – TUR<br />
celal93@yahoo.com<br />
N,N-dialkyl-N’-benzoylthioureas are extensively used as ligands <strong>in</strong> coord<strong>in</strong>ation chemistry<br />
due to the fact that these structures <strong>in</strong>clud<strong>in</strong>g very strong donor groups such<br />
as carbonyl and thioamide are able to coord<strong>in</strong>ate to especially transition metal ions<br />
as monoanionic bidentate ligands which are formed by deprotonation. [1,2] They have<br />
recently attracted great attention as versatile ligands <strong>in</strong> numerous applications such<br />
as <strong>in</strong> pharmaceutical and agrochemical <strong>in</strong>dustries for potential therapeutic agents.<br />
In this study, we have performed theoretical <strong>in</strong>vestigation on the bis(N,N-dimethyl-N’-<br />
(2-chloro)benzoylthioureato)nickel(II) and tris(N,N-dimethyl-N’-(2-chloro)benzoylthioureato)cobalt(III)<br />
complexes us<strong>in</strong>g density functional B3LYP, BLYP, OLYP,<br />
PBEPBE, and wB97XD methods with cc-pVDZ basis set. Optimized geometries,<br />
electronic and spectral properties of the complexes are compared with experimental<br />
data.<br />
Figure 1. Structures of Cu (left) and Ni (right) complexes<br />
Bis(N,N-dimethyl-N’-(2-chloro)benzoylthioureato)nickel(II) (right) and<br />
tris(N,N-dimethyl-N’-(2-chloro)benzoylthioureato)cobalt(III) (left) complexes<br />
[1] P. Muhl, K. Gloe, F. Dietze, E. Hoyer, L. Beyer, Z. Chem. 1986, 26, 81.<br />
[1] K. R. Koch, Coord. Chem. Rev. 2001, 473, 216-217.<br />
186 Thursday 17:40 - 20:10 Poster 129
Method of f<strong>in</strong>d<strong>in</strong>g of honey adulteration by means of<br />
determ<strong>in</strong>ation of 5-hydroxymethylfurfural presence<br />
Ir<strong>in</strong>a Alshakova, Peter Nalivayko<br />
Organic Chemistry – Belarussian State University – ul. Len<strong>in</strong>gradskaya, 14 – M<strong>in</strong>sk –<br />
BLR<br />
ialshakova@gmail.com<br />
Method of f<strong>in</strong>d<strong>in</strong>g of honey adulteration by means of determ<strong>in</strong>ation of 5-hydroxymethylfurfural<br />
presence was proposed <strong>in</strong> this article. Method <strong>in</strong>cludes synthesis of<br />
standart of 5-HMF, sample preparation of honey samples and follow<strong>in</strong>g chromatographic<br />
analysis by means of high performance liquid chromatography accord<strong>in</strong>gly<br />
to proposed conditions. The quality of synthesized standard was confirmed by gas<br />
chromatography-mass-spectrometry. Comparative characteristics of classical methods<br />
of determ<strong>in</strong>ation of 5-HMF <strong>in</strong> homey samples that was <strong>in</strong>troduced <strong>in</strong> this article<br />
confirm higher efficiency HPLC analysis as primary method of determ<strong>in</strong>ation of adulteration<br />
of honey samples.<br />
Poster 130 Thursday 17:40 - 20:10 187
Accurate anharmonic vibrational frequencies and<br />
Franck-Condon factors for SeH2/SeH + 2<br />
Patrick Meier ∗ , Joonsuk Huh † , Robert Berger † , Guntram Rauhut ∗<br />
∗ Institute of Theoretical Chemistry – University of Stuttgart – Pfaffenwaldr<strong>in</strong>g 55 –<br />
Stuttgart – GER<br />
† Clemens-Schöpf-Institute – Technical University of Darmstadt – Petersenstr. 22 –<br />
Darmstadt – GER<br />
patrick.meier@gmx.de<br />
Photoelectron spectra provide valuable <strong>in</strong>sight <strong>in</strong>to the vibronic structure of a molecule.<br />
In many cases a reliable <strong>in</strong>terpretation of such spectra requires the accurate simulation<br />
based on ab <strong>in</strong>itio calculations. If the relevant potential energy surfaces are expanded<br />
<strong>in</strong> different coord<strong>in</strong>ates, the Dusch<strong>in</strong>sky rotation needs to be taken <strong>in</strong>to account. This<br />
rotation <strong>in</strong> comb<strong>in</strong>ation with an accurate description of the vibrational wavefunctions<br />
by a l<strong>in</strong>ear comb<strong>in</strong>ation of distributed Gaussians leads to a computational bottleneck,<br />
which is subject to current research. Such an approach was tested quite recently. [1]<br />
A new program for the calculation of Franck-Condon factors mak<strong>in</strong>g use of these<br />
features has been developed with<strong>in</strong> the Molpro suite of ab <strong>in</strong>itio programs.<br />
Here we present highly accurate calculations on the vibronic transitions of the<br />
SeH2/ SeH +<br />
2 system based on wavefunctions obta<strong>in</strong>ed from vibrational configuration<br />
<strong>in</strong>teraction calculations. The potential energy surface has been obta<strong>in</strong>ed from CCS-<br />
DTQ calculations with basis sets up to quadruple-ζ quality. Moreover, relativistic and<br />
core correlation effects were found to be important and were thus <strong>in</strong>cluded with<strong>in</strong> the<br />
determ<strong>in</strong>ation of the 3-dimensional potential energy surface. Vibrational structure<br />
calculations make use of the full Watson Hamiltonian. Comparison with experimental<br />
data is provided.<br />
[1] J. Huh, M. Neff, G. Rauhut and R. Berger, Mol. Phys. 2009, 108, 409.<br />
188 Saturday 9:00 - 11:30 Poster 131
GC/MS Analysis of Extract and Essential Oil Samples from<br />
Wisteria s<strong>in</strong>ensis<br />
Justyna Sobczak, Elżbieta Huzar, Hal<strong>in</strong>a Kwiecień<br />
Department of Organic Synthesis and Drug Technology –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – al. Piastów 42 – 71-065 Szczec<strong>in</strong> –<br />
POL<br />
jsobczak@zut.edu.pl<br />
Wisteria s<strong>in</strong>ensis is a woody climb<strong>in</strong>g v<strong>in</strong>e of the family Legum<strong>in</strong>osae, that can reach<br />
a height of 20 m, characterized by pendent racemes of light blue-violet, scented flowers.<br />
Orig<strong>in</strong>ally from Ch<strong>in</strong>a, Japan and Southern USA, wisteria was brought <strong>in</strong>to<br />
Europe <strong>in</strong> the n<strong>in</strong>eteenth century.<br />
Several compounds isolated from different wisteria species have been reported to have<br />
antioxidant, antibacterial and anticancer activities. [1,2] Wisteria s<strong>in</strong>ensis flowers are<br />
known for their pleasant, creamy sweet smell. A survey of the literature showed that<br />
the key <strong>in</strong>gredients of the characteristic fragrance of Wisteria s<strong>in</strong>ensis flowers are two<br />
aromatic compounds: 7-hydroxy-6-methoxy-4H-1-benzopyran and 6,7-dimethoxy-4H-<br />
1-benzopyran. [3]<br />
We report our results on the analysis of solvent extracts and essential oils from Wisteria<br />
s<strong>in</strong>ensis flowers. The essential oil was obta<strong>in</strong>ed by steam distillation of the<br />
Wisteria s<strong>in</strong>ensis flowers collected <strong>in</strong> Poland with use of the Deryng apparatus. The<br />
extracts were prepared by maceration both fresh and dried flowers us<strong>in</strong>g methanol,<br />
chloroform and n-hexane as solvents. Samples were analyzed with use gas chromatograph<br />
with a mass selective detector. The compounds were identified us<strong>in</strong>g a NIST<br />
02 mass spectral library and the programmed temperature retention <strong>in</strong>dexes were also<br />
determ<strong>in</strong>ed. A prelim<strong>in</strong>ary analysis by GC/MS lead to characterize the essential oil<br />
and extracts of Wisteria s<strong>in</strong>ensis flowers. Methyl or ethyl esters of fatty acids such<br />
as 14-methylpentadecanoic, hexadecanoic, octadecanoic, 9,12,15-octadecatrienoic and<br />
l<strong>in</strong>oleic acid as well as 9-octadecenamide and aliphatic hydrocarbons such as heptacosane,<br />
eicosane were identified as the ma<strong>in</strong> components. Eugenol, 6,10,14-trimethyl-<br />
2-pentadecanon and phytosterols were also detected.<br />
Figure 1. Wisteria s<strong>in</strong>ensis<br />
[1]<br />
T. Konoshima, M. Takasaki, M. Kozuka, H. Tokuda, H. Nish<strong>in</strong>o, E. Matsuda, M. Ngai, Biol<br />
Pharm Bull, 1997, 20(8), 865-868.<br />
[2]<br />
M.A. Mohamed, M.M. Hamed, A.M. Abdou, W.S. Ahmed , A.M. Saad, Molecules, 2011, 16(5),<br />
4020-4030.<br />
[3]<br />
D. Joula<strong>in</strong>, R. Tabaccchi, Phytochemistry, 1994, 37(6), 1769-1770.<br />
Poster 132 Saturday 9:00 - 11:30 189
SPE-HPLC Onl<strong>in</strong>e Coupl<strong>in</strong>g for the Determ<strong>in</strong>ation of<br />
Zearalenone <strong>in</strong> Edible Oil: First Results<br />
Drzymala Sarah ∗ , Marten Silvia † , Stefan Risch † , Matthias Koch ∗<br />
∗ Department 1 – Federal Institute for Materials Research and Test<strong>in</strong>g –<br />
Richard-Willstätter-Str. 11 – Berl<strong>in</strong> – GER<br />
† Department "Applications and Columns" –<br />
Wissenschaftlicher Gerätebau, Dr. Ing. Herbert Knauer GmbH – Hegauer Weg 38 –<br />
Berl<strong>in</strong> – GER<br />
sarah.drzymala@bam.de<br />
Zearalenone (ZEN) is a non-steroidal hyperestrogenic mycotox<strong>in</strong> that contam<strong>in</strong>ates<br />
different crops worldwide. Due to its lipophilic nature it is often found <strong>in</strong> edible oil<br />
derived from contam<strong>in</strong>ated material. The dilemma of seperat<strong>in</strong>g an apolar analyte<br />
from an apolar matrix either leads to a lack of specifity or very laborious, cost <strong>in</strong>tensive<br />
techniques. Thus, the extraction and clean-up of ZEN from edible oil has long been<br />
termed problematic.<br />
In 2010, Siegel et al. [1] proposed a highly specific one-pot sample preparation technique.<br />
Carbonyl compounds as ZEN can be covalently bound to hydraz<strong>in</strong>e functionalized<br />
polymer particles. After the clean-up process ZEN is cleaved from the polymer<br />
and quantified by HPLC with fluorescence detection.<br />
The aim of this work was to f<strong>in</strong>d out if a covalent SPE approach is suitable for<br />
onl<strong>in</strong>e-coupl<strong>in</strong>g to HPLC.<br />
Seven different res<strong>in</strong>s, polymer and silica based, were tested for their suitability. One<br />
silica and one polymer res<strong>in</strong> were found to have superior k<strong>in</strong>etic properties and were<br />
chosen for SPE cartridge fill<strong>in</strong>gs. First results regard<strong>in</strong>g the technical setup, recovery<br />
and reusability rates are presented. This is the first work to explore whether a SPE<br />
based on covalent <strong>in</strong>teraction has the potential to be coupled to HPLC.<br />
[1] D. Siegel, K. Andrae, M. Proske, C. Kochan, M. Koch, M. Weber,I. Nehls, “Dynamic covalent<br />
hydraz<strong>in</strong>e chemistry as a selective extraction and cleanup technique for the quantification of the<br />
Fusarium mycotox<strong>in</strong> zearalenone <strong>in</strong> edible oils.” J.Chromatogr. A 2010, 1217 (15), 2206-2215.<br />
190 Saturday 9:00 - 11:30 Poster 133
Synthesis, characterization and sensory property of<br />
magnesium porphyraz<strong>in</strong>e possess<strong>in</strong>g<br />
methyl(2-thienylmethyl)am<strong>in</strong>o substituents <strong>in</strong> the periphery<br />
Wojciech Szczolko ∗ , Jacek Kujawski † , Zbigniew Dutkiewicz ∗ , Marek Bernard † ,<br />
Tomasz Gosl<strong>in</strong>ski ∗<br />
∗ Department of Chemical Technology of Drugs –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
† Department of Organic Chemistry – Poznan University of Medical Sciences –<br />
Grunwaldzka 6 – Poznan – POL<br />
wszczolko@ump.edu.pl<br />
INTRODUCTION Peripherally functionalized porphyraz<strong>in</strong>es (Pzs) 1 are isoelectronic<br />
with porphyr<strong>in</strong>s, but <strong>in</strong> comparison possess substantially different electronic properties.<br />
The first possibility to modify Pz is to substitute the core with metal entities<br />
(M), while the second one is connected with peripheral modifications (Figure). Pzs<br />
substituted <strong>in</strong> the periphery have many potential applications as photosensitizers<br />
<strong>in</strong> photodynamic therapy, sensors, molecular semiconductors and non-l<strong>in</strong>ear optical<br />
materials. [1]<br />
RESULTS Maleonitrile (3) was synthesized accord<strong>in</strong>g to the two approaches (Figure).<br />
In the first approach double-reductive alkylation of diam<strong>in</strong>omaleonitrile (2)<br />
was employed to yield 2,3-bis[(2-thienylmethyl)am<strong>in</strong>o]-2(Z)-butene-1,4-d<strong>in</strong>itrile (3)<br />
follow<strong>in</strong>g a method elaborated by the Sheppard [2] and Barrett-Hoffman [3] teams. In<br />
second approach maleonitrile 3 was synthesized <strong>in</strong> a one-step procedure us<strong>in</strong>g 5-ethyl-<br />
2-methylpyrid<strong>in</strong>e borane complex and acetic acid <strong>in</strong> methanol. [1] Alkylation reaction<br />
of 3 with dimethyl sulfate <strong>in</strong> THF led to the novel maleonitrile (4) which was subsequently<br />
used <strong>in</strong> L<strong>in</strong>stead macrocyclization reaction towards symmetrical porphyraz<strong>in</strong>e<br />
(5). Peripheral metallation study of Pz 5 with PdCl2 (PhCN)2 <strong>in</strong> the UV-Vis and<br />
NMR are ongo<strong>in</strong>g. Experimental results will be compared with the theoretical calculations<br />
(Gaussian G09 suite code). The structures of the different Pz 5 conformers with<br />
PdCl2 have been optimized accord<strong>in</strong>g to the density functional theory at B3LYP/6-<br />
31G(d,p) level, <strong>in</strong>clud<strong>in</strong>g PCM solvation model. Moreover, the related calculations<br />
will be compared to the experimental NMR spectra and analyzed us<strong>in</strong>g (i) IGLOII<br />
basis for H, C, N, O, S atoms, (ii) standard base cc-pVTZ for magnesium cation, and<br />
(iii) LANL2DZ ECP for palladium salt. [5,6]<br />
Figure<br />
[1]<br />
M. S. Rodriguez-Morgade, P. A. Stuzh<strong>in</strong>, J. Porphyr. Phthalocya. 2004, 8, 1129.<br />
[2]<br />
R. W. Begland, D. R. Hartter, F. N. Jones, D. J. Sam, W. A. Sheppard, O. W. Webster, F. J.<br />
Weigert, J. Org. Chem. 1974, 39, 2341.<br />
[3]<br />
L. S. Beall, N. S. Mani, A. J. P. White, D. J. Williams, A. G. M. Barrett, B. M. Hoffman, J.<br />
Org. Chem. 1998, 63, 5806.<br />
[4]<br />
E. R. Burkhardt, B. M. Coleridge, Tetrahedron Lett. 2008, 49, 5152.<br />
[5]<br />
J. Kujawski, M. Doskocz, H. Popielarska, A. Myka, J. Kruk, M. K. Bernard, Polyhedron <strong>2013</strong>,<br />
submitted.<br />
[6]<br />
P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270.<br />
Wojciech Szczołko and Jacek Kujawski are scholarship holders with<strong>in</strong> the project “Scholarship<br />
support for PH.D. students specializ<strong>in</strong>g <strong>in</strong> majors strategic for Wielkopolska’s development”, Submeasure<br />
8.2.2 Human Capital Operational Programme, co-f<strong>in</strong>anced by European Union under the<br />
European Social Fund. The authors acknowledge f<strong>in</strong>ancial support for the project from the Polish<br />
M<strong>in</strong>istry of Science and Higher Education (N N405 356339).<br />
Poster 134 Saturday 9:00 - 11:30 191
Synthesis of N-substituted<br />
3,4-dihydropyrimid<strong>in</strong>e-2(1H )-thiones via regioselective<br />
additions of organolithiums to pyrimid<strong>in</strong>e-2(1H )-thiones<br />
Łukasz Struk, Jacek G. Sośnicki<br />
Institute of Chemistry and Environmental Protection –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – Piastów Avenue 42 – Szczec<strong>in</strong> –<br />
POL<br />
lukasz.struk@zut.edu.pl<br />
In the last twenty years 3,4-dihydropyrimid<strong>in</strong>e-2(1H )-thiones were recognized as valuable<br />
pharmacophores, which show a wide range of pharmalogical activity. [1] A large<br />
majority of 3,4-dihydropyrimid<strong>in</strong>e-2(1H )-thione derivatives were synthesized accord<strong>in</strong>g<br />
to three-component protocol developed by Big<strong>in</strong>elli <strong>in</strong> 1893 (Scheme 1). To the<br />
present, a number of improvements have been <strong>in</strong>troduced <strong>in</strong> order to enhance the efficiency<br />
of this reaction. [2,3] As the result of the last attempts N-substituted derivatives<br />
were obta<strong>in</strong>ed start<strong>in</strong>g from N-substituted thiourea. [4] However, despite of the vast<br />
derivatization opportunities, Big<strong>in</strong>elli reaction suffers from the lack of the attachment<br />
of the optional substituent at C-5 and lead ma<strong>in</strong>ly to the derivatives with carbonyl<br />
groups bonded to this carbon atom. Recently, we have demonstrated a new synthetic<br />
approach to C-4 substituted, NH 3,4-dihydropyrimid<strong>in</strong>e-2(1H )-thiones via addition of<br />
organolithiums to commercially available NH pyrimid<strong>in</strong>e 2(1H )-thione. [5] Follow<strong>in</strong>g<br />
this strategy we present now the prelim<strong>in</strong>ary results of the synthesis of 4-alkil(aryl),<br />
5-(H)aryl N-substituted 3,4-dihydropyrimid<strong>in</strong>e-2(1H )-thiones (2). The efficiency and<br />
the regioselectivity of the addition of organolithium reagents are discussed. Besides,<br />
the synthesis of new 5-aryl N-substituted pyrimid<strong>in</strong>e 2(1H )-thiones (1) is presented.<br />
Acknowledgment<br />
F<strong>in</strong>ancial support by the National Science Center (N N204 219640) is gratefully<br />
acknowledged<br />
[1]<br />
J.-P. Wan, Y. Pan, M<strong>in</strong>i-Rev. Med. Chem. 2012, 12, 337.<br />
[2]<br />
Suresh, J.S. Sandhu, ARKIVOC 2012, 1, 66.<br />
[3]<br />
C. O. Kappe, Acc. Chem. Res. 2000, 33, 879.<br />
[4]<br />
H. Comas, D.-A. Buisson, R. Najman, F. Kozielski, B. Rousseau, R. Lopez. Synlett 2009,<br />
1737.<br />
[5]<br />
J.G. Sośnicki, Phosphorus, Sulfur, Silicon Relat. Elem. 2009, 184, 1946.<br />
192 Saturday 9:00 - 11:30 Poster 135
Synthesis of Highly Lum<strong>in</strong>escent Z<strong>in</strong>c Conta<strong>in</strong><strong>in</strong>g Indium<br />
Phosphide Nanoparticles<br />
Gordon M. Stachowski, Stephen G. Hickey, Alexander Eychmüller<br />
Physikalische Chemie/ Elektrochemie – Technische Universität Dresden –<br />
Bergstraße 66b – 01069 Dresden – GER<br />
Gordon.Stachowski@chemie.tu-dresden.de<br />
Progress <strong>in</strong> the field of semiconductor quantum dots has been driven ma<strong>in</strong>ly by research<br />
<strong>in</strong>to cadmium chalcogenides. As a result these materials are presently among<br />
the most <strong>in</strong>vestigated colloidal quantum dots and can be synthesized to possess high<br />
emission quantum yields across the visible spectral region. Unfortunately, with regard<br />
to bio-applications, the toxicity aspects argue aga<strong>in</strong>st the use of cadmium conta<strong>in</strong><strong>in</strong>g<br />
quantum dots. However, the more biocompatible material <strong>in</strong>dium phosphide can<br />
be synthesized such that it covers almost the same spectral range as the cadmium<br />
chalcogenides.<br />
In this work we present the synthesis and characterization of highly emitt<strong>in</strong>g <strong>in</strong>dium<br />
phosphide quantum dots with a dist<strong>in</strong>ct amount of z<strong>in</strong>c. The emission color of the<br />
as-formed material spans the visible spectrum from blue-green to red. A one-pot hot<br />
<strong>in</strong>jection dehalosilylation synthesis method has been comb<strong>in</strong>ed with a well-controlled<br />
temperature program to modify the reaction rate. The as-prepared quantum dots<br />
possess high quantum yields without the further requirement for a passivat<strong>in</strong>g shell.<br />
Furthermore the amount of z<strong>in</strong>c <strong>in</strong>corporated <strong>in</strong> the quantum dots has been <strong>in</strong>vestigated<br />
us<strong>in</strong>g ICP/OES and XPS. We have observed a relationship between the amount<br />
of z<strong>in</strong>c and the higher quantum yields as well as a shift of the emission profile to higher<br />
energies.<br />
Poster 136 Saturday 9:00 - 11:30 193
Five-membered, N-heterocyclic Ligands <strong>in</strong> Organometallic<br />
and Coord<strong>in</strong>ation Chemistry<br />
Markus Kreye ∗ , Andreas Glöckner ∗ , Constant<strong>in</strong> Daniliuc ∗ , Matthias Freytag ∗ ,<br />
Peter G. Jones ∗ , Matthias Tamm ∗ , Marc D. Walter ∗<br />
∗ Chemie – Institut für Anorganische und Analytische Chemie, TU Braunschweig –<br />
Hagenr<strong>in</strong>g 30 – 38106 Braunschweig – GER<br />
† Chemie – Organisch-Chemisches Institut, WWU Münster – Corrensstr. 40 –<br />
48149 Münster – GER<br />
markus.kreye@tu-bs.de<br />
In contrast to the well-developed chemistry of cyclopentadienyl ligands (Cp) and<br />
their complexes, the coord<strong>in</strong>ation chemistry of the related N-heterocyclic ligands is<br />
underdeveloped. First reported by Kuhn <strong>in</strong> 1991, the sterically demand<strong>in</strong>g 2,5-ditert-butyl-pyrrolyl<br />
(Pyr tBu2 ) was found to react as a Cp-analogue and to b<strong>in</strong>d <strong>in</strong> a<br />
eta 5 -fashion form<strong>in</strong>g diaza-metallocenes of Fe, Co, Ni, Sn and Pb. [1]<br />
We have recently begun to explore the coord<strong>in</strong>ation and reaction chemistry of sterically<br />
demand<strong>in</strong>g pyrrolyl and imidazolyl ligands with transition metals. [2] In this context<br />
the possibility to switch between different coord<strong>in</strong>ation modes was established<br />
with Cr(II) and Mn(II) centers. These and other results will be presented.<br />
[1] a.) N. Kuhn, K. Jendral, R. Boese, D. Bläser, Chem. Ber. 1991, 124, 89-91; b.) N. Kuhn,<br />
M. Köckerl<strong>in</strong>g, S. Stubenrauch, D. Bläser, R. Boese, J. Chem. Soc., Chem. Commun. 1991,<br />
1368-1370; c.) N. Kuhn, G. Henkel, J. Kreutzberg, S. Stubenrauch, J. Organomet. Chem. 1993,<br />
456, 97-106; d.) N. Kuhn, G. Henkel, S. Stubenrauch, J. Chem. Soc., Chem. Commun. 1992,<br />
760; e.) N. Kuhn, G. Henkel, S. Stubenrauch, Angew. Chem. 1992, 104, 766-768.<br />
[2] M. Kreye, A. Glöckner, C. G. Daniliuc, M. Freytag, P. G. Jones, M. Tamm, M. D. Walter,<br />
Dalton Trans. <strong>2013</strong>, 42, DOI: 10.1039/c2dt32433d.<br />
194 Saturday 9:00 - 11:30 Poster 137
SiO6 conta<strong>in</strong><strong>in</strong>g Silicophosphates - Syntheses at Room<br />
Temperature<br />
Sandra Jähnigen ∗ , Erica Brendler † , Uwe Böhme ∗ , Edw<strong>in</strong> Kroke ∗<br />
∗ Institut für Anorganische Chemie – TU Bergakademie Freiberg – Leipziger Straße 29 –<br />
Freiberg – GER<br />
† Institut für Analytische Chemie – TU Bergakademie Freiberg – Leipziger Straße 29 –<br />
Freiberg – GER<br />
Sandra.Jaehnigen@chemie.tu-freiberg.de<br />
In nature, only a few silicates are known where silicon is coord<strong>in</strong>ated with six oxygen<br />
atoms, e.g. stishovite. [1,2] Most of them are formed at high-pressure. Silicophosphates<br />
also conta<strong>in</strong> SiO6 octahedra but the ma<strong>in</strong> difference lies <strong>in</strong> their formation at normal<br />
pressure. Examples for it are SiP2O7 [3] and Si5P6O25 [4] phases. However, their<br />
syntheses still require high temperatures or the addition of alkali or alkal<strong>in</strong>e earth<br />
halides.<br />
Recently [5,6] we developed a novel synthesis of silicophosphates start<strong>in</strong>g from anhydrous<br />
H3PO4. We also <strong>in</strong>vestigated one of the products by s<strong>in</strong>gle crystal X-ray<br />
structure analysis (Fig. 1). In addition to established but parameter dependend reactions<br />
at high temperatures or sol-gel-techniques, we were now able to synthesize<br />
silicophosphates at room temperature and normal pressure.<br />
Fig. 1 Si V I (PO4 )6 (Si IV O4 Et2 )6 -Ion 5 with SiO6 located <strong>in</strong> the center of the<br />
complex.<br />
[1] S.M. Stishov, S.V. Popova, Geokhimiya 1961, 837.<br />
[2] E.C.T. Chao, J.J. Fahey, J. Littler, J. Geophys. Res. 1962, 67, 419.<br />
[3] E. Tillmanns, W. Gebert, W.H. Baur, J. Solid State Chem. 1973, 7, 69.; G. Bissert, F.<br />
Liebau, Acta Cryst. 1970, B26, 233.; F. Liebau, K.F. Hesse, Z.Kristallogr. 1971, 133, 213.<br />
[4] H. Mayer, Monatsh. Chem. 1974, 105, 46.<br />
[5] S. Jähnigen, E. Brendler, U. Böhme, E. Kroke, Chem. Commun. 2012, 48, 7675.<br />
[6] S. Jähnigen, U. Böhme, E. Brendler, G. Heide, E. Kroke, “Silikat-Phosphat-Materialien (SiOPs)<br />
- Verfahren zu deren Herstellung und Anwendungen”, Deutsche Patentanmeldung 10 2012 011<br />
034.0, Anmeldetag 05.06.2012.<br />
Poster 138 Saturday 9:00 - 11:30 195
Synthesis of benzo[1,4]oxaz<strong>in</strong>-3-one derivatives with potential<br />
biological activity<br />
Małgorzata Śmist, Michal<strong>in</strong>a Adaszyńska, Hal<strong>in</strong>a Kwiecień<br />
Department of Organic Synthesis and Drug Technology –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – Al. Piastów 42 – Szczec<strong>in</strong> – POL<br />
maugustyniak@zut.edu.pl<br />
The benzo[1,4]oxaz<strong>in</strong>e scaffold is an <strong>in</strong>terest<strong>in</strong>g structural unit which occurs <strong>in</strong> a large<br />
number of biologically active natural and synthetic compounds. Some of them were<br />
found to be antibacterial and antifungal agents. For example, ofloxac<strong>in</strong> [1] is a drug<br />
active aga<strong>in</strong>st Gramnegative bacteria, while the analogues of fluconazole were found<br />
to be a novel class of antifungal agents active aga<strong>in</strong>st Candida albicans. [2] Moreover,<br />
natural derivatives of benzo[1,4]oxaz<strong>in</strong>e were found to be plant allelochemicals, wellknown<br />
for their phytotoxic activity and for tak<strong>in</strong>g part <strong>in</strong> the defense strategies of<br />
Gram<strong>in</strong>eae, Ranunculaceae, and Scrophulariceae plants. [3]<br />
The aim of our research was to obta<strong>in</strong> novel halo-substituted benzo[1,4]oxaz<strong>in</strong>-3ones<br />
as the compounds with potential antifungal and pharmacological properties.<br />
The synthesis starts from 2-nitrophenols (1) and methyl 2-bromoalkanoates (2) and<br />
proceeds by reductive cyclization of methyl 2-(2-nitrophenoxy)alkanoates (3) to give<br />
the desired benzo[1,4]oxazep<strong>in</strong>-3-ones (4). The dibromo derivatives (6) were f<strong>in</strong>ally<br />
obta<strong>in</strong>ed by further brom<strong>in</strong>ation of unsubstituted 2-alkylbenzo[1,4]oxaz<strong>in</strong>-3-ones (5).<br />
Accord<strong>in</strong>g to our expectations some of the products exhibited antifungal activity (<strong>in</strong><br />
vitro tests).<br />
Scheme 1.<br />
[1] th<br />
A. Kleeman, J. Engel, Pharmaceutical substances, Thieme, Stuttgart-New York, 4 Edition,<br />
2001.<br />
[2]<br />
H. B. Borate, S. R. Maujan, S. P. Sawargave, M. A. Chandavarkar, S. R. Vaiude, V. A. Joshi,<br />
R. D. Wakharkar, R. Iyer, R. G. Kelkar, S. P. Chavan, S. S. Kunte, Bioorg. Med. Chem. 2010,<br />
20, 722-725.<br />
[3]<br />
H. M. Niemeyer, J. Agric. Food Chem. 2009, 57, 1677-1696.<br />
196 Saturday 9:00 - 11:30 Poster 139
Synthetic applications of<br />
3-alcoxycarbonyl-4-alkynylcoumar<strong>in</strong>s<br />
Amparo Sanz-Marco, Gonzalo Blay, José Ramón Pedro<br />
Química Orgánica – Universitat de València – Dr. Mol<strong>in</strong>er n o 50 – Burjassot – ESP<br />
amparo.sanz-marco@uv.es<br />
The 3,4-dihydrocoumar<strong>in</strong> r<strong>in</strong>g system constitutes the core of many natural products<br />
and biologically active compounds. [1] In this context, we have described the enantioselective<br />
synthesis of 4-substituted dihydrocoumar<strong>in</strong>s through a new Zn-bis(hydroxyamide)-catalyzed<br />
conjugate addition of term<strong>in</strong>al alkynes. Because of the synthetic versatility<br />
of the triple bond compounds like 1 can be used as build<strong>in</strong>g blocks <strong>in</strong> organic<br />
synthesis.<br />
In this communication, we describe this synthetic potential by carry<strong>in</strong>g out different<br />
transformations <strong>in</strong>volv<strong>in</strong>g the coumar<strong>in</strong> skeleton and/or the triple bond. Thus,<br />
the triple bond can be totally or partially hydrogenated to give C -4 alkylated 2 or<br />
alkenylated 3 dihydrocoumar<strong>in</strong>s, respectively. On the other hand, hydrogenation and<br />
descarboxylation, followed by reduction of the lactone and Mitsunobu reaction give<br />
alkynylated chromane 4 used <strong>in</strong> the synthesis of others chromanes with antihypertensive<br />
activity. [2] Besides, by gold-catalyzed cyclization leads to fused acetal 5 hav<strong>in</strong>g<br />
the tetrahydrofuro[2,3-b]benzofuran skeleton characteristic of fungal metabolite aflatox<strong>in</strong>s<br />
and other natural products. [3] All these synthetic transformations are carried<br />
out with excellent yields and without loss of optical purity.<br />
F<strong>in</strong>ancial support from the M<strong>in</strong>isterio de Ciencia e Innovación and FEDER (CTQ2009-<br />
13083) and from Generalitat Valenciana (ACOMP/2012/212 and ISIC/2012/001) is acknowledged.<br />
A S-M thanks the MICINN for a pre-doctoral grant (FPI).<br />
[1] a) F. Roelens, K. Huvaere, W. Dhooge, M. Van Cleemput, F. Comhaire, D. de Keukeleire, Eur.<br />
J. Med. Chem. 2005, 40, 1042; b) A. Kumar, B. K. S<strong>in</strong>gh, R. Tyagi, S. K. Ja<strong>in</strong>, S. K. Sharma,<br />
A. K. Prasad, H. G. Raj, R. C. Rastogi, A. C. Watterson, V. S. Parmar, Bioorg. Med. Chem.<br />
2005, 13, 4300.<br />
[2] a) E. Tyrell, K. Mazloumi, D. Banti, P. Sajdak, A. S<strong>in</strong>clair, A. Le Gresley, Tetrahedron Lett.<br />
2012, 53, 4280; b) E. Tyrrell, K.-H. Tesfa, I. Greenwood, A. Mann, Bioorg. Med. Chem. Lett.<br />
2008, 18, 1237.<br />
[3] S. Bakirdere, S. Bora, E. G. Bakirderel, F. Ayd<strong>in</strong>, Y. Arslan, O. T. Komesli, I. Ayd<strong>in</strong>, E.<br />
Yildirim, Centr. Eur. J. Chem. 2012, 10, 875.<br />
Poster 140 Saturday 9:00 - 11:30 197
Diversity oriented synthesis <strong>in</strong> the row of 4-Qu<strong>in</strong>alones<br />
Mariia Miliut<strong>in</strong>a, Anton Ivanov, Peter Langer, Viktor O. Iaroshenko<br />
Organic chemistry – University of Rostock – Albert E<strong>in</strong>ste<strong>in</strong> str. 3a – 18059-Rostock –<br />
GER<br />
miamasha@mail.ru<br />
Wide application of qu<strong>in</strong>olones <strong>in</strong> plenty of medic<strong>in</strong>al spheres motivates to go further<br />
<strong>in</strong> search for new efficient and rapid approaches to synthesis of differently substituted<br />
representatives of this structural type. [1-3]<br />
Herewith we present convenient method for synthesis of 4-qu<strong>in</strong>olones via [5+1] cyclization<br />
of o-chloroaryl acetylene ketones 3 and primary am<strong>in</strong>es 4 (Scheme 1). Start<strong>in</strong>g<br />
from 2-chloro-5-nitro-benzoic acid chloranhydride 1 and vary<strong>in</strong>g appropriate acetylenes<br />
2 and am<strong>in</strong>es 4 on the step of cyclization we afforded a row of differently substituted<br />
4-qu<strong>in</strong>olones with yields from good to excellent.<br />
Besides we showed 4-qu<strong>in</strong>olones as a substrate for further functionalizations. Among<br />
them are brom<strong>in</strong>ation, arylation by Susuki-Miaura cross-coupl<strong>in</strong>g reaction and <strong>in</strong>troduction<br />
of trifluoromethyl group <strong>in</strong>stead of brom<strong>in</strong>e <strong>in</strong> third position of the 4qu<strong>in</strong>olone<br />
skeleton as well as reduction of nitrogroup to am<strong>in</strong>ogroup, change of the<br />
latter to brom<strong>in</strong>e with subsequent arylation towards sixth position of the molecule.<br />
Novel polysubstituted compounds 5 and 6 obta<strong>in</strong>ed by the mentioned methods are<br />
of considerable <strong>in</strong>terest as potentially bioactive agents.<br />
Scheme 1. Reagents and conditions: (i) 0.01 eq. Pd(PPh3)2Cl2, 0.02 eq. CuI, THF,<br />
1.3 eq. Et3N, 1.3 eq. of appropriate acetylene, r.t., 6 h; (ii) 1.7 eq. of appropriate am<strong>in</strong>e,<br />
2 eq. K2CO3 or K3PO4, DMF, 120 ◦ C, 6 h.<br />
[1]<br />
L. A. Mitscher, Chem. Rev. 2005, 105, 559-592.<br />
[2]<br />
Cl. Mugna<strong>in</strong>i, Ch. Falciani, M. d. Rosa, A. Brizzi, S. Pasqu<strong>in</strong>i, F. Corelli, Tetrahedron 2011,<br />
67, 5776-5783.<br />
[3]<br />
V. O. Iaroshenko, I. Knepper, M. Zahid, R. Kuzora, S. Dudk<strong>in</strong>, A. Vill<strong>in</strong>ger, P. Langer, Org.<br />
Biomol. Chem. 2012, 10, 2955-2959.<br />
198 Saturday 9:00 - 11:30 Poster 141
Studies Towards the Total Synthesis of Glyceoll<strong>in</strong>es<br />
Marcus Blümel, Susann Baier, Peter Metz<br />
Fachrichtung Chemie und Lebensmittelchemie – University of Techology Dresden –<br />
Bergstraße 66 – 01062 Dresden – GER<br />
Marcus.Bluemel@chemie.tu-dresden.de<br />
The glyceoll<strong>in</strong>s, as a subgroup of isoflavonoids, belong to the naturally anabolized<br />
polyphenols. In case of fungal, viral, or bacterial attack these phytoalex<strong>in</strong>s are formed<br />
and act as anti-microbial agents. [1] For the reason of their structural similarity to human<br />
hormones, such as 17β-estradiol (E2), the isoflavonoids <strong>in</strong> general and glyceoll<strong>in</strong>s<br />
<strong>in</strong> particular are able to <strong>in</strong>teract with the human hormone balance. Thus, a broad<br />
spectrum of applications results <strong>in</strong> order to treat diseases associated with unbalanced<br />
hormone level, such as breast cancer, atherosclerosis, and osteoporosis. [2,3,4] Consequently,<br />
these glyceoll<strong>in</strong>s have attracted much attention <strong>in</strong> the past decades.<br />
The first total synthesis of racemic as well as (+)-, and (-)-glyceoll<strong>in</strong> was published<br />
by Erhardt and coworkers <strong>in</strong> 2008 and recently scaled up to multigram-scale. As<br />
key step a Sharpless oxidation with stoichiometric amounts of OsO4 was used. [5,6]<br />
For our approach toward the glyceoll<strong>in</strong> total synthesis we used a gold catalyzed cyclization.<br />
Coupl<strong>in</strong>g of two fragments derived from commercially available 4-bromo resorc<strong>in</strong>ol<br />
4 is supposed to yield our key <strong>in</strong>termediate, the orthogonal protected isoflavene 5.<br />
A catalytic epoxidation of the central double-bond of isoflavene 5 should open access<br />
to an enantioselective route without us<strong>in</strong>g great amounts of toxic OsO4. Previous research<br />
<strong>in</strong> our group suggests a successful synthesis of (-)-glyceoll<strong>in</strong>s if the enantiopure<br />
epoxide <strong>in</strong>termediate is ga<strong>in</strong>ed.<br />
[1]<br />
T. Aoki, T. Akashi, S.-I. Ayabe, J. Plant Res. 2000, 113, 475-488.<br />
[2]<br />
V. A. Salvo, S. M. Boue, J. P. Fonseca, Cl<strong>in</strong>. Cancer Res. 2006, 12, 7159-7164.<br />
[3]<br />
E. W. Ra<strong>in</strong>es, R. Ross, J. Nutr. 1995, 125, S624-S630.<br />
[4]<br />
T. Usui, Endocr<strong>in</strong>e Journal 2006, 53, 7-20.<br />
[5]<br />
R. S. Khupse, P. W. Erhardt, Org. Lett. 2008, 10, 5007-5010.<br />
[6]<br />
A. Luniwal, R. Khupse, M. Reese, J. Liu, M. El-Dakdouki, N. Malik, L. Fang, P. Erhardt,<br />
Org. Process Res. Dev. 2011, 15, 1149-1162.<br />
Poster 142 Saturday 9:00 - 11:30 199
Design, synthesis and transformation of some<br />
heteroannulated 3-am<strong>in</strong>opyrid<strong>in</strong>es-pur<strong>in</strong>e isosteres with<br />
exocyclic nitrogen atom<br />
Qnar Araqelyan, Ashot Gevorgyan, Satenik Mkrtchyan, Marcelo Vilches-Herrera,<br />
Dmitro Ostrovskyi, Muhammad S.A. Abbasi, L<strong>in</strong>da Supe, Ani Hakobyan,<br />
Viktor Iaroshenko<br />
Faculty of Chemistry – University Rostock – Albert E<strong>in</strong>ste<strong>in</strong> str. 3a, 18059 Rostock –<br />
Rostock – GER<br />
sm19860214@gmail.com<br />
Pur<strong>in</strong>es and pur<strong>in</strong>e-like scaffolds are compounds with extensive application portfolio<br />
<strong>in</strong> the life science and medic<strong>in</strong>e sector. The substances from the pur<strong>in</strong>e/pseudopur<strong>in</strong>e<br />
family have been hav<strong>in</strong>g a significant impact on drug design and drug-development. [1]<br />
Recently, laboratory of Iaroshenko have published a number of methods related to<br />
the synthesis of various heterocycle condensed pyrid<strong>in</strong>e/pyrimid<strong>in</strong>e derivatives via<br />
the [3+3] heteroannulation reaction of pyrid<strong>in</strong>e/pyrimid<strong>in</strong>e moiety on the core of<br />
electron-rich am<strong>in</strong>oheterocycles and anil<strong>in</strong>es <strong>in</strong>volv<strong>in</strong>g set of 1,3-CCC- and 1,3-CNCdielectrophiles.<br />
[2] Cont<strong>in</strong>u<strong>in</strong>g this research synthesis of 1-deazapur<strong>in</strong>es and isosteres<br />
bear<strong>in</strong>g the exocyclic nitrogen atom at position-3 was developed bas<strong>in</strong>g on the formal<br />
[3+3]-cyclization reaction of nitro-malonaldehyde with the set of electron-rich am<strong>in</strong>oheterocycles<br />
(Figure 1). Through the functionalization of the pur<strong>in</strong>e-like scaffolds<br />
synthesized the diversity of compounds furnished <strong>in</strong> the possition-3 with aryl, alk<strong>in</strong>yl,<br />
and v<strong>in</strong>yl rests, were obta<strong>in</strong>ed (Figure 1). [3]<br />
Figure 1. Synthesis of 1-deazapur<strong>in</strong>es and isosteres bear<strong>in</strong>g the exocyclic nitrogen<br />
[1] a) W. B. Parker, Chem. Rev. 2009, 2880; b) P. G. Baraldi, M. A. Tabrizi, S. Gessi, P. A.<br />
Borea, Chem. Rev. 2008, 238.<br />
[2] a) S. Mkrtchyan, V. O. Iaroshenko, S. Dudk<strong>in</strong>, A. Gevorgyan, M. Vilches-Herrera, G. Ghazaryan,<br />
D. Volochnyuk, D.Ostrovskyi, Z. Ahmed, A. Vill<strong>in</strong>ger, V.Y. Sosnovskikh, p. Langer, Org.<br />
Biomol. Chem. 2010, 5280; b) V. O. Iaroshenko, S. Mkrtchyan, A. Gevorgyan, M. Vilches-<br />
Herrera, D. V. Sevenard, A. Vill<strong>in</strong>ger, T. V. Ghochikyan, A. Saghiyan, V. Ya. Sosnovskikh, P.<br />
Langer, Tetrahedron 2012, 2532.<br />
[3] V.O. Iaroshenko, M. Vilches-Herrera, A. Gevorgyan, S. Mkrtchyan, K. Arakelyan, D. Ostrovskyi,<br />
S. A. A. Muhammad, L. Supe, A. Hakobyan, A. Vill<strong>in</strong>ger, D.M. Volochnyuk, A. Tolmachev,<br />
Tetrahedron <strong>2013</strong>, <strong>in</strong> press, DOI: 10.1016/j.tet.2012.11.026.<br />
200 Saturday 9:00 - 11:30 Poster 143
A Trispyrazolylborato Iron Cyste<strong>in</strong>ato Complex as a<br />
Functional Model for the Cyste<strong>in</strong>e Dioxygenase<br />
Madleen Sallmann, Christian Limberg<br />
Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 –<br />
12489 Berl<strong>in</strong> – GER<br />
madleen.sallmann@web.de<br />
The cyste<strong>in</strong>e dioxygenase (CDO) is a non-heme mononuclear iron enzyme that catalyzes<br />
the irreversible oxidation of cyste<strong>in</strong>e by dioxygen to yield cyste<strong>in</strong>e sulf<strong>in</strong>ic acid,<br />
which is the first major step <strong>in</strong> cyste<strong>in</strong>e catabolism <strong>in</strong> mammalian tissues. [1] While<br />
the function of many oxygenat<strong>in</strong>g non-heme iron enzymes could be successfully imitated<br />
with<strong>in</strong> the last decades us<strong>in</strong>g molecular model compounds, [2] to date there are<br />
hardly any reports <strong>in</strong> the literature on biomimetic models for the CDO.<br />
Unlike other mononuclear non-heme iron dioxygenases, the active sites of which typically<br />
conta<strong>in</strong> a 2-histid<strong>in</strong>e-1-carboxylate coord<strong>in</strong>ation motive, the iron ion of CDO is<br />
bound by three histid<strong>in</strong>e ligands. [1] To this unit, the substrate cyste<strong>in</strong>e coord<strong>in</strong>ates<br />
through the sulfur atom and the nitrogen atom as a chelat<strong>in</strong>g ligand.<br />
Here we present the successful coord<strong>in</strong>ation and dioxygenation of a protected cyste<strong>in</strong>ato<br />
ligand to a (His)3 Fe II analogue (see Scheme): [3] In complex [Tp Me,P h FeCysOEt],<br />
the Tp Me,P h ligand excellently mimics the (His)3-coord<strong>in</strong>ation sphere and also the<br />
function is simulated, as treatment with dioxygen ma<strong>in</strong>ly leads to cyste<strong>in</strong>e sulf<strong>in</strong>ic<br />
acid. 1 is thus the hitherto most realistic model for the active site of the CDO.<br />
[1] C. A. Joseph, M. J. Maroney, Chem. Commun. 2007, 3338-3349.<br />
[2] a) M. Costas, M. P. Mehn, M. P. Jensen, L. Que, Jr., Chem. Rev. 2004, 104, 939-986; b) W.<br />
Nam, Acc. Chem. Res. 2007, 40, 465-465; c) I. Siewert, C. Limberg, Chem. Eur. J. 2009, 15,<br />
10316-10328; d) S. Friedle, E. Reisner, S. J. Lippard, Chem. Soc. Rev. 2010, 39, 2768-2779.<br />
[3] M. Sallmann, I. Siewert, L. Fohlmeister, C. Limberg, C. Knispel, Angew. Chem. Int. Ed.<br />
2012, 51, 2234-2237.<br />
Poster 144 Saturday 9:00 - 11:30 201
Cell culture analysis of select<strong>in</strong>-b<strong>in</strong>d<strong>in</strong>g bioactive<br />
nanoparticles<br />
Isabella Tavernaro ∗ , Katja Tr<strong>in</strong>kaus † , Léa Bouche ‡ , Figen Beceren-Braun ⋄ ,<br />
Jens Dernedde ⋄ , Hans-Ulrich Reissig ‡ , Katr<strong>in</strong> Susanne Lips † , Sab<strong>in</strong>e Schlecht ∗<br />
∗ Institue of Inorganic and Analytical Chemistry – Justus Liebig University Giessen –<br />
He<strong>in</strong>rich-Buff-R<strong>in</strong>g 58 – 35392 Giessen – GER<br />
† Laboratory of Experimental Trauma Surgery – Justus Liebig University Giessen –<br />
Kerkrader Str. 9 – 35394 Giessen – GER<br />
‡ Institute of Organic Chemistry – FU Berl<strong>in</strong> – Takustr. 3 – 14195 Berl<strong>in</strong> – GER<br />
⋄ Institute of Laboratory Medic<strong>in</strong>e, Cl<strong>in</strong>ical Chemistry and Pathobiochemistry –<br />
Charité Berl<strong>in</strong> – H<strong>in</strong>denburgdamm 30 – 12203 Berl<strong>in</strong> – GER<br />
Isabella.Tavernaro@Anorg.chemie.uni-giessen.de<br />
Interest <strong>in</strong> nanoparticles and their possible use <strong>in</strong> medical applications has significantly<br />
<strong>in</strong>creased <strong>in</strong> recent years. Although still at the beg<strong>in</strong>n<strong>in</strong>g of its development, first<br />
successful results <strong>in</strong>dicate the great potential of this research area.<br />
Some ligands tend to b<strong>in</strong>d only weakly to their complementary receptors <strong>in</strong> biological<br />
systems. Stronger b<strong>in</strong>d<strong>in</strong>g or enhanced <strong>in</strong>hibition can be achieved by the use of<br />
multivalent <strong>in</strong>teractions. [1] Due to their remarkably high surface-to-volume ratio <strong>in</strong><br />
comb<strong>in</strong>ation with their high stability, nanoparticles are well suited as templates for<br />
the multivalent presentation of functional groups. Because of this, they are used <strong>in</strong><br />
this project for the immobilization of potential select<strong>in</strong>-<strong>in</strong>hibitors. Select<strong>in</strong>s are a<br />
natural class of carbohydrate b<strong>in</strong>ders, and play an essential role <strong>in</strong> the <strong>in</strong>flammation<br />
process.<br />
We synthesized water-soluble and biocompatible nanoparticles of different sizes with a<br />
term<strong>in</strong>ally functionalized organic thiol shell, to present multivalently select<strong>in</strong> ligands<br />
to the respective lect<strong>in</strong>s. This multivalent presentation of select<strong>in</strong>-b<strong>in</strong>d<strong>in</strong>g structures<br />
led to highly improved b<strong>in</strong>d<strong>in</strong>g properties compared to the monovalent structures. [2]<br />
Tests were conducted to <strong>in</strong>vestigate the behavior of the functionalized nanoparticles<br />
<strong>in</strong> cell cultures.<br />
[1] G. M. Whitesides et al. Angew. Chem. 1998, 110, 2908-2953.<br />
[2] M. Roskamp et al. Org Biomol. Chem. 2011, 9, 7448-7456.<br />
202 Saturday 9:00 - 11:30 Poster 145
A new approach to α-(trifluoromethyl)benzyl substituted<br />
oxazirid<strong>in</strong>es<br />
Greta Utecht, Emilia Obijalska, Grzegorz Mlostoń<br />
Organic and Applied Chemistry – University of Lodz, Faculty of Chemistry –<br />
Tamka 12 – Lodz – POL<br />
gretautecht@gmail.com<br />
The chemistry of organofluor<strong>in</strong>e compounds is <strong>in</strong>tensively developed part of modern<br />
organic chemistry. Insertion of fluor<strong>in</strong>e atoms to the molecules causes significant<br />
changes <strong>in</strong> their chemical, biological and physical properties, <strong>in</strong> comparison with<br />
their nonfluor<strong>in</strong>ated analogues. [1,2] Perfluor<strong>in</strong>ated oxazirid<strong>in</strong>es were used as powerful<br />
oxidation agents. [3]<br />
The synthesis of new, N -substituted oxazirid<strong>in</strong>es 3,4 bear<strong>in</strong>g an α-(trifluromethyl)benzyl<br />
substituent at C(3) was achieved by m-CPBA oxidation of the correspond<strong>in</strong>g<br />
α-hydroxy-α-(trifluoromethyl)benzyl im<strong>in</strong>es 1,2 and their trimethylsilyl protected<br />
derivatives, respectively. In all cases, mixtures of diastereoisomers were formed. Result<strong>in</strong>g<br />
compounds 3,4 were used <strong>in</strong> the model reaction of oxidation of tioanisole to<br />
mono-S-oxide.<br />
R 1 =Ph, p-MeOC6H4, p-NO2C6H4R 2 =t-Bu, i-Pr<br />
[1]<br />
P. Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, We<strong>in</strong>heim, Germany, 2004.<br />
[2]<br />
L. Carroccia, S. Fioravanti, L. Pellacani, C. Sadun, P.A. Tardella, Tetrahedron 2011, 67,<br />
5375-5381.<br />
[3]<br />
V.A. Petrov, G. Resnati, Chemical Reviews 1996, 96 (5), 1809-1823.<br />
Authors thank the National Science Center (Poland) for f<strong>in</strong>ancial support (Grant ‘SONATA’ #<br />
DEC-2011/03/D/ST5/05231)<br />
Poster 146 Saturday 9:00 - 11:30 203
Cisplat<strong>in</strong>–COX Inhibitor Conjugates<br />
Wilma Neumann, Evamarie Hey-Hawk<strong>in</strong>s<br />
Institute of Inorganic Chemistry – Universität Leipzig – Johannisallee 29 –<br />
04103 Leipzig – GER<br />
wilma.neumann@chemie.uni-leipzig.de<br />
Cisplat<strong>in</strong> is one of the most widely used drugs <strong>in</strong> the treatment of cancer. However,<br />
conventional plat<strong>in</strong>um-based chemotherapy is often associated with strong side<br />
effects, and the efficacy of anti-tumour drugs is strongly limited by <strong>in</strong>tr<strong>in</strong>sic and<br />
treatment-<strong>in</strong>duced resistance of tumour cells. An enzyme which is overexpressed <strong>in</strong><br />
several tumour tissues and is <strong>in</strong>volved <strong>in</strong> tumour onset and progression is COX-2,<br />
an isoform of cyclooxygenase (COX). [1] Cl<strong>in</strong>ical studies revealed that target<strong>in</strong>g the<br />
COX-2 pathway is a promis<strong>in</strong>g strategy for the prevention and treatment of tumours.<br />
Furthermore, promis<strong>in</strong>g results were obta<strong>in</strong>ed with comb<strong>in</strong>atorial treatments with<br />
chemotherapeutic agents, such as cisplat<strong>in</strong>, and COX <strong>in</strong>hibitors. [2]<br />
These observed synergistic effects could be improved by comb<strong>in</strong><strong>in</strong>g both molecules <strong>in</strong><br />
one compound. A covalent bond between the chemotherapeutic agent and the COX<br />
<strong>in</strong>hibitor should ensure a concerted transport of the drugs through the body and<br />
uptake <strong>in</strong>to tumour cells. Furthermore, b<strong>in</strong>d<strong>in</strong>g of the coupled COX <strong>in</strong>hibitor at COX-<br />
2 could prevent an efflux of the plat<strong>in</strong>um complex. Besides an <strong>in</strong>creased accumulation<br />
of the drugs <strong>in</strong> the tumour cells, coupl<strong>in</strong>g of cisplat<strong>in</strong> with COX <strong>in</strong>hibitors could<br />
further enhance the efficacy of the chemotherapeutic agent by enabl<strong>in</strong>g a simultaneous<br />
action of both drugs <strong>in</strong> COX-2 overexpress<strong>in</strong>g tumour cells.<br />
[1] N. Ghosh, R. Chaki, V. Mandal, S. C. Mandal, Pharmacol. Rep. 2010, 62, 233-244.<br />
[2] M. Og<strong>in</strong>o, S. M<strong>in</strong>oura, Int. J. Cl<strong>in</strong>. Oncol. 2001, 6, 84-89.<br />
204 Saturday 9:00 - 11:30 Poster 147
Metal-Free Iod<strong>in</strong>e(III)-Promoted Direct Intermolecular<br />
C-H-Am<strong>in</strong>ation Reactions of Acetylenes<br />
Peter Becker, José A. Souto, Álvaro Iglesias, Kilian Muñiz<br />
ICIQ – Av. Països Catalans 16 – Tarragona – ESP<br />
peter.becker1@rwth-aachen.de<br />
Ynamides represent a unique build<strong>in</strong>g block for organic synthesis and they have been<br />
referred to as a modern functional group. [1,2] The synthesis of ynamides through<br />
a direct CN bond form<strong>in</strong>g process between amides and acetylenes is an attractive<br />
method. This has been reported us<strong>in</strong>g copper <strong>in</strong> either stoichiometric or catalytic<br />
amounts, however, more efficient metal-free processes are needed for the preparation<br />
of ynamides. [3-5]<br />
A particularly <strong>in</strong>terest<strong>in</strong>g preparation of ynamides was reported by Stang, [5] us<strong>in</strong>g hypervalent<br />
iod<strong>in</strong>e(III) chemistry. [6] The reaction requires the formation of acetylenyl<br />
iodonium(III) salts 1 and suitable nitrogen nucleophiles, usually <strong>in</strong> their metallated<br />
form, which react <strong>in</strong> a Michael-type addition followed by aryl migration to form the<br />
correspond<strong>in</strong>g ynamide product. [7] This method suffers from limitations such as the<br />
need to <strong>in</strong>dividually perform both metallated amides and acetylenyl iodonium(III)<br />
salts 1.<br />
Here, we present the development of an alternative, direct, metal-free oxidative C(sp1)-<br />
N bond form<strong>in</strong>g reaction us<strong>in</strong>g economically <strong>in</strong>terest<strong>in</strong>g term<strong>in</strong>al acetylenes and def<strong>in</strong>ed<br />
hypervalent iod<strong>in</strong>e(III) reagents. [8] This method provides a simple, rapid and<br />
robust protocol for the synthesis of a diverse series of ynamides <strong>in</strong> a s<strong>in</strong>gle-step<br />
operation. [9]<br />
[1]<br />
K. A. DeKorver, A. G. Lohse, R. Hayashi, Z. Lu, Y. Zhang, R. P. Hsung, Chem. Rev. 2010,<br />
110, 5064.<br />
[2] [1]<br />
For reviews see and (a) G. Evano, A. Coste, K. Jouv<strong>in</strong>, Angew. Chem. Int. Ed. 2010,<br />
49, 2840; (b) J. A. Mulder, K. C. M. Kurtz, R. P. Hsung, Synlett2003 , 1379; (c) C. A. Zificsak,<br />
J. A. Mulder, R. P. Hsung, C. Rameshkumar, L.-L. Wei, Tetrahedron 2001, 57, 7575.<br />
[3]<br />
T. Hamada, X. Ye, S. S. Stahl, J. Am. Chem. Soc. 2008, 130, 833.<br />
[4]<br />
A. Laouiti, M. M. Rammah, M. B. Rammah, J. Marrot, F. Couty, G. Evano, Org. Lett. 2012,<br />
14, 6.<br />
[5]<br />
(a) C. Zhang, N. Jiao, J. Am. Chem. Soc. 2010, 128, 28; (b) W. Jia, N. Jiao, Org. Lett.<br />
2010, 12, 2000.<br />
[6]<br />
P. Murch, B. L. Williamson, P. J. Stang, Synthesis 1994, 1255.<br />
[7]<br />
For a review on the chemistry of hypervalent acetylenyl iod<strong>in</strong>e(III) reagents see: V. V. Zhdank<strong>in</strong>,<br />
P. J. Stang, Tetrahedron 1998, 54, 10927.<br />
[8]<br />
For chemistry of hypervalent iod<strong>in</strong>e(III) reagents see: (a) V. V. Zhdank<strong>in</strong>, P. J. Stang, Chem.<br />
Rev. 2008, 108, 5299; (b) V. V. Zhdank<strong>in</strong>, P. J. Stang, Chem. Rev. 2002, 102, 2523; (c) P. J.<br />
Stang, V. V. Zhdank<strong>in</strong>, Chem. Rev. 1996, 96, 1123; (j) M. Ochiai, Chem. Rec. 2007, 7, 12; (l)<br />
M. S. Yusubov, A. V. Maskaev, V. V. Zhdank<strong>in</strong>, Arkivoc 2011, 1, 370.<br />
[9]<br />
J. A. Souto, P. Becker, Á. Iglesias, K. Muñiz, J. Am. Chem. Soc. 2012, 134, 15505.<br />
Poster 148 Saturday 9:00 - 11:30 205
Am<strong>in</strong>omethylphosphonic Systems Bear<strong>in</strong>g 5-membered<br />
Heteroaromatic Moiety and Their Properties<br />
Agnieszka Matusiak ∗ , Jarosław Lewkowski ∗ , Anna Agnieszka Klimczak † ,<br />
Janusz Szemraj † , Piotr Rychter ‡ , Robert Biczak ‡<br />
∗ Department of Organic Chemistry, Faculty of Chemistry – University of Lodz –<br />
Tamka 12 – Lodz – POL<br />
† Department of Medic<strong>in</strong>al Biochemistry – Medical University of Lodz –<br />
Mazowiecka 6/8 – Lodz – POL<br />
‡ Environment Protection and Biotechnology – Jan Dlugosz University –<br />
13/15 Armii Krajowej Av. – Czestochowa – POL<br />
agusk@poczta.fm<br />
Several N -aryl substituted am<strong>in</strong>ophosphonates have been synthesized s<strong>in</strong>ce a last<br />
decade [1,2] and our scientific group has contributed to this topic too. [3] Kraicheva et al.<br />
have reported recently that diethyl N -4-methylphenylam<strong>in</strong>o(2-furyl)methylphosphonate<br />
showed <strong>in</strong> vitro action towards several tumor cell l<strong>in</strong>es. [4] Therefore, we synthesized<br />
several new N -aryl-substituted am<strong>in</strong>omethyl phosphonates derived from furanic series<br />
<strong>in</strong> hope of their cytostatic activity.<br />
Am<strong>in</strong>ophosphonates 4e-g and im<strong>in</strong>es 2a-f were analyzed <strong>in</strong> the viewpo<strong>in</strong>t of <strong>in</strong>fluence<br />
on cancer cell l<strong>in</strong>es. For the experiments, KYSE 30, KYSE 150 and KYSE 270,<br />
esophageal cancer cell l<strong>in</strong>es were chosen and immortalized esophageal cell l<strong>in</strong>e HET 1<br />
A was used as a control group. Toxicity was evaluated us<strong>in</strong>g the MTT assay. Among<br />
our 12 am<strong>in</strong>ophosphonates a few of them were found to be cytotoxic, but only 4a<br />
had IC50 lower than 100 µM and acted as a potential cancer drug. SAR studies were<br />
attempted.<br />
In this communication, we will present results of these pharmacological studies.<br />
Moreover some of the im<strong>in</strong>es showed <strong>in</strong>terest<strong>in</strong>g biological properties. It demonstrated<br />
significant phytotoxicity parameters for radish (Raphanus sativus) and oats (Avena)<br />
after add<strong>in</strong>g the appropriate amounts of im<strong>in</strong>es to the soil.<br />
Reactions of Schiff bases 2a–f with phosphites 3a–c.<br />
[1]<br />
X.-J. Mu, M.-Y. Lei, J.-P. Zou, W. Zhang, Tetrahedron Lett. 2006, 47, 1125-1127.<br />
[2]<br />
S. Chandrasekhar, S. Jaya Prakash, Tetrahedron Lett. 2001, 42, 5561-5563.<br />
[3]<br />
A. A. Klimczak, A. Kuropatwa, J. Lewkowski, Szemraj, J. Med. Chem. Res. 2012, 21, DOI<br />
10.1007/s00044-012-0065-3.<br />
[4]<br />
I. Kraicheva, A. Bogomilova, I. Tsacheva, Europ. J. Med. Chem. 2009, 44, 3363-3367.<br />
206 Saturday 9:00 - 11:30 Poster 149
Stereoselective Am<strong>in</strong>e-Catalyzed Elongation of unprotected<br />
Carbohydrates<br />
Benjam<strong>in</strong> Voigt, Anastassia Matviitsuk, Ra<strong>in</strong>er Mahrwald<br />
Institute of Chemistry – Humboldt-University Berl<strong>in</strong> – Brook-Taylor-Str. 2 – Berl<strong>in</strong> –<br />
GER<br />
voigtbex@chemie.hu-berl<strong>in</strong>.de<br />
Cha<strong>in</strong> elongated carbohydrates - higher carbon sugars - are important compounds<br />
with biologically fundamental properties. Nature realizes these important transformations,<br />
apparently effortless, through a deployment of dist<strong>in</strong>ctly work<strong>in</strong>g aldolases<br />
and ketolases with extremely high degrees of stereoselectivity. However this high<br />
specificity is limited to a small number of substrates. Also, not all possible stereoisomers<br />
can be accessed by enzymatic transformations.<br />
We have developed an organocatalyzed aldol addition of unprotected carbohydrates<br />
to 1.3-dicarbonyl compounds without us<strong>in</strong>g the classical tedious protect<strong>in</strong>g and deprotect<strong>in</strong>g<br />
procedure. In addition condensation reaction and subsequently rearrangements<br />
are avoided follow<strong>in</strong>g this protocol.<br />
These <strong>in</strong>vestigations show great advantages <strong>in</strong> terms of time and atom economy. Also,<br />
this operationally simple transformation mimics aldolase-catalyzed transformations,<br />
which were identified <strong>in</strong> many biochemical processes. Further optimization and enlargement<br />
of this methodology to more general C-C bond formation processes of<br />
unprotected carbohydrates are under way.<br />
[1] Benjam<strong>in</strong> Voigt, Ulf Scheffler, Ra<strong>in</strong>er Mahrwald, Chem. Commun. 2012, 48, 5304-5306<br />
Poster 150 Saturday 9:00 - 11:30 207
Unexpected transformation of diarylethenes <strong>in</strong>duced by<br />
secondary am<strong>in</strong>es<br />
Dmytro Sysoiev ∗ , Ulrich Groth ∗ , Elke Scheer †<br />
∗ Chemistry – Konstanz University – Universitätsstr., 10 – Konstanz – GER<br />
† SFB 767 – Konstanz University – Universitätsstr., 10 – Konstanz – GER<br />
sonder83@mail.ru<br />
Diarylethenes can undergo a reversible transformation between two geometrically and<br />
electronically different states by irradiation at different wavelengths. In general, the<br />
"open" state is a mixture of rotamers, which turns <strong>in</strong>to diastereomers <strong>in</strong> "closed"<br />
state <strong>in</strong> UV light and forms by-products by further cont<strong>in</strong>uous irradiation. When<br />
condensat<strong>in</strong>g malononitrile and difurylethene bear<strong>in</strong>g an aldehyde group with piperid<strong>in</strong>e<br />
as a catalyst, our attention was drawn to an unusual colour change of the reaction<br />
mixture to deep purple. Successful isolation of reproducibly formed new product and<br />
its structure analysis allowed us to suggest an irreversible cyclization pathway for<br />
diarylethenes <strong>in</strong> absence of irradiation.<br />
208 Saturday 9:00 - 11:30 Poster 151
Synthesis of a Tripodal Germanium Based Ligand Precursor<br />
and its Reactivity at Ruthenium<br />
Roy Herrmann, Thomas Braun<br />
Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Straße 2 – Berl<strong>in</strong> –<br />
GER<br />
roy.herrmann@chemie.hu-berl<strong>in</strong>.de<br />
The design of podand-type ligand backbones often allows an elaborated adjustment<br />
of their steric and electronic properties at the metal center to provide a high flexibility<br />
and versatility at the ligand backbone. Examples for heavier group 14 elements <strong>in</strong><br />
the backbone of tetradentate tripodal ligands are rare, whereas tetradentate tripodal<br />
ligands with group 13 and 15 elements as backbone atoms are well established. [1]<br />
The reaction of the germane [Ge(H)(2-C6H4PPh2)3] with [Ru(Cl)2(PPh3)3] <strong>in</strong> the<br />
presence of an excess of NEt3 results <strong>in</strong> the formation of the ruthenium complex<br />
[Ru(Cl)Ge(2-C6H4PPh2)3] (1) (Scheme 1), which bears the Ge(2-C6H4PPh2)3 entity<br />
as a tetradentate tripodal ligand. The Ge-Ru bond length of complex 1 is at the<br />
shorter end of Ge-Ru distances which are reported <strong>in</strong> the literature and the value<br />
is comparable to the Ge-Ru distances <strong>in</strong> a couple of known ruthenium germylene<br />
complexes.<br />
Treatment of complex 1 with HCl results <strong>in</strong> a cleavage of one of the Ge-C bonds to<br />
give the ruthenium complex [Ru(Cl)Ge(Cl)(2-C6H4PPh2)2(PPh3)] (2) (Scheme 1).<br />
Therefore, the podand-type ligand can be transformed <strong>in</strong>to a p<strong>in</strong>cer-type ligand. The<br />
Ge(Cl)(2-C6H4PPh2)2 unit represents a rare example for p<strong>in</strong>cer-type ligands with<br />
germanium <strong>in</strong> the backbone.<br />
Scheme 1: Formation and reactivity of ruthenium complex 1.<br />
[1] I. Kuzu, I. Krummenacher, J. Meyer, F. Armbruster, F. Breher, Dalton Trans. 2008, 5836-<br />
5865.<br />
Poster 152 Saturday 9:00 - 11:30 209
Approaches to synthesis of gold(III) carboxylate complexes<br />
Nailya Akhmadull<strong>in</strong>a ∗ , Aleksandra Borissova † , Oleg Shishilov ‡<br />
∗ Baikov Institute of Metallurgy and Material Science of RAS – Len<strong>in</strong>sky pr., 49 –<br />
Moscow – RUS<br />
† Nesmeyanov Institute of Organoelement Compounds of RAS – Vavilova st., 28 –<br />
Moscow – RUS<br />
‡ Kurnakov Institute of General and Inorganic Chemistry of RAS – Len<strong>in</strong>sky pr., 31 –<br />
Moscow – RUS<br />
nakhmadull<strong>in</strong>a@mail.ru<br />
There are two general approaches to synthesis of carboxylate complexes. The first<br />
one is reactions of b<strong>in</strong>ary carboxylates with different ligands. This approach is used<br />
for all noble metals exclud<strong>in</strong>g gold, s<strong>in</strong>ce gold b<strong>in</strong>ary carboxylates are very unstable<br />
compounds which are extremely difficult to isolate. The second approach is a substitution<br />
of other acido ligands by carboxylate groups. This reaction works perfectly for<br />
halide complexes if silver(I) carboxylate is used as a halide acceptor. The method is<br />
applicable for both gold(I) and gold(III) compounds.<br />
We tested different approaches to synthesis of gold(III) carboxylate complexes. First<br />
we tried to prepare gold(III) acetates us<strong>in</strong>g reaction of chlorides [(L)AuCl2]Cl (L<br />
= bipy and phen) with sodium acetate <strong>in</strong> glacial acetic acid at 80-100C. However,<br />
it was found that for complex with phenanthrol<strong>in</strong>e the reaction leads to significant<br />
rearrangement of gold coord<strong>in</strong>ation sphere and formation of [(phen)AuCl2][AuCl4]<br />
complex <strong>in</strong>stead of any carboxylate derivative.<br />
Four-coord<strong>in</strong>ated cationic gold(III) chloride complexes [(L)AuCl2]BF4 (L = bipy,<br />
phen) react with silver(I) carboxylate RCO2Ag (R = CH3, CMe3, CF3) <strong>in</strong> acetonitrile<br />
media giv<strong>in</strong>g correspond<strong>in</strong>g carboxylate derivatives [(L)Au(RCO2)2]BF4, which were<br />
fully characterized <strong>in</strong>clud<strong>in</strong>g X-Ray diffraction study of [(bipy)Au(CF3CO2)2]BF4.<br />
At the same time pseudo five-coord<strong>in</strong>ated gold(III) complexes LAuCl3 (where L =<br />
2,9-dimethyl-1,10-phenanthrol<strong>in</strong>e and 2,2’-bisqu<strong>in</strong>ol<strong>in</strong>e) do not form stable products<br />
<strong>in</strong> the reaction, most likely, due to unfavourable steric features of the proposed carboxylate<br />
compounds. F<strong>in</strong>ally, we carried out IR-spectroscopic studies for all the<br />
prepared complexes <strong>in</strong> order to expla<strong>in</strong> their stability and reactivity.<br />
We are grateful to the Council of the President of the Russian Federation for young<br />
scientists for f<strong>in</strong>ancial support (project 977.2012.3).<br />
Molecular structure of [(bipy)Au(CF3CO2)2]BF4<br />
210 Saturday 9:00 - 11:30 Poster 153
Push-Pull Chromophores with Planarized Triphenylam<strong>in</strong>e<br />
Donors<br />
Bett<strong>in</strong>a Gliemann, Michael Grunst, Milan Kivala<br />
Department of Chemistry and Pharamcy, Institute of Organic Chemistry I –<br />
Friedrich-Alexander-Universität Erlangen-Nürnberg – Henkestrasse 42 – Erlangen – GER<br />
bett<strong>in</strong>a.gliemann@chemie.uni-erlangen.de<br />
About 40 years ago, Hellw<strong>in</strong>kel and co-workers realized planarized triphenylam<strong>in</strong>e<br />
scaffolds by connect<strong>in</strong>g the three benzene r<strong>in</strong>gs of triphenylam<strong>in</strong>e via carbonyl- or<br />
dimethylmethylene-bridg<strong>in</strong>g units. [1] While numerous chromophores consist<strong>in</strong>g of triphenylam<strong>in</strong>e<br />
donors and various acceptors connected through a suitable π-conjugated<br />
l<strong>in</strong>ker have already been <strong>in</strong>vestigated <strong>in</strong> organic light emitt<strong>in</strong>g diodes (OLEDs) and<br />
dye-sensitized solar cells, such comb<strong>in</strong>ations <strong>in</strong>volv<strong>in</strong>g the bridged triphenylam<strong>in</strong>es as<br />
donors have not been thoroughly <strong>in</strong>vestigated yet. [2]<br />
Here, we report the synthesis and optoelectronic properties of a series of novel pushpull<br />
chromophores <strong>in</strong>volv<strong>in</strong>g the planar triphenylam<strong>in</strong>e donor decorated with various<br />
electron acceptors (A).<br />
Figure 1. Schematic set-up of synthesized push-pull chromophores.<br />
[1] a) D. Hellw<strong>in</strong>kel, M. Melan, Chem. Ber. 1971, 104, 1001-1016; b) Z. Fang, T.-L. Teo, L. Cai,<br />
Y.-H. Lai, A. Samoc, M. Samoc, Org. Lett. 2009, 11, 1-4.<br />
[2] a) Z. Jiang, T. Ye, C. Yang, D. Yang, M. Zhu, C. Zhong, J. Q<strong>in</strong>, D. Ma, Chem. Mater. 2011,<br />
23, 771-777; b) K. Do, D. Kim, N. Cho, S. Paek, K. Song, J. Ko, Org. Lett. 2012, 14, 222-225.<br />
Poster 154 Saturday 9:00 - 11:30 211
Novel Metallasilatrane Complexes: Neutral Monomers and<br />
Cationic Dimers<br />
Gisela Warncke, Jörg Wagler<br />
Inst. f. Anorg. Chem. – TU Bergakademie Freiberg – Leipziger Straße 29 –<br />
09596 Freiberg – GER<br />
Gisela.Warncke@chemie.tu-freiberg.de<br />
The first metallasilatrane complexes, which are group 14 relatives of the nowadays<br />
widely explored metallaboratrane compounds [1] , bear the <strong>in</strong>terest<strong>in</strong>g structural motif<br />
of a dative TM→Si bond. The first representatives of these methimazole-buttressed<br />
paddlewheel-shaped complexes (with TM = Ni 2+ , Pd 2+ , Pt 2+ ) [2] exhibited very poor<br />
solubility <strong>in</strong> various solvents, which causes difficulties for characterization (e.g. NMR<br />
spectroscopy) and potential applications (e.g. homogeneous catalysis) <strong>in</strong> solution.<br />
Hence, their special molecular structures and 29 Si NMR spectroscopic properties were<br />
established by crystal structure analyses, solid state NMR spectroscopy and quantum<br />
chemical calculations. [3]<br />
With the aid of bulkier substituents (such as t-butyl or 2,6-dimethylphenyl) at the<br />
silatrane cage the solubility of metallasilatrane complexes was enhanced remarkably.<br />
In addition to neutral monomeric molecules, upon replacement of the TM-bound<br />
anion these compounds can form dimeric dications. The unexpected TM···TM contact<br />
of the latter is unbridged and can be rationalized by the spatial demand of the<br />
substituent R 1 .<br />
[1] M. Spicer, J. Regl<strong>in</strong>ski Eur. J. Inorg. Chem. 2009, 1553.<br />
[2] a) J. Wagler, E. Brendler Angew. Chem. Int. Ed. 2010, 49, 624; b) J. Wagler, A. F. Hill, T.<br />
He<strong>in</strong>e Eur. J. Inorg. Chem. 2008, 4225.<br />
[3] L. A. Truflandier, E. Brendler, J. Wagler, J. Autschbach Angew. Chem. Int. Ed. 2011, 50,<br />
255.<br />
212 Saturday 9:00 - 11:30 Poster 155
Conjugates of ruthenium(II)-polypyridyl complexes with<br />
fluorene-based electron donors<br />
Ralf Albrecht, Christoph Tzschucke<br />
Department of Chemistry and Biochemistry – Freie Universität Berl<strong>in</strong> – Takustr. 3 –<br />
14195 Berl<strong>in</strong> – GER<br />
ralf.albrecht@fu-berl<strong>in</strong>.de<br />
Ruthenium(II)-polypyridyl complexes covalently attached to electron donor or electron<br />
acceptor units have been frequently used as model systems for light <strong>in</strong>duced electron<br />
transfer and charge separation. [1] We describe the synthesis of electron donor conjugates<br />
of ruthenium(II)-polypyridyl complexes. As ligands, substituted bipyrid<strong>in</strong>es<br />
were prepared by palladium-catalyzed direct arylation of pyrid<strong>in</strong>e N -oxides and subsequent<br />
reduction. [2]<br />
As electron donor, 9,9-diarylfluorenes, with different redox potentials were prepared<br />
and attached to the ruthenium(II) complex by an amide l<strong>in</strong>kage. Correlation of the<br />
redox potentials and the light <strong>in</strong>duced charge separation behavior will be discussed.<br />
Ruthenium(II)-polypyridyl complexe with fluorene-based electron donor.<br />
[1] D. Polyansky, D. Cabelli, J. T. Muckerman, E. Fujita, T. Koizumi, T. Fukushima, T. Wada, K.<br />
Tanaka, Angew. Chem. Int. Ed. 2007, 46, 4169; C. Herrero, B. Lassalle-Kaiser, W. Leibl, A.<br />
W. Rutherford, A. Aukauloo, Coord. Chem. Rev. 2008, 252, 456; A. Magnuson, M. Anderlund,<br />
O. Johansson, P. L<strong>in</strong>dblad, R. Lomoth, T. Polivka, S. Ott, K. Stensjö, S. Styr<strong>in</strong>g, V. Sundström,<br />
L. Hammarström, Acc. Chem. Res. 2009, 42, 1899.<br />
[2] S. Duric, C. C. Tzschucke, Org. Lett. 2011, 13, 2310.<br />
Poster 156 Saturday 9:00 - 11:30 213
Photophysical, Photochemical and BQ Quench<strong>in</strong>g Properties<br />
of Z<strong>in</strong>c Phthalocyan<strong>in</strong>es with Fused Extended Conjugation<br />
Gulsah Gumrukcu ∗ , Gulnur Keser Karaoglan ∗ , Ali Erdogmus ∗ , Ahmet Gul † ,<br />
Ulvi Avciata ∗<br />
∗ Chemistry – Technical University of Yildiz – Davutpasa / 34210 – Istanbul – TUR<br />
† Chemistry – Technical University of Istanbul – Maslak / 34469 – Istanbul – TUR<br />
gumrukcugulsah@hotmail.com<br />
Metallophthalocyan<strong>in</strong>es (MPcs) derivatives display <strong>in</strong>terest<strong>in</strong>g chemical and physical<br />
properties, so they have been studied extensively. [1] The PDT properties of the phthalocyan<strong>in</strong>e<br />
dyes are strongly <strong>in</strong>fluenced by the presence and nature of central metal<br />
ion and substituents <strong>in</strong>troduced on the periphery of the phthalocyan<strong>in</strong>es. Metallation<br />
of phthalocyan<strong>in</strong>e with transition metals gives dyes with short lifetimes. [1]<br />
The effects of substituents and solvents on the photophysical and photochemical parameters<br />
of z<strong>in</strong>c(II) phthalocyan<strong>in</strong>es conta<strong>in</strong><strong>in</strong>g four Schiff’s base substituents attached<br />
directly on peripheral positions are reported. The group effects on pheripheral<br />
position and the cont<strong>in</strong>ual conjugation of the phthalocyan<strong>in</strong>e molecules on the<br />
photophysical and photochemical properties are also <strong>in</strong>vestigated. General trends<br />
are described for photodegradation, s<strong>in</strong>glet oxygen and fluorescence quantum yields<br />
of these compounds <strong>in</strong> dimethylsulfoxide (DMSO), dimethylformamide (DMF) and<br />
tetrahydrofurane (THF). The fluorescence of the substituted z<strong>in</strong>c (II) phthalocyan<strong>in</strong>e<br />
complexes is effectively quenched by 1,4-benzoqu<strong>in</strong>one (BQ) <strong>in</strong> the solvents used.<br />
[1] C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyan<strong>in</strong>es, Properties and Applications, vols. 1–4,<br />
VCH, New York, 1989, 1993, 1996.<br />
[2] H. Ali, J. E. van Lier, Chem. Rev. 1999, 99, 2379.<br />
214 Saturday 9:00 - 11:30 Poster 157
The circular dichroism spectroscopy application for<br />
determ<strong>in</strong>ation of 2,2’-spirobi-1,3-benzodioxol derivates<br />
absolute configuration.<br />
Ewa Wrona, Mateusz Brela, Maria Owińska, Barbara Rys<br />
Department of Organic Chemistry – Faculty of Chemistry, Jagiellonian University –<br />
Ingardena 3 – Cracow – POL<br />
ewa.wrona@uj.edu.pl<br />
Circular dichroism is one of the methods for determ<strong>in</strong>ation the spiranes absolute configuation,<br />
<strong>in</strong>clud<strong>in</strong>g 2,2‘-spirobi-(1,3-benzodioxoles) and 2,2’-spirobi-(1,3-benzodioxol-<br />
4-carboxylic) acids, which obta<strong>in</strong>ed diastereoisomers, have been separated via fractional<br />
crystallization.<br />
For each of the compounds, several circular dichroism spectra had been computed<br />
(TD-DFT, B3LYP, 6-311G** ). In all cases two counter Cotton effects have been<br />
noticed. The wave length for both the effects (c.a. 200nm) is different to the one<br />
predicted (c.a. 230nm for π → π* benzoic acid transfer). Furthermore, an analysis<br />
of atomic orbitals <strong>in</strong>dicates, that the Cotton effects are not due to exciton coupl<strong>in</strong>g.<br />
Nevertheless, the bands observed still follow the correlation between the Cotton effects<br />
abundance and the chirality of molecule. Thus, hav<strong>in</strong>g based on the circular dichroism<br />
spectroscopy as well as computational chemistry calculations the determ<strong>in</strong>ation<br />
of synthetized compounds absolute configuration was possible.<br />
The CD spectra of (P)-2,2’-spirobi-(1,3-benzodioxol-4-carboxylic) acid<br />
N,N’-di-[(1S)-phenylethyl]amide; theoretical (left) and experimental (right)<br />
[1]<br />
J. Grochowski, M. Rutkowska, B. Rys, P. Serda, G. Snatzke, Chem. Ber. 1992, 125, 1837.<br />
[2]<br />
M. Clpas, N. Par<strong>in</strong>ello, C. Saá, J.A. Varela, S. Caccamese, C. Ros<strong>in</strong>i, Tetrahedron: Assymetry<br />
2006, 17, 1387.<br />
[3]<br />
N. Harada, K. Nakanishi, Circular dichroic spectroscopy - exciton coupl<strong>in</strong>g <strong>in</strong> organic chemistry,<br />
Mill Valey, CA: University Science Books, 1983.<br />
Poster 158 Saturday 9:00 - 11:30 215
Cycloadditions: Concerted vs Diradical Stepwise<br />
Mechanisms. The Case of Nitrones Dimerization<br />
David Roca-López , Tomás Tejero, Pedro Mer<strong>in</strong>o<br />
Dpto. de Síntesis y Estructura de Biomoléculas –<br />
Instituto de Síntesis Química y Catálisis Homogénea – Universidad de Zaragoza –<br />
C/ Pedro Cerbuna, 12 – Zaragoza – ESP<br />
drl@unizar.es<br />
The [3+2] cycloaddition reaction of olef<strong>in</strong>ic dipolarophiles with 1,3-dipoles, such as<br />
nitrile oxides or nitrones, is one of the best known and most widely used method for<br />
construct<strong>in</strong>g five-membered heterocycles. [1] Nitrile oxides easily dimerize to furoxans,<br />
and the mechanism of the process has been already elucidated. [2] However, the analogous<br />
process with nitrones is a rarely reported event witnessed previously <strong>in</strong> few cases<br />
for cyclic nitrones.<br />
Recently, the cyclodimerization of several six-membered nitrones was <strong>in</strong>vestigated, [3]<br />
but only configurational and conformational features of the dimers were studied, without<br />
shedd<strong>in</strong>g light on the mechanism, which rema<strong>in</strong>s <strong>in</strong> controversy. Especially, because<br />
the apparent dimerization process consists <strong>in</strong> an unfavored thermal [4π+4π]<br />
cycloadition reaction, and no <strong>in</strong>formation exists to date about the electronic and<br />
steric effects on dimerization of nitrones and the nature of the transition states for<br />
such a process.<br />
In this work, we report DFT studies (both open- and closed-shell) on the dimerization<br />
of nitrones, first on a simple model and after on the 2,3,4,5-tetrahydropyrid<strong>in</strong>e-1-oxide,<br />
us<strong>in</strong>g up to the PCM(dichloromethane)/M06–2X/cc–pVTZ level of calculation.<br />
Concerted closed-shell mechanism (left) versus stepwise open-shell one (middle and right).<br />
Acknowledgements:<br />
D. R.-L. thanks the Spanish M<strong>in</strong>istry of Education (MED) for a FPU-Predoctoral grant.<br />
The authors thank the computer resources from “Term<strong>in</strong>us” and technical assistance provided by<br />
the Institute for Biocomputation and Physics of Complex Systems (BIFI) - University of Zaragoza<br />
(UZ).<br />
References:<br />
[1] Synthetic applications of 1,3-dipolar cycloaddition chemistry toward heterocycles and natural<br />
products. A. Padwa, W. H. Pearson (Eds.). John Wiley & sons: New York. 2002.<br />
[2] Z.-X. Yu, P. Caramella, K. N. Houk, J Org. Chem. 2003, 125, 15420-15425.<br />
[3] S. A. Ali, A. Alsbaiee, M. I. M. Wazeer, Phys. Org. Chem. 2010, 23, 488-496.<br />
216 Saturday 9:00 - 11:30 Poster 159
1,8-Anthracene Bridged Ruthenium and Osmium V<strong>in</strong>yl<br />
Complexes as Possible Candidates for the Synthesis of<br />
Anisotropic Supramolecular Rectangles<br />
Daniel F<strong>in</strong>k, Evelyn Wuttke, Ra<strong>in</strong>er W<strong>in</strong>ter<br />
Fachbereich Chemie – Universität Konstanz – Universitätsstr. 10 – Konstanz – GER<br />
daniel.f<strong>in</strong>k@uni-konstanz.de<br />
Discrete supramolecular objects featur<strong>in</strong>g transition metal corners are <strong>in</strong> the focus<br />
of current <strong>in</strong>terest <strong>in</strong> the field of organometallic supramolecular chemistry. For the<br />
preparation of rectangular shaped molecular objects 1,8-disubstituted anthracenes<br />
are particularly suitable, because self-assembly of these molecular clips with bidentate<br />
bridg<strong>in</strong>g ligands such as bipyrid<strong>in</strong>es <strong>in</strong>evitably leads to the formation of the<br />
desired structures. P. J. Stang and coworkers have already <strong>in</strong>troduced these k<strong>in</strong>ds<br />
of supramolecular complexes <strong>in</strong> 2001 [1] and a lot of further <strong>in</strong>vestigations have been<br />
made ever s<strong>in</strong>ce. The obta<strong>in</strong>ed structures mostly conta<strong>in</strong> square planar Pt(II) or<br />
Pd(II) metal centers. However, there is no known example for an anisotropic structure<br />
up to now, due to the fact that the required experimental procedures appear to<br />
be far more challeng<strong>in</strong>g. Possible solutions might be the usage of partially protected<br />
precursors or a comb<strong>in</strong>ation of donor and acceptor molecules.<br />
Here<strong>in</strong> we report the synthesis of two promis<strong>in</strong>g candidates as molecular acceptor<br />
clips for the formation of asymmetric supramolecular rectangles. The complex<br />
[[RuCl(CO)(P i Pr3)2]2(µ-CH=CH-anthracen-CH=CH-1,8)] was obta<strong>in</strong>ed by a hydrometallation<br />
reaction. It was possible to isolate the <strong>in</strong>termediate [Ru(CH=CH-anthracen-C≡CH-1,8)Cl(CO)(P<br />
i Pr3)2] thereby enabl<strong>in</strong>g the synthesis of the novel heterobimetallic<br />
complex [RuCl(CO)(P i Pr3)2OsCl(CO)((P i Pr3)2(µ-CH=CH-anthracen-<br />
CH=CH-1,8)]. Despite the close structural similarity to a published complex [2] improved<br />
reversibilities of the redox processes are observed via cyclovoltammetric exam<strong>in</strong>ations,<br />
thus provid<strong>in</strong>g the possibility to perform spectroelectrochemical studies.<br />
These po<strong>in</strong>t to sizable electronic coupl<strong>in</strong>g between the different metal sites <strong>in</strong> the<br />
mixed-valent radical cations and, <strong>in</strong> agreement with the results EPR studies <strong>in</strong>dicate<br />
high ligand character of the correspond<strong>in</strong>g SOMOs. Furthermore, the experimental<br />
f<strong>in</strong>d<strong>in</strong>gs agree well with the results of accompany<strong>in</strong>g DFT calculations. [3]<br />
The vacant coord<strong>in</strong>ation sites located at the metal centers can be used to <strong>in</strong>troduce<br />
various donor functions lead<strong>in</strong>g to anisotropic molecular objects. Suitable donor clip<br />
molecules have yet to be found and are <strong>in</strong> the focus of further studies.<br />
[1]<br />
C. J. Kuehl, S. D. Huang, P. J. Stang, Journal of the American Chemical Society 2001,<br />
123, 9634-9641.<br />
[2]<br />
Y.-P. Ou, C. Jiang, D. Wu, J. Xia, J. Y<strong>in</strong>, S. J<strong>in</strong>, G.-A. Yu, S. H. Liu, Organometallics 2011,<br />
30, 5763-5770.<br />
[3]<br />
D. F<strong>in</strong>k Bachelor Thesis 2012.<br />
Poster 160 Saturday 9:00 - 11:30 217
Attempts synthesize new 3- and 4- (trifluoromethyl)<br />
azetid<strong>in</strong>-2-ones Staud<strong>in</strong>ger reaction conditions<br />
Rafal Kluza, Emilia Obijalska, Grzegorz Mloston<br />
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 –<br />
Lodz – POL<br />
rafal.kluza@gmail.com<br />
(Trifluoromethyl) azetid<strong>in</strong>-2-ones comb<strong>in</strong>e the unique physical, chemical, biological<br />
and synthetic utility result<strong>in</strong>g from the presence both of the CF3 group and the βlactam<br />
skeleton. For this reasons, compounds of this type functionalized with CF3<br />
group are an attractive class of substrates for use <strong>in</strong> organic synthesis, as well as<br />
substances with potential biological activity. The literature describes few examples of<br />
methods of preparation of azetid<strong>in</strong>-2-ones bear<strong>in</strong>g CF3 substituent at positions C(3)<br />
or C(4) <strong>in</strong> heterocyclic r<strong>in</strong>g.<br />
The ma<strong>in</strong> goal of presented study was to develop method for obta<strong>in</strong><strong>in</strong>g new 4 or 3-<br />
CF3-β-lactams with usage a start<strong>in</strong>g materials N-(tert-butylsulph<strong>in</strong>yl) im<strong>in</strong>e derivated<br />
from fluoral (1) and 3,3,3-trifluoropropionic acid (2).<br />
Preparation of racemic substrate 1 was unsuccessful. In each case, product was isolated<br />
<strong>in</strong> a appropriate hemiam<strong>in</strong>alan form. That is why, all reactions were carried out<br />
with commercially available (S)-1. Both used substrates 1 and 2 were not convenient<br />
reagents for preparation desired compounds <strong>in</strong> Staud<strong>in</strong>ger type reactions (with acid<br />
chlorides, carboxylic acids or α-diazoketones). Only <strong>in</strong> the case of condensation (S)-1<br />
with enolate anion generated from ethyl propionate gave 4 CF3-β-lactam.<br />
218 Saturday 9:00 - 11:30 Poster 161
N6 − α-Halogenacyl-derivatives of Sydnone Im<strong>in</strong>es<br />
Al<strong>in</strong>a S. Samarskaya, Il’ia A. Cherepanov, Valery N. Kal<strong>in</strong><strong>in</strong><br />
Chemistry of Organoelement Compounds –<br />
A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences –<br />
Vavilov St. 28, 119334 – Moskow – RUS<br />
loi_iver2003@list.ru<br />
Sydnone im<strong>in</strong>es are the most studied representatives of mesoionic heterocyclic compounds.<br />
Their synthesis and study<strong>in</strong>g of their properties are of great <strong>in</strong>terest because<br />
of broad spectrum of sydnone im<strong>in</strong>e’s pharmacological activity. Recently it was shown<br />
that sydnone im<strong>in</strong>es were effective exogenous donors of nitrogen oxide (NO) an unique<br />
<strong>in</strong>tracellular regulator of metabolism <strong>in</strong> liv<strong>in</strong>g organism.<br />
At the moment, there are only unitary examples of N6 − α-halogenacyl- derivatives<br />
of sydnone im<strong>in</strong>es at literature and their reactivity is virtually un<strong>in</strong>vestigated. The<br />
aim of our study was to fill these exist<strong>in</strong>g gaps <strong>in</strong> the chemistry of sydnone im<strong>in</strong>es.<br />
We have obta<strong>in</strong>ed a wide range of N6 − α-halogenacyl-derivatives of sydnone im<strong>in</strong>es<br />
1 by the featured way of the <strong>in</strong>teraction of chloroanhidrides of α-halogensubstituted<br />
carboxylic acids with sydnone im<strong>in</strong>es hydrochlorides.<br />
It has been shown that these derivatives 1 are smoothly <strong>in</strong>teract with different dialkylam<strong>in</strong>es<br />
(Scheme 1) and S-nucleophiles (Scheme 2).<br />
In addition, it has been shown that <strong>in</strong> case of N6 − α-(2-thio-3-cyanopyrid<strong>in</strong>es)acetylderivatives<br />
4 the course of the reaction of <strong>in</strong>tramolecular cyclisation (Thorpe-Ziegler<br />
reaction) <strong>in</strong> 3-am<strong>in</strong>othienopyrid<strong>in</strong>es 5 is possible <strong>in</strong> good-to-excellent yields (Scheme<br />
3).<br />
Thus, a wide range of novel representatives of sydnone im<strong>in</strong>es have b<strong>in</strong> obta<strong>in</strong>ed.<br />
These derivatives are of great <strong>in</strong>terest as potential pharmacological active compounds.<br />
Poster 162 Saturday 9:00 - 11:30 219
(Iso)qu<strong>in</strong>ol<strong>in</strong>ocoumar<strong>in</strong>s: a novel class of bright fluorescent<br />
dyes with large Stokes shift<br />
Maksim V. Sednev, Shamil Nizamov, Vladimir N. Belov, Stefan W. Hell<br />
Department of NanoBiophotonics – Max Planck Institute for Biophysical Chemistry –<br />
Am Fassberg 11 – Gött<strong>in</strong>gen – GER<br />
msednev@gwdg.de<br />
Dyes with large Stokes shifts (80–200 nm) are easy to detect, due to m<strong>in</strong>imal sensitivity<br />
losses caused by reabsorption of light. Large Stokes shifts also facilitate spectral<br />
separation of the emission signal from the scattered excitation light, as well<br />
as from the background fluorescence of biological samples, which usually exhibits<br />
only small Stokes shift. [1] Photostable and bright fluorescent dyes with large Stokes<br />
shifts are rare and only few of them commercially available. Nearly all of them<br />
conta<strong>in</strong> the coumar<strong>in</strong> fragment as a fluorophore. Recently, we reported the synthesis<br />
of 3-heteroarylcoumar<strong>in</strong>s emitt<strong>in</strong>g green light, possess<strong>in</strong>g Stokes shifts of ca.<br />
70 nm, and perform<strong>in</strong>g quite well <strong>in</strong> optical microscopy applications, <strong>in</strong> particular,<br />
super-resolution imag<strong>in</strong>g based on stimulated emission depletion (STED). [2] In the<br />
present study, we show that the Stokes shift can be nearly doubled by fusion of the<br />
coumar<strong>in</strong> system with the (iso)qu<strong>in</strong>ol<strong>in</strong>e r<strong>in</strong>g. For that, an ethene unit was <strong>in</strong>corporated<br />
between C-4 of the fluorophore and the pyrid<strong>in</strong>e r<strong>in</strong>g (compound 3). The new<br />
(iso)qu<strong>in</strong>ol<strong>in</strong>ocoumar<strong>in</strong>s 3 emit yellow or orange light and have the Stokes shifts of<br />
ca. 140 nm. They were prepared from organot<strong>in</strong> precursors 1 and bromoheteroarylcarbaldehydes<br />
2 us<strong>in</strong>g a Stille coupl<strong>in</strong>g reaction followed by cyclization of the <strong>in</strong>termediates<br />
<strong>in</strong> protic solvents and <strong>in</strong> the presence of a base. The large Stokes shifts<br />
and the good quantum yields <strong>in</strong> polar solvents (30 % <strong>in</strong> methanol) suggest that the<br />
modified (iso)qu<strong>in</strong>ol<strong>in</strong>ocoumar<strong>in</strong>s can be applied as photostable markers <strong>in</strong> multicolor<br />
STED microscopy.<br />
[1] F. Vollmer, W. Rettig, E. Birckner, J. Fluoresc. 1994, 4, 65-69.<br />
[2] S. Nizamov, K. I. Willig, M. V. Sednev, V. N. Belov, S. W. Hell, Chem. Eur. J. 2012, 18,<br />
16339-16348.<br />
220 Saturday 9:00 - 11:30 Poster 163
Simple new method of synthesis alkyl nitrites<br />
Tomasz Klucznik<br />
Department of Chemistry – Gdansk University of Technology – Narutowicza 11/12 –<br />
Gdansk – POL<br />
observer9@wp.pl<br />
Alkyl nitrites belong to a class of organic compounds with the general formula RONO,<br />
where R is an alkyl group. Thus, they are esters of nitrous acid. Alkyl nitrites are<br />
useful reagents for organic synthesis, an example for synthesis organic or <strong>in</strong>organic<br />
azides from compounds conta<strong>in</strong> hydraz<strong>in</strong>e group.<br />
Classic methods of synthesis alkyl nitrites [1-4] base on add drop by drop cool alcohol<br />
and acid solution to water solution of sodium or potassium nitrite. Nitrite solution<br />
are cool<strong>in</strong>g <strong>in</strong> water and br<strong>in</strong>e bath. Control of temperature and add<strong>in</strong>g reagents<br />
to reaction mixture are crucial parts of alkyl nitrites synthesis. High temperature<br />
favour hydrolysis and evaporation of f<strong>in</strong>al product. That the temperature control<br />
is so important. But us<strong>in</strong>g the bath cool<strong>in</strong>g <strong>in</strong> this case are <strong>in</strong>effective. Time of<br />
reaction are f<strong>in</strong>ally <strong>in</strong>acceptable long. Add<strong>in</strong>g too much acid <strong>in</strong> one pot, <strong>in</strong>iciate<br />
irreversible hydrolysis of alkyl nitrite. F<strong>in</strong>al products of hydrolysis alkyl nitrites are<br />
easy to identify reddish-brown nitrogen dioxide which leaves reaction mixture. That<br />
are most important problems connection with alkyl nitrite synthesis.<br />
My reply for that synthesis troubles are the new easy to implementation method of<br />
synthesis alkyl nitrites. The key ideas are cancellation cool bath and change form of<br />
sodium nitrite. I used the easiest self cooll<strong>in</strong>g mixture as ice blocks. Stoichiometric<br />
(1,1eq) solution of sodium or potassium nitrite was cool<strong>in</strong>g <strong>in</strong> the refrigerator as long<br />
as they are not freeze to cubes. That form of sensitive reagent has many advantages.<br />
Problem of add alcohol and acid solution is elim<strong>in</strong>ation too. Yields of this simply<br />
method are good or very good. The most important part of my solution are easy<br />
applicable to high scale production. Elim<strong>in</strong>ation add<strong>in</strong>g reagents <strong>in</strong> portions and self<br />
controlled temperature are promote this method to technology scale of production.<br />
Ryc.1. The difference between two methods of synthesis alkyl nitrites<br />
[1]<br />
R. Adams, O. Kamm, J. Am.<br />
organiczna 1984, WNT, 347-348.<br />
Chem. Soc. 1918, 40, 1285.<br />
[2]<br />
A. I. Vogel, Preparatyka<br />
[3]<br />
W. A. Noyes, Org. Synth. 1943, Coll. Vol. 2, 108; 1936, Vol. 16, 7.<br />
[4] R. A. Miller, Inorg. Synth. 1946, 2, 139.<br />
Poster 164 Saturday 9:00 - 11:30 221
Synthesis, structure and electrochemical properties of novel<br />
Co(III) complex with 2-acetylpyrid<strong>in</strong>e<br />
S-methylisothiosemicarbazone<br />
Marko Rodić, Mirjana Lalović, Ljiljana Voj<strong>in</strong>ović-Ješić, Ljiljana Jovanović,<br />
Vukad<strong>in</strong> Leovac<br />
Faculty of Sciences – University of Novi Sad – Trg Dositeja Obradovića 3 – Novi Sad –<br />
SRB<br />
marko.rodic@dh.uns.ac.rs<br />
2-acetylpyrid<strong>in</strong>e thiosemicarbazone and its N(4)-substituted derivatives have wide<br />
range of biological activity. This has been the ma<strong>in</strong> reason for <strong>in</strong>tensive study of this<br />
ligand group complexes with transition and non-transition metals. On the contrary, a<br />
limited number of transition metal complexes with 2-acetylpyrid<strong>in</strong>e S-methylisothiosemicarbazone<br />
(HL) is known, of which only few mono-ligand Cu(II) and bis-ligand<br />
Co(III) complexes have been characterized with X-ray analyses.<br />
The paper is concerned with the crystal structure and electrochemical characteristics<br />
of the cobalt(III) complex with 2-acetylpyrid<strong>in</strong>e S-methylisothiosemicarbazone<br />
(HL), of the coord<strong>in</strong>ation formula [CoL2][Co II pyCl3] · Me2CO. X-ray crystallography<br />
revealed that Co(III) is situated <strong>in</strong> a slightly deformed octahedral environment<br />
formed by six nitrogen atoms of the two L molecules <strong>in</strong> the meridional positions.<br />
The ligands molecules coord<strong>in</strong>ate with Co(III) <strong>in</strong> a usual way, i.e. via the pyrid<strong>in</strong>e,<br />
azometh<strong>in</strong>e, and isothioamide nitrogen atoms, each form<strong>in</strong>g two five-membered metallocycles.<br />
Electrochemical studies of the complex <strong>in</strong> DMF showed that the electrode<br />
processes are accompanied by chemical reactions and the correspond<strong>in</strong>g mechanism<br />
was proposed. The obta<strong>in</strong>ed complex was also characterized by elemental analysis,<br />
conductometric measurements and UV–Vis and IR spectroscopy.<br />
Molecular structure of the complex<br />
222 Saturday 9:00 - 11:30 Poster 165
Reactions of 3-acylchromones with dimethyl<br />
1,3-acetonedicarboxylate and 1,3-diphenylacetone: one-pot<br />
synthesis of functionalized 2-hydroxybenzophenones,<br />
6H-benzo[c]chromenes and benzo[c]coumar<strong>in</strong>s<br />
Iryna Savych, Alexander Vill<strong>in</strong>ger, Vyacheslav Sosnovskikh, Peter Langer,<br />
Viktor Iaroshenko<br />
Department of Chemistry – University of Rostock – Albert E<strong>in</strong>ste<strong>in</strong> Str. 3a – GER<br />
savychiryna@gmail.com<br />
Chromones are very attractive targets for comb<strong>in</strong>atorial library synthesis due to<br />
their wide range of valuable biological activities. [1] The biological and <strong>in</strong>dustrial<br />
importance of chromones has led to a considerable amount of synthetic work <strong>in</strong><br />
the field of 3-substituted chromones, especially 3-formylchromone [2] , which conta<strong>in</strong><br />
three electrophilic centers. We envisaged that <strong>in</strong>troduction of powerful electronwithdraw<strong>in</strong>g<br />
groups as methoxalyl, polyfluoroacyl and aroyl <strong>in</strong>to the 3-position of<br />
chromone would <strong>in</strong>crease its reactivity toward nucleophilic reagents. Unlike, these<br />
3-substituted chromones 1-3 have not received much attention despite their potential<br />
<strong>in</strong>terest as build<strong>in</strong>g blocks <strong>in</strong> organic synthesis via the reactions with 1,3-C,Cd<strong>in</strong>ucleophiles.<br />
A fact prompt<strong>in</strong>g us to <strong>in</strong>vestigate their reaction with dimethyl 1,3acetonedicarboxylate<br />
and 1,3-diphenylacetone.<br />
We are report<strong>in</strong>g now, that reactions of 3-substituted chromones 1-3 with dimethyl<br />
1,3-acetonedicarboxylate and 1,3-diphenylacetone <strong>in</strong> the presence of DBU proceed at<br />
the C-2 atom of the chromone system with pyrone r<strong>in</strong>g-open<strong>in</strong>g and subsequent formal<br />
[3+3] cyclocondensation and led to the formation of functionalized 2-hydroxybenzophenones,<br />
6H-benzo[c]chromenes and benzo[c]coumar<strong>in</strong>s, depend<strong>in</strong>g on the substituent<br />
at the 3-position (Figure 1). [3]<br />
The obta<strong>in</strong>ed products constitute an important structural subunit of a variety of<br />
biologically active compounds [4] , which are not readily available by other methods. In<br />
further experiments we studied the base-mediated hydrolysis of the products 4,5. It is<br />
also important to notice, that due to the strong UV-absorption properties synthesized<br />
products can f<strong>in</strong>d a use <strong>in</strong> the preparation of the sun-protective materials and creams.<br />
Figure 1. Synthesis of obta<strong>in</strong>ed products 4-7.<br />
[1] S. T. Saengchantara, T. W. Wallace, Nat. Prod. Rep. 1986, 465-475.<br />
[2] H. Chen, F. Xie, J. Gong, Y. Hu, J. Org. Chem. 2011, 76, 8495-8500.<br />
[3] Viktor O. Iaroshenko, Iryna Savych, Alexander Vill<strong>in</strong>ger, Vyacheslav Ya. Sosnovskikh, Peter<br />
Langer, Org. Biomol. Chem. 2012, 10, 9344-9348.<br />
[4] (a) T. Tzanova, M. Gerova, O. Petrov, M. Karaivanova, D. Bagrel, Eur. J. Med. Chem. 2009,<br />
44, 2724-2730; (b) R. W. Pero, D. Harvan, M. C. Blois, Tetrahedron Lett. 1973, 14, 945-948.<br />
Poster 166 Saturday 9:00 - 11:30 223
Direct reductive am<strong>in</strong>ation of methyl<br />
2-(2-formyl-4-nitrophenoxy)alkanoates. Synthesis of<br />
2-alkyl-1,4-benzoxazep<strong>in</strong>-3-ones.<br />
Agata Wrześniewska, Hal<strong>in</strong>a Kwiecień<br />
Department of Organic Synthesis and Drug Technology –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – 42 Piastów Ave. – Szczec<strong>in</strong> – POL<br />
awrzesniewska@zut.edu.pl<br />
Reductive am<strong>in</strong>ation is the reaction of aldehydes and ketones with ammonia or primary/secondary<br />
am<strong>in</strong>es <strong>in</strong> presence of a selective reduc<strong>in</strong>g agent. It is one of the most<br />
important tools <strong>in</strong> the synthesis of am<strong>in</strong>es. [1]<br />
Our previous research has shown that the reductive am<strong>in</strong>ation of methyl 2-(2-formylphenoxy)alkanoates<br />
with hydraz<strong>in</strong>e leads to the formation of correspond<strong>in</strong>g primary<br />
am<strong>in</strong>o esters, which immediately underwent cyclization to 1,4-benzoxazep<strong>in</strong>-3-ones. [2]<br />
1,4-Benoxazep<strong>in</strong>e derivatives are well-known as compounds possess<strong>in</strong>g antidepressant<br />
or antihistam<strong>in</strong>ic properties. [3]<br />
Here, we report the results of our study of direct reductive am<strong>in</strong>ation of methyl 2-<br />
(2-formyl-4-nitrophenoxy)alkanoates 1 to the correspond<strong>in</strong>g am<strong>in</strong>o esters 3 via Schiff<br />
base <strong>in</strong>termediates 2, followed by the cyclization of the obta<strong>in</strong>ed am<strong>in</strong>o esters to the<br />
1,4-bnzoxazep<strong>in</strong>-3-ones 4. The reductive am<strong>in</strong>ation process was carried out at ambient<br />
temperature with use of sodium triacetoxyborohydride as the selective reduc<strong>in</strong>g<br />
agent and 1,2-dichloroethane as the solvent (Figure 1). The process of obta<strong>in</strong><strong>in</strong>g<br />
1,4-benzoxazep<strong>in</strong>-3-ones by <strong>in</strong>tramolecular cyclization of N-arylated am<strong>in</strong>o esters 3<br />
took several attempts us<strong>in</strong>g a variety solvents, catalysts, and different reaction times.<br />
Optimal results were achieved when the am<strong>in</strong>o esters were heated for 6h at 200-205 o C.<br />
All am<strong>in</strong>o esters and 1,4-benzoxazep<strong>in</strong>-3-ones are new compounds and their structures<br />
were confirmed by spectroscopic methods.<br />
Figure 1. Synthesis of N -phenyl-2-alkyl-7-nitro-1,4-benzoxazep<strong>in</strong>-3-ones from methyl<br />
2-(2-formyl-4-nitrophenoxy)alkanoates.<br />
[1]<br />
S. Gomez, J. A. Peters, T. Maschmeyer, Adv. Synth. Catal. 2002, 344, 1037.<br />
[2]<br />
H. Kwiecień, M. Szychowska, Synth. Comm. 2007, 37, 3599.<br />
[3]<br />
H. Kwiecień, M. Śmist, A. Wrześniewska, Curr. Org. Synth. 2012, 9, 828.<br />
224 Saturday 9:00 - 11:30 Poster 167
Valence isomery <strong>in</strong> phenoxyl ferrocenyl radicals<br />
Andreas Neidl<strong>in</strong>ger, Katja He<strong>in</strong>ze<br />
Institute of Inorganic and Analytical Chemistry – Johannes Gutenberg-University –<br />
Duesbergweg 10-14 – Ma<strong>in</strong>z – GER<br />
neidl<strong>in</strong>g@uni-ma<strong>in</strong>z.de<br />
Electron transfer (ET) is one of the fundamental and most important phenomena <strong>in</strong><br />
chemistry and biology. Mixed-valence and mixed metal compounds are extremly valuable<br />
systems for study<strong>in</strong>g optically and thermally driven electron transfer reactions.<br />
We have been engaged <strong>in</strong> the synthesis of oligopeptides built from 1-am<strong>in</strong>oferrocene-<br />
1’-carboxylic acid [1] which can be oxidized to mixed-valent ferrocene/ferrocenium<br />
peptides. [2,3]<br />
Unlike ET between chemically similar moieties, ET between chemically different<br />
build<strong>in</strong>g blocks is less well explored, even though dissimilar redox partners play a<br />
crucial role <strong>in</strong> many biological ET systems, e.g. <strong>in</strong> photosystem II where phenoxyl<br />
radicals <strong>in</strong> the form of tyrosyl radicals are one of the central redox sites between the<br />
special pair P680 and the oxygen evolv<strong>in</strong>g complex. [4] Interest<strong>in</strong>gly, the formal redox<br />
potentials of the biologically relevant phenolate/phenoxyl pair and the organometallic<br />
ferrocene/ferrocenium pair can be very similar when us<strong>in</strong>g appropriate substituents.<br />
We have designed 2,4-di-tert-butyl-6-(2-ferrocenyl-carbamoyl)-phenol H-1, which, after<br />
deprotonation to 1 − , provides the chemically very different redox centers phenolate<br />
and ferrocene with similar redox potentials. [2,3,5]<br />
A priori it is not obvious which redox site of the dissymmetric phenolate-ferrocene<br />
conjugate 1 − will be oxidized <strong>in</strong> 1 . (valence ambiguity). The behavior of this system<br />
was probed by cyclic voltammograms, UV/Vis/NIR, IR and EPR spectroscopy under<br />
oxidiz<strong>in</strong>g and alkal<strong>in</strong>e conditions <strong>in</strong> different solvents. Density Functional Calculations<br />
were also performed <strong>in</strong> different solvents to <strong>in</strong>terpret the f<strong>in</strong>d<strong>in</strong>gs.<br />
[1] K. He<strong>in</strong>ze, M. Schlenker, Eur. J. Inorg. Chem. 2004, 2974-2988.<br />
[2] D. Siebler, M. L<strong>in</strong>seis, T. Gasi, L. M. Carrella, R. F. W<strong>in</strong>ter, C. Förster, K. He<strong>in</strong>ze, Chem.<br />
Eur. J. 2010, 17, 4540-4551.<br />
[3] D. Siebler, C. Förster, K. He<strong>in</strong>ze, Dalton Trans. 2011, 40, 3558-3575.<br />
[4] J. M. Mayer, I. J. Rhile, F. B. Larsen, E. A. Mader, T. F. Markle, A. G. DiPasquale, Photosynthesis<br />
Research 2006, 87, 3–20.<br />
[5] R. Wanke, L. Benisvy, M. L. Kuznetsov, M. F. C. Guedes da Silva, A. J. L. Pombeiro, Chem.<br />
Eur. J. 2011, 17, 11882-11892.<br />
Poster 168 Saturday 9:00 - 11:30 225
Lacunary dodecavanadate clusters: Versatile build<strong>in</strong>g blocks<br />
for transition metal functionalized polyoxovanadates<br />
Kathar<strong>in</strong>a Kastner, Carsten Streb<br />
Department Chemie und Pharmazie –<br />
Friedrich-Alexander-Universität Erlangen-Nürnberg – Egerlandstraße 1 – Erlangen –<br />
GER<br />
ka.kastner@gmx.de<br />
Polyoxometalates (POMs) are metal oxide clusters based on high-valent early transition<br />
metals such as Mo, W or V. [1] Reactivity as well as wide structural diversity<br />
make POMs <strong>in</strong>terest<strong>in</strong>g candidates for applications <strong>in</strong> areas such as electronic and<br />
magnetic molecular materials, catalysis, medic<strong>in</strong>e and materials science. [2] Despite<br />
the wide structural variety of POM clusters, the targeted synthesis of a cluster framework<br />
for specific applications is still a huge challenge as formation mechanisms are<br />
hard to predict and control. Here, we present a promis<strong>in</strong>g route which enables us to<br />
access a new family of transition-metal substituted polyoxovanadate clusters through<br />
targeted syntheses with predictable outcome. A novel, chloride- templated dodecavanadate<br />
cluster featur<strong>in</strong>g two hexagonal coord<strong>in</strong>ation sites was developed based our<br />
earlier work on cluster assembly under non-aqueous conditions. [3] The cluster is used<br />
as a molecular host for the b<strong>in</strong>d<strong>in</strong>g of a wide range of transition metals whilst reta<strong>in</strong><strong>in</strong>g<br />
the orig<strong>in</strong>al cluster framework. The concept is closely related to the classical<br />
use of organic ligands, allow<strong>in</strong>g us to consider the dodecavanadate cluster as stable,<br />
purely <strong>in</strong>organic ligands. The modification of the physical properties and electronic<br />
and magnetic structure of transition-metal substituted clusters are explored and selective<br />
metal substitution will be employed for the development of stable and highly<br />
active molecular catalysts.<br />
Figure 1 Reaction scheme of the syntheses of transition metal (Fe, Co, Cu) conta<strong>in</strong><strong>in</strong>g<br />
polyoxovanadate clusters start<strong>in</strong>g with a chloride templated dodecavanadate cluster as a<br />
molecular host.<br />
[1]<br />
M. T. Pope, Y. Jeann<strong>in</strong>, M. Fournier, Heteropoly and isopoly oxometalates, Spr<strong>in</strong>ger-Verlag<br />
Berl<strong>in</strong>, 1983.<br />
[2]<br />
Special polyoxometalate issue: L. Cron<strong>in</strong>, A. Müller (guest eds.), Chem. Soc. Rev. 2012,<br />
7325-7648.<br />
[3]<br />
(a) J. Tucher, L. C. Nye, I. Ivanovic-Burmazovic, A. Notarnicola, C. Streb, Chem. Eur. J.<br />
2012, 18, 10494-10453; (b) J. Forster, B. Rösner, R. H. F<strong>in</strong>k, L. C. Nye, I. Ivanovic-Burmazovic,<br />
K. Kastner, J. Tucher, C. Streb, Chem. Sci. <strong>2013</strong>, DOI: 10.1039/c2sc20942j; (c) K. Kastner, B.<br />
Puscher, C. Streb, Chem. Commun. <strong>2013</strong>, DOI:10.1039/C2CC36638J.<br />
226 Saturday 9:00 - 11:30 Poster 169
Advanced materials <strong>in</strong> controlled drug delivery systems<br />
Anna Dabrowska, Marta Gawel, Agnieszka Kierys<br />
Department of Adsorption – Faculty of Chemistry,Maria Curie-Sklodowska University –<br />
Pl. M. Curie-Sklodowskiej 3, 20-031 – Lubl<strong>in</strong> – POL<br />
dabrowska.umcs@gmail.com<br />
Multi-component <strong>in</strong>organic/organic composites have attracted great <strong>in</strong>terest as a new<br />
class of porous solids with potential application <strong>in</strong> gas separation, catalysis, drug<br />
delivery systems or host for <strong>in</strong>clusion compounds. The silica gel is considered to be a<br />
fasc<strong>in</strong>at<strong>in</strong>g and <strong>in</strong>terest<strong>in</strong>g material for many applications due to its porous <strong>in</strong>ternal<br />
structure and morphological characteristics. Therefore, the use of silica gel as fillers<br />
is grow<strong>in</strong>g <strong>in</strong> particular due to the silanol groups presence on its surface which make<br />
it easily modifiable with different functional groups.<br />
One can easily observe the development made <strong>in</strong> recent years <strong>in</strong> the areas of polymer<br />
science, biomaterials, composite systems, and other related fields which has resulted <strong>in</strong><br />
great medical and pharmaceutical progress. Particular significance is the progress that<br />
has been made <strong>in</strong> the areas of the controlled drug delivery systems. The undoubted<br />
advantage of these systems is the susta<strong>in</strong>ed release of a drug at a therapeutic level over<br />
the long period of time. As a consequence, the dos<strong>in</strong>g frequency can be considerably<br />
reduced without los<strong>in</strong>g of effectiveness of therapeutic activity. Therefore, a much<br />
attention and efforts are devoted to prepare a new materials which could be used <strong>in</strong><br />
the controlled drug delivery systems.<br />
It was demonstrated that the release of the drugs out of polymer-based carrier systems<br />
can be achieved by controll<strong>in</strong>g a simple diffusion process. [1] However, the effectiveness<br />
of such delivery systems, is limited by the e.g. stability, porosity or biocompatibility<br />
of the carriers network. Therefore, by us<strong>in</strong>g the polymer-silica composites as a<br />
drug carrier matrix the formation of an appropriate porosity and an improvement of<br />
stability of the polymeric network can be achieved.<br />
In this paper we present the polymer-silica composite which can serve as a carrier<br />
<strong>in</strong> drug release system. The composite was synthesised by the method which consist<br />
<strong>in</strong> swell<strong>in</strong>g of preformed porous polymer particles <strong>in</strong> tetraethoxysilane TEOS. [2,3] It<br />
has been shown that this composite exhibits a relatively high porosity with<strong>in</strong> both<br />
the polymer and silica component. Because of an <strong>in</strong>teraction between the system<br />
components dur<strong>in</strong>g the swell<strong>in</strong>g and the condensation of SiO2 <strong>in</strong> polymer matrix, the<br />
diffusion of the drug is significantly limited and can be controlled. We demonstrate<br />
the profiles of naproxen release and report on the composite system characteristics<br />
through porosity, TEM, SEM and NMR studies.<br />
[1] A. Bernkop-Schnürch, S. Scholler, R. G. and Biebel, “Development of controlled drug release<br />
systems based on polymer-cyste<strong>in</strong>e conjugates”, Journal of Controlled Release 2000, 66, 39.<br />
[2] R. Zaleski, A. Kierys, M. Grochowicz, M. Dziadosz, J. Goworek, “Synthesis and characterization<br />
of nanostructural polymer–silica composite: Positron annihilation lifetime spectroscopy study”,<br />
Journal of Colloid and Interface Science 2011, 358, 268.<br />
[3] R. Zaleski, A. Kierys, M. Dziadosz, J. Goworek, I. Halasz, “Positron annihilation and N2<br />
adsorption for nanopore determ<strong>in</strong>ation <strong>in</strong> silica-polymer composites”, RSC Advances 2012, 2,<br />
3729.<br />
Poster 170 Saturday 9:00 - 11:30 227
The physicochemical properties of novel porphyraz<strong>in</strong>es<br />
possess<strong>in</strong>g an alternate system of 2,5-dimethylpyrrol-1-yl and<br />
dimethyloam<strong>in</strong>o peripheral substituents<br />
Tomasz Koczorowski ∗ , Wojciech Szczolko ∗ , Lukasz Sobotta † , Marc<strong>in</strong> Wierzchowski ∗ ,<br />
Piotr Fita ‡ , Aleksandra Orzechowska ⋄ , Kvetoslava Burda ⋄ , Jadwiga Mielcarek † ,<br />
Tomasz Gosl<strong>in</strong>ski ∗<br />
∗ Department of Chemical Technology of Drugs – University of Medical Sciences –<br />
Grunwaldzka 6 – Poznan – POL<br />
† Department of Inorganic and Analytical Chemistry – University of Medical Sciences –<br />
Grunwaldzka 6 – Poznan – POL<br />
‡ Institute of Experimental Physics, Faculty of Physics – University of Warsaw –<br />
Hoza 69 – Warsaw – POL<br />
⋄ Faculty of Physics and Applied Computer Science –<br />
AGH University of Science and Technology – al. Mickiewicza 30 – Kracow – POL<br />
tkoczorowski@gmail.com<br />
Introduction<br />
For the last 30 years, porphyraz<strong>in</strong>es (Pzs) substituted at their β-positions with nitrogen,<br />
oxygen or sulfur residues have been synthesized and subjected to various<br />
physicochemical as well as biological studies. [1] Pzs have been <strong>in</strong>vestigated as potential<br />
photosensitizers for biomedical, analytical applications, and as compounds for<br />
materials chemistry. [2] Although, there are many examples of Pzs conta<strong>in</strong><strong>in</strong>g peripherally<br />
annulated heteroarene r<strong>in</strong>gs [3] , there are limited data on Pzs substituted directly<br />
at their β-position with five-membered heteroaromatic r<strong>in</strong>gs. [4,5]<br />
Results and Discussion<br />
In the course of our research, novel Pzs conta<strong>in</strong><strong>in</strong>g peripheral 2,5-dimethylpyrrol-1-yl<br />
and dimethylam<strong>in</strong>o groups were synthesized, purified and characterized us<strong>in</strong>g NMR<br />
and X-ray crystallography. Spectroscopic studies performed on Pzs encompassed<br />
steady state absorption and emission measurements, fluorescence decays, femtosecond<br />
transient absorption spectra and thermolum<strong>in</strong>escence. Moreover, the potential<br />
photosensitiz<strong>in</strong>g activity of novel Pzs was evaluated by measur<strong>in</strong>g their ability for<br />
s<strong>in</strong>glet oxygen production us<strong>in</strong>g 1,3-diphenylisobenzofuran.<br />
Fluorescent properties of the Pzs studied were typical for porphyr<strong>in</strong>oids with very low<br />
dipole moment. Time resolved fluorescence studies revealed a significant difference of<br />
fluorescence decays between metallated and free-base Pzs as well as a dependence of<br />
excited-state lifetime on a particular metal ion. Transient absorption measurements<br />
carried out <strong>in</strong> a 2 ns temporal w<strong>in</strong>dow with femtosecond temporal resolution do not<br />
<strong>in</strong>dicate any excited-state processes other than energy relaxation and <strong>in</strong>tersystem<br />
cross<strong>in</strong>g. Thermolum<strong>in</strong>escence measurements showed that Pzs conta<strong>in</strong><strong>in</strong>g Mg, Zn or<br />
Fe ions <strong>in</strong> THF are able to stabilize metastable states under short (a half-width of<br />
about 4 µs) saturat<strong>in</strong>g flash. This effect vanished <strong>in</strong> samples dissolved <strong>in</strong> pyrid<strong>in</strong>e.<br />
[1]<br />
S.L.J. Michel, B.M. Hoffman, S.M. Baum, A.G.M. Barrett Progress <strong>in</strong> Inorganic Chemistry;<br />
Karl<strong>in</strong> K.D., Ed., J. Wiley & Sons: New York, 2001, 50, 473-590.<br />
[2]<br />
R. R. Allison, C. H. Sibata, Photodiagn. Photodyn. Ther. 2010, 7, 61.<br />
[3]<br />
M.P. Donzello, C. Ercolani, P.A. Stuzh<strong>in</strong>, Coord. Chem. Rev. 2006, 250, 1530.<br />
[4]<br />
Q. Luo, S. Cheng, H. Tian Tetrahedron Lett. 2004, 45, 7737.<br />
[5]<br />
S. Szczolko, L. Sobotta, P. Fita, T. Koczorowski, M. Mikus, M. Gdaniec, A. Orzechowska, K.<br />
Burda, S. Sobiak, M. Wierzchowski, J. Mielcarek, E. Tykarska, T. Gosl<strong>in</strong>ski Tetrahedron Lett.<br />
2012, 53, 2040.<br />
This study was supported by the National Science Centre under Grant No. N N404 069440.<br />
228 Saturday 9:00 - 11:30 Poster 171
A Bunch of Novel Cobaltocenium Cations on the Way to<br />
Azo-Bridged Bicobaltocenes<br />
Anne Wolter, Jürgen Heck<br />
Department of Chemistry – University of Hamburg – Mart<strong>in</strong>-Luther-K<strong>in</strong>g-Platz 6 –<br />
20146 Hamburg – GER<br />
woltera@chemie.uni-hamburg.de<br />
Molecular photochromic switches are molecules that can be changed reversibly between<br />
two different (meta)-stable states due to irradiation with light of an appropriate<br />
wavelength. These two isomers have different chemical and physical properties. The<br />
change of the properties can be useful <strong>in</strong> various photonic devices. [1]<br />
A very important photochromic switch is the well-<strong>in</strong>vestigated azo-group. The azoswitch<br />
changes its properties by irradiation due to a change of the configuration, a<br />
E-Z photoisomerisation (Fig.1). The E-isomer is planar and elongated, the Z -isomer<br />
is bent and more compact. [2]<br />
In our work<strong>in</strong>g group we <strong>in</strong>vestigate the <strong>in</strong>teraction of paramagnetic oligonuclear<br />
metallocene derivatives [3] <strong>in</strong> particular azo-bridged paramagnetic metallocenes. Our<br />
target is to l<strong>in</strong>k two paramagnetic metallocenes with an azo-bridge. Due to the<br />
configurationally change of the bridge the magnetic exchange coupl<strong>in</strong>g J 1,2 (Fig.1a)<br />
could change significantly between two paramagnetic cobaltocene moieties and, thus,<br />
changes the magnetic properties of the whole molecule as well. On the way to the<br />
azo-cobaltocene novel functionalized cobaltocenium cations could be synthesized <strong>in</strong><br />
several steps (Fig.1b).<br />
Figure 1. a) E-Z photoisomerisation of the azo-switch b) Key compounds on the way to<br />
the azo-cobaltocene<br />
[1]<br />
M. Irie, Chem. Rev. 2000, 100, 1685-1716.<br />
[2]<br />
M. Kurihara, H. Nishihara, Coord. Chem.<br />
Rev. 2002, 226, 125-135.<br />
[3]<br />
a) N. Pagels, O. Albrecht, D. Görlitz, A. Y. Rogachev, M. H.<br />
Prosenc, J. Heck, Chem. Eur. J., 2011, 17, 4166-4176. b) S. Trtica, M. H. Prosenc, M. Schmidt,<br />
J. Heck, Inorg. Chem., 2010, 49, 1667-1673.<br />
Poster 172 Saturday 9:00 - 11:30 229
Transition Metal-Bismuth Donor-Acceptor Interactions<br />
Supported by Ambiphilic PBiP P<strong>in</strong>cer Ligands<br />
Carol<strong>in</strong> Tschersich, Christian Limberg<br />
Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 – Berl<strong>in</strong> –<br />
GER<br />
carol<strong>in</strong>.tschersich@cms.hu-berl<strong>in</strong>.de<br />
Although bismuthanes can act as donor ligands for transition metal ions, [1] they<br />
do not possess a donor strength comparable to e.g. the one of phosphanes, their<br />
lighter homologues. By contrast Bi III compounds often show dist<strong>in</strong>ct Lewis acidic<br />
properties, especially if electronegative ligands, X, are bound. [2]<br />
The σ-donor behavior of electron rich transition metal ions towards unsaturated Lewis<br />
acidic ma<strong>in</strong> group elements has been demonstrated some time ago, and very recently<br />
also compounds have been reported, where transition metal complex fragments act<br />
as donors for saturated Lewis acidic centers like Si IV , Sn IV and Sb V . [3] Such <strong>in</strong>teractions<br />
are also conceivable for Bi centers and the possibility to <strong>in</strong>fluence the reactivity<br />
and catalytic activity (selectivity) of a late-metal complex by Lewis acidic bismuth<br />
moieties appears highly attractive. However, closed-shell M-Bi <strong>in</strong>teractions, for M<br />
represent<strong>in</strong>g a late transition metal, are still virtually unexplored.<br />
To stabilize complexes exhibit<strong>in</strong>g such metallic contacts with pronounced MBi character,<br />
we have developed an ambiphilic ligand system, where a Lewis acidic Bi–X unit<br />
is comb<strong>in</strong>ed with two Lewis basic phosphane donor functions that may serve to place<br />
the Bi atom close to a transition metal center. After the successful synthesis of such<br />
PBiP p<strong>in</strong>cer ligands, we have tested their potential to establish MBi <strong>in</strong>teractions<br />
for d 8 -configurated Pt II characterized by a filled Lewis basic d 2 z orbital, and for Au I ,<br />
s<strong>in</strong>ce the latter can be expected to lead to large relativistic effects. We report on the<br />
results of our efforts that led to complexes <strong>in</strong>corporat<strong>in</strong>g strong PtBi and AuBi<br />
<strong>in</strong>teractions. [4]<br />
[1] a) S. Roggan, C. Limberg, Inorg. Chim. Acta. 2006, 359, 4698-4722; b) H. Braunschweig, P.<br />
Cogswell, K. Schwab, Coord. Chem. Rev. 2011, 255, 101-117.<br />
[2] W. Clegg, R. J. Err<strong>in</strong>gton, G. A. Fisher, D. C. R. Hockless, N. C. Norman, A. G. Orpen, S. E.<br />
Stratford, Dalton Trans. 1992, 1967-1974.<br />
[3] a) A. Amgoune, D. Bourissou, Chem. Commun. 2011, 47, 859-871; b) C. R. Wade, F. P.<br />
Gabbaï, Angew. Chem. Int. Ed. 2011, 50, 7369-7372.<br />
[4] a) C. Tschersich, C. Limberg, S. Roggan, C. Herwig, N. Ernst<strong>in</strong>g, S. Kovalenko, S. Mebs,<br />
Angew. Chem. Int. Ed. 2012, 51, 4989–4992; b) T.-P. L<strong>in</strong>, I.-S. Ke, F.P. Gabbaï, Angew.<br />
Chem. Int. Ed. 2012, 51, 4985-4988.<br />
230 Saturday 9:00 - 11:30 Poster 173
Surface functionalization of hybrid core/shell nanoparticles<br />
based on rare earth ions for bio-applications<br />
Sangeetha Balabhadra, Marc<strong>in</strong> Runowski, Stefan Lis<br />
Department of chemistry – University of Adam Mickiewicz – Grunwaldzka 6 – Poznań –<br />
POL<br />
sangeetha.balabhadra@gmail.com<br />
Nanoparticles coated with organic compounds are an <strong>in</strong>terest<strong>in</strong>g new class of materials.<br />
The organic coat<strong>in</strong>gs protect the nanoparticles aga<strong>in</strong>st aggregation, control its<br />
growth and give them the capability to work as receptors for biomolecules. Lum<strong>in</strong>escent<br />
nanoparticles are an important class of novel functional materials because<br />
they open a way to use the lum<strong>in</strong>escence of <strong>in</strong>organic compounds with<strong>in</strong> an organic<br />
environment. Inorganic compounds doped with lanthanide ions are widely used as<br />
the lum<strong>in</strong>escent materials <strong>in</strong> light<strong>in</strong>g, protect<strong>in</strong>g and trac<strong>in</strong>g techniques, as well as<br />
displays, optical amplifiers, and lasers. [1,2] These modifications can be applied <strong>in</strong> a<br />
hybrid type of nanomaterials, so called core/shell nanostructures. [3]<br />
The doped lanthanide fluorides as core nanoparticles were synthesized via a simple coprecipitation<br />
process, then covered with silica and modified with am<strong>in</strong>e groups. Further<br />
organic modification was performed us<strong>in</strong>g carboxylic acid chloride. The successful<br />
reaction between am<strong>in</strong>e and carboxylic acid was confirmed by FT-IR. The structure<br />
and morphology of the obta<strong>in</strong>ed nano-composites were exam<strong>in</strong>ed with TEM (Transmission<br />
electron microscopy) and powder X-ray diffraction. Spectroscopic properties<br />
of nanomaterials were studied by measur<strong>in</strong>g their excitation and emission spectra as<br />
well as their lum<strong>in</strong>escence decay curves.<br />
Surface functionalized hybrid core/shell nanoparticles, doped with rare earth ions<br />
emerg<strong>in</strong>g new class of bio-probes, which can be an alternative to conventional molecular<br />
probes such as lanthanide chelates and organic dyes. They attract grow<strong>in</strong>g attention<br />
due to its potential applications <strong>in</strong> areas as diverse as bio-detection, bioimag<strong>in</strong>g,<br />
ow<strong>in</strong>g to their superior features such as long lum<strong>in</strong>escence lifetime, high chemical<br />
stability, resistance to photobleach<strong>in</strong>g, and low toxicity.<br />
[1]<br />
S. Zhou, D. Tu, Z. Chen, M. Huang, H. Zhu, E. Ma, X. Chen, J. Am.<br />
134(36), 15083-15090.<br />
[2]<br />
S. Pate, B. K. Mishra, Talanta 2004, 62, 1005-1028.<br />
[3]<br />
J. Hughey, NNIN REU Research Accomplishments 2005, 55-57.<br />
Chem. Soc. 2012,<br />
Poster 174 Saturday 9:00 - 11:30 231
An attempt to synthesize a metallocarbonyl cyclooctyne<br />
derivatives<br />
Aleksandra Kubicka ∗ , Bogna Rudolf † , Emilia Fornal ∗<br />
∗ Department of Organic Chemistry – University of Lodz, Faculty of Chemistry –<br />
Tamka 12 – Lodz – POL<br />
† Chemistry Department – The John Paul II Catholic University of Lubl<strong>in</strong> –<br />
Al. Krasnicka 102 – Lubl<strong>in</strong> – POL<br />
alex.chemi@wp.pl<br />
The Cu(I)-catalysed azide-alkyne cycloaddition (CuAAC) is one of the best methods<br />
for connect<strong>in</strong>g build<strong>in</strong>g blocks conta<strong>in</strong><strong>in</strong>g various functional groups by covalent<br />
bounds and it is commonly applied <strong>in</strong> organic synthesis, surface and polymer chemistry<br />
or medic<strong>in</strong>al chemistry. [1] This reaction is known as an extremely fast and effective<br />
click reaction for bioconjugation. However, Cu(I) has undesirable cytoxicity<br />
even at low concentrations. [2] Alternative to CuAAC is the stra<strong>in</strong>-promoted alkyneazide<br />
cycloaddition (SPAAC) between cyclooctyne and azide. The use of SPAAC<br />
for bio-conjugation was first described by Bertozzi and coworkers <strong>in</strong> 2004. [3] In an<br />
attempt to develop a new method for the <strong>in</strong>corporation of metallocarbonyl labels<br />
<strong>in</strong>to biomolecules, we synthesized a metallocarbonyl cyclooctyne derivative which can<br />
undergo highly efficient SPAAC reaction with azide or other 1,3-dipolar compounds.<br />
Metallocarbonyl complexes display specific IR absorption bands assigned to the stretch<strong>in</strong>g<br />
vibrations of carbonyl ligands occurr<strong>in</strong>g <strong>in</strong> the range of 1850 to 2150 cm −1 , which<br />
is usually free from absorption bands of biomolecules. Thus they can be applied as IRdetectable<br />
markers for the monitor<strong>in</strong>g of biochemical processes such as ligand-receptor<br />
or antigen-antibody <strong>in</strong>teractions. [4]<br />
[1] J. E. He<strong>in</strong>, V. V. Fok<strong>in</strong>, Chem. Soc. Rev. 2010, 39 (4), 1302-1315.<br />
[2] J. C. Jewett, E. M. Sletten, C. R. Bertozzi, J. Am. Chem. Soc. 2010, 132, 3688-3690.<br />
[3] N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc. 2004, 126, 15046-15047.<br />
[4] N. Fischer-Durand, M. Salma<strong>in</strong>, B. Rudolf, L. Dai, L. Juge, V. Guer<strong>in</strong>eau, O. Laprevote,<br />
A.Vessieres, G. Jaouen, Anal. Biochem. 2010, 407, 211-219.<br />
232 Saturday 9:00 - 11:30 Poster 175
Synthesis and studies on the catalytic activity of new chiral<br />
azirid<strong>in</strong>yl ligands<br />
Szymon Jarzynski, Stanislaw Lesniak, Michal Rachwalski<br />
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 –<br />
Lodz – POL<br />
szymonjarzynski@wp.pl<br />
Asymmetric synthesis is one of the most important areas of research <strong>in</strong> synthetic<br />
organic chemistry and has wide-rang<strong>in</strong>g <strong>in</strong>dustrial applications. It <strong>in</strong>cludes methods<br />
and strategies for the preparation of chiral, enantiomerically pure compounds by us<strong>in</strong>g<br />
stereoselective reactions. We would like to present the synthesis of series of chiral<br />
ligands be<strong>in</strong>g azirid<strong>in</strong>e alcohols which are built on achiral platform and application<br />
of these ligands as chiral catalysts. All the ligands conta<strong>in</strong><strong>in</strong>g enantiomerically pure<br />
azirid<strong>in</strong>es, namely (S)-2-methylazirid<strong>in</strong>e and (S)-2-isopropylazirid<strong>in</strong>e were synthesized<br />
<strong>in</strong> very good chemical yields.<br />
All obta<strong>in</strong>ed products were applied as chiral catalysts <strong>in</strong> asymmetric addition of diethylz<strong>in</strong>c<br />
to benzaldehyde. These reactions were produced <strong>in</strong> good chemical yields<br />
and very high enantiomeric excess values. [1,2]<br />
[1]<br />
S. Leśniak, M. Rachwalski, E. Sznajder, P. Kiełbasiński, Tetrahedron Asymmetry 2009, 20,<br />
2311.<br />
[2]<br />
M. Rachwalski, S. Leśniak, P. Kiełbasiński, Tetrahedron Asymmetry 2010, 21, 2687.<br />
Poster 176 Saturday 9:00 - 11:30 233
Alkylisocorroles and strategies towards biomimetic heme<br />
analogs<br />
Mart<strong>in</strong> Hoffmann, Birte Böker, Benedikt Wolfram, Mart<strong>in</strong> Brör<strong>in</strong>g<br />
Chemistry – Institute of Inorganic and Analytical Chemistry, TU Braunschweig –<br />
Hagenr<strong>in</strong>g 30 – Braunschweig – GER<br />
mart<strong>in</strong>.hoffmann@tu-bs.de<br />
Site-directed mutagenesis of the peptide scaffold, especially <strong>in</strong> the active pocket region,<br />
has long been the method of choice for the <strong>in</strong>vestigation of functional aspects <strong>in</strong> heme<br />
prote<strong>in</strong>s. [1] An alternative, but much less studied approach, is cofactor exchange. [2]<br />
Extract<strong>in</strong>g the native prosthetic group leads to the formation of an apoprote<strong>in</strong>, which<br />
can be reconstituted with an artificial heme-analogous molecule afterwards.<br />
Apart from modified porphyr<strong>in</strong>s, other tetrapyrroles like phthalocyan<strong>in</strong>e, porphycene<br />
and corrole have been used <strong>in</strong> this regard. [2]<br />
In comparison to the well-known tetrapyrroles porphyr<strong>in</strong> and corrole, 10-isocorrole<br />
(short: isocorrole) beares a disubstituted 10-meso position (Fig. 1). Therefore it<br />
exhibits characteristics of porphyr<strong>in</strong> (dianionic character) and corrole (smaller cavity),<br />
but conta<strong>in</strong>s a non-aromatic, electronically dist<strong>in</strong>ct ligand backbone. [3]<br />
In this poster the metal-templated synthesis of Nickel- and Palladium alkylisocorroles<br />
is presented. Further strategies towards biomimetic heme analogs of the isocorrole<br />
type are demonstrated.<br />
Fig 1: Core-structures of porphyr<strong>in</strong>, isocorrole and corrole.<br />
[1] Y. Lu, S. M. Berry, T. D. Pfister, Chem. Rev. 2001, 101, 3047-3080.<br />
[2] L. Fruk, C.-H. Kuo, E. Torres, C. M. Niemeyer, Angew. Chem. 2009, 121, 1578-1603;<br />
Angew. Chem. Int. Ed. 2009, 48, 1550-1574.<br />
M. Brör<strong>in</strong>g, F. Brégier, O. Burghaus, C. Kleeberg, Z. Anorg. Allg. Chem. 2010, 636, 1760-1766.<br />
[3] G. Hohlneicher, D. Bremm, J. A. Wytko, J. Bley-Escrich, J.-P. Gisselbrecht, M. Gross, M.<br />
Michels, J. Lex, E. Vogel, Chem. Eur. J. 2003, 9, 5636-5642.<br />
234 Saturday 9:00 - 11:30 Poster 177
Synthesis and Characterization of a New Phthalocyan<strong>in</strong>e<br />
Includ<strong>in</strong>g Pentanuclear Z<strong>in</strong>c (II) Complexes<br />
Gulnur Keser Karaoglan ∗ , Gulsah Gumrukcu ∗ , Ali Erdogmus ∗ , Ahmet Gul † ,<br />
Ulvi Avciata ∗<br />
∗ Chemistry – Technical University of Yildiz – Davutpasa / 34210 – Istanbul – TUR<br />
† Chemistry – Technical University of Istanbul – Maslak / 34469 – Istanbul – TUR<br />
gulnurkeser@hotmail.com<br />
Metallophthalocyan<strong>in</strong>es (MPcs) derivatives display <strong>in</strong>terest<strong>in</strong>g chemical and physical<br />
properties, so they have been studied extensively. MPcs enjoy many applications <strong>in</strong><br />
fields such as non-l<strong>in</strong>ear optics chemical sensors, semiconductors, liquid crystals and<br />
catalysis. [1] The <strong>in</strong>creas<strong>in</strong>g importance and use of phthalocyan<strong>in</strong>es as advanced materials<br />
have created impetus for design variables of the central metal ion and peripheral<br />
substituents to reach the desired properties. [2]<br />
In the present study, complexation on the periphery to obta<strong>in</strong> pentanuclear complex<br />
has been accomplished through the reaction of the phthalocyan<strong>in</strong>e carry<strong>in</strong>g salicylideneim<strong>in</strong>o<br />
ligat<strong>in</strong>g groups with z<strong>in</strong>c (II) complex of 8-hydroxyqu<strong>in</strong>ol<strong>in</strong>e. The new<br />
compounds have been characterized by elemental analysis FTIR, 1H-NMR, UV-Vis<br />
and mass spectra.<br />
[1] G. K. Karaoglan, G. Gumrukcu, A. Koca, A. Gul, “The synthesis, characterization, electrochemical<br />
and spectroelectrochemical properties of a novel, cationic, water-soluble Zn phthalocyan<strong>in</strong>e<br />
with extended conjugation”, Dyes Pigm 2011, 88, 247-256.<br />
[2] H. Kantek<strong>in</strong>, Y. Gok, M. B. Kilicaslan, I. Acar “Synthesis and characterization of new metalfree<br />
and nickel(II) phthalocyan<strong>in</strong>es conta<strong>in</strong><strong>in</strong>g hexaazadioxa macrobicyclic moieties”, J. Coord.<br />
Chem. 2008, 61 (2), 229-236.<br />
Poster 178 Saturday 9:00 - 11:30 235
Transformations of 2-(2-cyano-2-carbamoyl-1-ethynyl)-3-oxo-<br />
1-cyclohexen-1-olates <strong>in</strong><br />
water<br />
Mariia Vodolazhenko ∗ , Nikolay Gorobets ∗ , Oleg Zhikol ‡ , Sergey Desenko ∗<br />
∗ Department of Heterocyclic Compounds Chemistry –<br />
SSI “Institute for S<strong>in</strong>gle Crystals” NAS of Ukra<strong>in</strong>e – Len<strong>in</strong> ave. 60 – Kharkiv – UKR<br />
‡ Department of X-ray Diffraction Studies and Quantum Chemistry –<br />
SSI “Institute for S<strong>in</strong>gle Crystals” NAS of Ukra<strong>in</strong>e – Len<strong>in</strong> ave. 60 – Kharkiv – UKR<br />
vodolazhenko.maria@yandex.ua<br />
A simple method for synthesis of polyfunctional resonance stabilized 2-(2-cyano-2carbamoyl-1-ethynyl)-3-oxo-1-cyclohexen-1-olates<br />
4 has been previously <strong>in</strong>troduced<br />
by our group. [1] These solts have high solubility <strong>in</strong> water or alcohols and act as reactive<br />
<strong>in</strong>termediates <strong>in</strong> the synthesis of various heterocyclic compounds. In this report our<br />
study of their transformations <strong>in</strong> water under different conditions is presented.<br />
Screen<strong>in</strong>g of the reaction conditions [2] for one-pot three-stage selective synthesis of<br />
2-pyrons 6 we found that <strong>in</strong> the presence of acid the desired compounds 6 are formed<br />
as a ma<strong>in</strong> product of the reaction and 2-pyridones 7 as by-products. [3]<br />
Interest<strong>in</strong>gly, that <strong>in</strong> pure water the transformation of the salts 4 has changed its<br />
direction towards 3-cyano-2-pyridones 8. This method for synthesis of 8 is more<br />
simple then our previous one, [4] and allowed us to understand some aspects of the<br />
reaction mechanism.<br />
S<strong>in</strong>ce the direct hydrolysis of a cyano group requires much more vigorous reaction<br />
conditions than the applied for the hydrolysis of salts 1, we believe that both products<br />
6 and 7 are formed via <strong>in</strong>termediate 2-im<strong>in</strong>opyrans 5. This suggestion was confirmed<br />
by quantum chemical calculations us<strong>in</strong>g DFT B3LYP/aug-cc-pvdz method.<br />
Synthesis of the salts 4 and their transformations <strong>in</strong> water<br />
[1] S. A. Yermolayev, N. Yu. Gorobets, E. V. Luk<strong>in</strong>ova, O. V. Shishk<strong>in</strong>, S. V. Shishk<strong>in</strong>a, S. M.<br />
Desenko, Tetrahedron 2008, 64, 4649-4655.<br />
[2] M. A. Vodolazhenko, N. Yu. Gorobets, S. A. Yermolayev, V. V. Musatov, V. A. Chebanov, S.<br />
M. Desenko, RSC Advances 2012, 2, 1106-1111.<br />
[3] N. Yu. Gorobets, B. H. Yousefi, F. Belaj, C. O. Kappe, Tetrahedron 2004, 60, 8633-8644.<br />
[4] S. A. Yermolayev, N. Yu. Gorobets, S. M. Desenko, J. Comb. Chem. 2009, 11, 44-46.<br />
236 Saturday 9:00 - 11:30 Poster 179
Utilization of cross-coupl<strong>in</strong>g reactions<br />
for the synthesis of 3D-NLOphores<br />
Elisabeth Ziemann, Jürgen Heck<br />
Institute of Applied and Inorganic Chemistry – University of Hamburg –<br />
Mart<strong>in</strong>-Luther-K<strong>in</strong>g-Platz 6 – 20146 Hamburg – GER<br />
ziemann@chemie.uni-hamburg.de<br />
In times of persistent grow<strong>in</strong>g <strong>in</strong>formation technology markets there is by nature a<br />
great demand for more efficient data transmission methods. Nonl<strong>in</strong>ear optical (NLO)<br />
active materials play a very important role for this enhancement, but to <strong>in</strong>crease the<br />
application range it is necessary to optimize the NLOphores, especially <strong>in</strong> terms of<br />
response time and size of the exam<strong>in</strong>ed NLO-effect. [1]<br />
Besides exam<strong>in</strong><strong>in</strong>g dendritic structures [2] we are directed towards so-called<br />
“3D-NLOphores” which are based on a 1,3,5-trisubstituted benzene r<strong>in</strong>g coord<strong>in</strong>ated<br />
to a cationic cyclopentadienyl-ruthenium unit serv<strong>in</strong>g as an acceptor, metallocenes<br />
fulfill the donor function.<br />
Their NLO-activity has already been successfully characterized us<strong>in</strong>g Hyper-Rayleigh-<br />
Scatter<strong>in</strong>g (e.g. compound A) [3] , our ongo<strong>in</strong>g research now focusses on tun<strong>in</strong>g this<br />
effect (quantified by the value β0) by expand<strong>in</strong>g the π-electron-system, vary<strong>in</strong>g the<br />
metal centers, the substitution pattern of acceptor and donor function, and the<br />
counter ion (compound B).<br />
The expansion of the π-electron-system should be achieved by the <strong>in</strong>troduction of<br />
eth<strong>in</strong>ylbridges. To prevent observed undesired C-C-cleavage processes [4] we needed<br />
to <strong>in</strong>vestigate different synthetic routes for example <strong>in</strong>clud<strong>in</strong>g Hiyama-, Sonogashiraand<br />
Stille-cross coupl<strong>in</strong>g reactions. We are present<strong>in</strong>g the different results of these<br />
approaches and the characterization of the new eth<strong>in</strong>ylferrocene-substituted complex<br />
[RuCp(C6H3(C ≡ C − F c)3)] + .<br />
[1] N. J. Long, Angew. Chem. 1995, 107, 37-56.<br />
[2] J. Holtmann, E. Walczuk, M. Dede, C. Wittenburg, J. Heck, G. Archetti, R. Wortmann, H.-G.<br />
Kuball, Y.-H. Wang, K. Liu, Y. Luo, J. Phys. Chem. B, 2008, 112, 14751.<br />
[3] S. Steffens, M. H. Prosenc, J. Heck, I. Asselberghs, K. Clays, Eur. J. Inorg. Chem. 2008,<br />
1999–2006. [4] S. Steffens, Dissertation, University of Hamburg, 2005.<br />
Poster 180 Saturday 9:00 - 11:30 237
Synthesis and complexation abilities of new <strong>in</strong>dazole<br />
derivatives with expected cytostatic activity<br />
Jacek Kujawski ∗ , Hanna Popielarska ∗ , Beata Drab<strong>in</strong>ska ∗ , Anna Myka ∗ ,<br />
Sab<strong>in</strong>a Smusz ‡,† , Rafal Kurczab † , Andrzej Bojarski †<br />
∗ Department of Organic Chemistry – Poznan University of Medical Sciences –<br />
Grunwaldzka 6 – Poznan – POL<br />
† Department of Medic<strong>in</strong>al Chemistry –<br />
Institute of Pharmacology, Polish Academy of Sciences – Smetna 12 – Krakow – POL<br />
‡ Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Krakow – POL<br />
jacekkuj@ump.edu.pl<br />
A series of new dimeric <strong>in</strong>dazole derivatives 5 (A) was obta<strong>in</strong>ed by a four-step synthesis<br />
that <strong>in</strong>cluded classical aromatic nucleophilic substitution, Vicarious Nucleophilic<br />
Substitution of Hydrogen (VNS) ortho to the nitro group, reduction of the latter<br />
functionality and cyclization to a pyrazole r<strong>in</strong>g by diazotization. The use of Raney<br />
nickel together with hydraz<strong>in</strong>e hydrate as a source of molecular hydrogen allowed for<br />
considerable shorten<strong>in</strong>g of the hydrogenation time. As the resulted am<strong>in</strong>es 4 were<br />
usually <strong>in</strong>soluble <strong>in</strong> water, the diazotization was carried out <strong>in</strong> solid phase us<strong>in</strong>g the<br />
microwave method (MAOS). The prelim<strong>in</strong>ary biological tests showed that some of<br />
the f<strong>in</strong>al products 5 had cytotoxic activity <strong>in</strong> cell-based bioassays. [1] The cytotoxicity<br />
mechanism may be connected with the compounds ability either to complex metal<br />
ions present at the active sites of prote<strong>in</strong>s or to bond with the nucleic base pairs.<br />
Thus, the simulation of complexation with magnesium ions was performed for compound<br />
5b (B) on this account. [2] Moreover, the theoretical calculations (long range<br />
DFT- B3LYP/6-31G(d,p), and QTAIM methods), us<strong>in</strong>g the Gaussian G09 program,<br />
showed the ability of compound 5b to form strong and weak hydrogen bonds with<br />
guan<strong>in</strong>e, cytos<strong>in</strong>e, [3] as well as urid<strong>in</strong>e (C). Some physicochemical properties of the<br />
compounds 5 (log P and pKa) were additionally calculated based on mach<strong>in</strong>e learn<strong>in</strong>g<br />
algorithms – support vector regression and multilayer perceptron.<br />
Synthesis of <strong>in</strong>dazole derivatives 5 and complexes of 5b wit Mg (B) and urid<strong>in</strong>e (C).<br />
[1]<br />
E. Totoń, E. Ignatowicz, M.K. Bernard, J. Kujawski, M. Rybczyńska, J. Phys. Pharmacol.<br />
2012, submitted.<br />
[2]<br />
J. Kujawski, M. Doskocz, H. Popielarska, A. Myka, J. Kruk, M. K. Bernard, Polyhedron <strong>2013</strong>,<br />
submitted.<br />
[3]<br />
J. Kujawski, H. Popielarska, B. Drabińska, E. Jodłowska, J. Adamus, K. Czaja, A. Myka,<br />
M. K. Bernard, “New pyrazole derivatives with potential biological activity: theoretical studies<br />
on complexation of small-molecule ligands” 5th Conversatory on Medic<strong>in</strong>al Chemistry, Lubl<strong>in</strong>,<br />
13-15.09.2012.<br />
Investigations were supported by PCSS grant No. 96/2011, SBN grant No. 126/2012, polish<br />
National Science Centre (NCN) grants No. N N401 642340 and NNZ2/02478, EU scholarship<br />
for PhD students (Poznan, WUP, Task 8.2.2. PO KL 2011-2012).<br />
238 Saturday 9:00 - 11:30 Poster 181
Synthesis and properties of C-phosphonate nucleotide<br />
analogues bear<strong>in</strong>g alkyne moiety for label<strong>in</strong>g via CuAAC<br />
reactions<br />
Sylwia Walczak, Joanna Kowalska, Błażej Wojtczak, Jacek Jemielity<br />
Division of Biophysics, Institute of Experimental Physics, Faculty of Physics –<br />
University of Warsaw – Zwirki i Wigury 93 – Warsaw – POL<br />
sylwalczak@gmail.com<br />
“Click chemistry” is a modern approach towards the synthesis of compounds by jo<strong>in</strong><strong>in</strong>g<br />
small units <strong>in</strong> high-yield<strong>in</strong>g, stereospecific and simple reactions such as Cu-catalyzed<br />
azide-alkyne cycloaddition. The considerable part of grow<strong>in</strong>g applications of CuAAC<br />
<strong>in</strong>cludes modifications of nucleosides and oligonucleotides. Therefore, more and more<br />
attention is paid to the synthesis of specifically designed analogues of nucleosides<br />
that may be used as reagents for 1,3-dipolar Huisgen cycloaddition. In order to<br />
take advantage of CuAAC as a powerful chemical strategy of jo<strong>in</strong><strong>in</strong>g our analogues<br />
of nucleotides with different entities we synthesized the C-phosphonate analogue<br />
of N 7 -methyl-guanos<strong>in</strong>e-5’-monophosphate with 4-butynyl substituent (m 7 GppC4H5;<br />
Fig.1a). Both the presence of term<strong>in</strong>al alkyne and excellent solubility make it a good<br />
substrate for click reaction with azide-modified molecules.<br />
Hav<strong>in</strong>g synthesized m 7 GppC4H5, we ligated it <strong>in</strong> a simple click reaction to azidemodified<br />
fluorescent dyes (Fig.1c) and magnetic nanoparticles. The former compounds<br />
would enable biologists to visualize biomolecules <strong>in</strong>teract<strong>in</strong>g with their nucleic<br />
part whereas the latter conjugates might be found applicable to modern technics of<br />
the aff<strong>in</strong>ity chromatography. In order to explore whether triazole r<strong>in</strong>g could mimic<br />
phosphate moiety, we have synthesized d<strong>in</strong>ucleotide cap analogue with triazole r<strong>in</strong>g<br />
with<strong>in</strong> 5’-5’ phosphate bridge (Fig.1b). It may serve as a tool for selective <strong>in</strong>hibition or<br />
activation of the processes <strong>in</strong> which cap structure is <strong>in</strong>volved i.e. mRNA maturation,<br />
<strong>in</strong>tracellular transport, translation and degradation.<br />
Fig.1. a) N 7 -methyl-guanos<strong>in</strong>e-5’-monophosphate with 4-butynyl substituent<br />
(m 7 GppC4H5); b) The cap analogue with triazole r<strong>in</strong>g with<strong>in</strong> 5’-5’ triphosphate bridge;<br />
c) m 7 GppC4H5 attached to fluorescent dye<br />
Poster 182 Saturday 9:00 - 11:30 239
Mechanistic <strong>in</strong>sight <strong>in</strong>to the palladium(II)-catalyzed<br />
oxidative cyclization of diaryl am<strong>in</strong>es<br />
Tobias Gensch, Ingmar Bauer, Hans-Joachim Knölker<br />
Department of Chemistry – Technische Universität Dresden – Bergstraße 66 – Dresden –<br />
GER<br />
tobias.gensch@chemie.tu-dresden.de<br />
The palladium(II)-catalyzed oxidative cyclization of diarylam<strong>in</strong>es to carbazoles is of<br />
great importance for the construction of a wide range of natural products with the<br />
carbazole structure [1] and is an example of a twofold direct C–H-activation for C–Cbond<br />
formation (Fig. 1 A). Insights <strong>in</strong>to the mechanism of this transformation were<br />
ga<strong>in</strong>ed by isolat<strong>in</strong>g and characteriz<strong>in</strong>g an <strong>in</strong>termediate diarylpalladium(II) complex<br />
(Fig. 1 B) that consists of a palladacycle connect<strong>in</strong>g both aromatic r<strong>in</strong>gs. [2] This<br />
complex undergoes facile conversion to carbazole and palladium(0) and was shown<br />
to be catalytically active for the oxidative cyclization of diarylam<strong>in</strong>es. Its isolation<br />
was possible by the twofold chelation with coord<strong>in</strong>at<strong>in</strong>g, ortho-direct<strong>in</strong>g substituents<br />
at the diarylam<strong>in</strong>e. Characterization of this new class of palladium(II) complexes<br />
offers an understand<strong>in</strong>g of the mechanism of direct C–H-activation and reductive<br />
elim<strong>in</strong>ation.<br />
Figure 1. A : Oxidative cyclization of diarylam<strong>in</strong>es to carbazoles catalyzed by Pd(II).<br />
B: Example of a stable palladacycle <strong>in</strong>termediate of the oxidative cyclization.<br />
[1] a) I. Bauer, H.-J. Knölker, Top. Curr. Chem. 2012, 309, 203–253; b) A. W. Schmidt, K. R.<br />
Reddy, H.-J. Knölker, Chem. Rev. 2012, 112, 3193–3328.<br />
[2] T. Gensch, M. Rönnefahrt, R. Czerwonka, A. Jäger, O. Kataeva, I. Bauer, H.-J. Knölker, Chem.<br />
Eur. J. 2012, 18, 770–776.<br />
240 Saturday 9:00 - 11:30 Poster 183
Hexaphenoxycyclotriphosphazen as a flame retardant for<br />
transparent Polycarbonat<br />
Bert Käbisch ∗ , Ulrich Fehrenbacher ∗ , Edw<strong>in</strong> Kroke †<br />
∗ Environmental Eng<strong>in</strong>eer<strong>in</strong>g – Fraunhofer – Joseph-von-Fraunhofer-Str. 7 – Pf<strong>in</strong>tztal –<br />
GER<br />
† Inorganic Chemistry – TU Bergakademie Freiberg – Leipziger Straße 29 –<br />
Freiberg – GER<br />
bert.kaebisch@ict.fraunhofer.de<br />
The protection of plastics with flame retardants is one of the important topics for<br />
<strong>in</strong>troduc<strong>in</strong>g a material to the market and for its end application. Because of new<br />
regulations most of the current used flame retardants are evaluated because of their<br />
toxicity and their environmental impact. Also by add<strong>in</strong>g particular additive flame<br />
retardants to a polymer the mechanical properties are most times negetively affected.<br />
One of these properties is the transparancy of a polymer, e.g. polycarbonate, which<br />
normally will be very negatively affected by us<strong>in</strong>g an particular additive flame retardant.<br />
Therefore, nonhazardous flame retardants with good compatibillity to the<br />
polymer needs to be <strong>in</strong>vestigated. By <strong>in</strong>troduc<strong>in</strong>g Hexaphenoxycyclotriphosphazen<br />
(1) as a particalur flame retardant to protect polycarbonate it is possible to obta<strong>in</strong> a<br />
trasparent material while us<strong>in</strong>g a particular, nonhazardous additive. The <strong>in</strong>vestigated<br />
concentrations of 1 <strong>in</strong> polycarbonate are 0, 1, 2, 5 and 10 mass%. The mechanical<br />
properties of the protected polymer, tenacity, tensile elongation, dynamic mechanical<br />
analysis, Charpy impact and transparency were characterized. The flame retardancy<br />
was evaluated with LOI and the UL94 test and shows, even with the big differnce of<br />
the decomposition temperature of 1 and polycarbonate, a very promis<strong>in</strong>g effect.<br />
Poster 184 Saturday 9:00 - 11:30 241
Bromodimethylsulfonium Bromide (BDMS) Mediated-<br />
Synthesis of Urea via Lossen Rearrangement<br />
Deepak K. Yadav, Arv<strong>in</strong>d K. Yadav, Vishnu P. Srivastava, Geeta Watal, L. D. S. Yadav<br />
University of Allahabad – Allahabad – IND<br />
deepakanu123@gmail.com<br />
Bromodimethylsulfonium bromide (BDMS) was found to be a very efficient reagent<br />
for Lossen rearrangement of hydroxamic acids to the correspond<strong>in</strong>g isocyantes which<br />
were subsequently trapped <strong>in</strong>-situ with various am<strong>in</strong>es afford<strong>in</strong>g ureas <strong>in</strong> good to<br />
excellent yields. The protocol is experimentally simple, mild and represents valuable<br />
alternatives to phosgene-based approaches for the preparation of isocyanates.<br />
Bromodimethylsulfonium bromide (BDMS); Lossen rearrangement; Hydroxamic acid; Isocyanates;<br />
Ureas<br />
242 Saturday 9:00 - 11:30 Poster 185
Synthesis of Phosphorylated Iso<strong>in</strong>dol<strong>in</strong>one Derivatives<br />
Piotr Zagórski ∗ , Andrzej Jóźwiak ∗ , Dariusz Cal † , Mieczysław W. Płotka ∗<br />
∗ Department of Organic Chemistry – University of Lodz – Tamka 12 – 91-403 Lodz –<br />
POL<br />
† Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 –<br />
91-403 Lodz – POL<br />
zagorek@op.pl<br />
Iso<strong>in</strong>dol<strong>in</strong>one build<strong>in</strong>g block is present <strong>in</strong> many natural alcaloids like Lennoxam<strong>in</strong>e. [1]<br />
There are other synthetic drugs that conta<strong>in</strong> iso<strong>in</strong>dol<strong>in</strong>ones moiety, for example<br />
Pagoclone. [2] In recent years a lot of attention has been paid to the synthesis of<br />
phosphorylated iso<strong>in</strong>dol<strong>in</strong>one derivatives. [3-6] Our research aim is to enrich a modest<br />
library of new phosphonic acids and esters conta<strong>in</strong><strong>in</strong>g an iso<strong>in</strong>dol<strong>in</strong>one structure.<br />
A key step <strong>in</strong> the synthesis is lithiation of iso<strong>in</strong>dol<strong>in</strong>one (1) us<strong>in</strong>g sec-buthyllithium<br />
<strong>in</strong> tetrahydrofuran followed by a reaction of the generated lithiated species with diethyl<br />
v<strong>in</strong>ylphosphonate (for products 2a) or diethyl(3-bromopropyl)phosphonate (for<br />
products 2b).<br />
[1]<br />
J. R. Fuchs, R. L. Funk, Organic Letters 2001, 3, 3923-3925.<br />
[2]<br />
T. L. Stuk, B. K. Ass<strong>in</strong>k, D. T. Erdman, V. Fedij, S. M. Jenn<strong>in</strong>gs, J. A. Lassig, R. J. Smith,<br />
T. L. Smith, Organic Process Research & Development 2003, 7, 851-855.<br />
[3]<br />
J. L. Viveros-Ceballos, M. Ordonez, C. Cativiela, Tetrahedron: Asymmetry 2011, 22, 1479-<br />
1484.<br />
[4]<br />
A. Couture, E. Dienau, P. Woisel, P. Grandclaudon, Synthesis 1997, 12, 1439-1445.<br />
[5]<br />
G. O. Kachkovskyi, O. I. Kolodiazhnyi, Phosphorus, Sulfur and Silicon and the Related<br />
Elements 2010, 185, 2441-2448.<br />
[6]<br />
M. Ordonez, G. D. Tibhe, A. Zamudio-Med<strong>in</strong>a, J. L. Viveros-Ceballos, Synthesis 2012, 44,<br />
569-574.<br />
Poster 186 Saturday 9:00 - 11:30 243
Mesomorphic properties of some<br />
4-(4-alkoxybenzylideneam<strong>in</strong>o)azobenzenes<br />
Anna Lesniak, Agnieszka Puchala<br />
Institute of Chemistry – Jan Kochanowski University – Swietokrzyska 15G – Kielce –<br />
POL<br />
plesniaczek26@wp.pl<br />
Azometh<strong>in</strong>e compounds are important due to their applications <strong>in</strong> dyes, pigments,<br />
functional materials and they were early recognized as the liquid-crystall<strong>in</strong>e compounds.<br />
Azometh<strong>in</strong>e bond (CH=N) <strong>in</strong>corporated <strong>in</strong>to the molecular structure cause<br />
<strong>in</strong>crease the length and polarizability anisotropy of the molecular core <strong>in</strong> order to<br />
enhance liquid crystal phase stability.<br />
We present synthesis and the liquid crystall<strong>in</strong>e properties of the series of 4-(4-alkoxybenzylideneam<strong>in</strong>o)azobenzenes.<br />
The synthesis were carried out <strong>in</strong> a two-step process.<br />
The start<strong>in</strong>g 4-alkyloxybenzaldehydes were obta<strong>in</strong>ed <strong>in</strong> the usual way by the reaction<br />
of 4-hydroxybenzaldehyde with the appropriate n-alkylbromide. 4-(4-Alkoxybenzylideneam<strong>in</strong>o)azobenzenes<br />
were prepared by the condensation of the correspond<strong>in</strong>g aldehydes<br />
with 4-am<strong>in</strong>oazobenzene us<strong>in</strong>g a microwave oven (PLAZMATRONICA RM800).<br />
The use of such reaction conditions, compared to classical heat<strong>in</strong>g, reveals several features<br />
like: better selectivity, shorter reaction time and easier of work-up after reaction.<br />
All f<strong>in</strong>al products were purified by chromatography on silica gel with chloroform as an<br />
eluent and characterized by IR, NMR and mass spectroscopy. The mesophases of the<br />
4-(4-alkoxybenzylideneam<strong>in</strong>o)azobenzenes were studied by polariz<strong>in</strong>g optical microscope<br />
(POM) and differential scann<strong>in</strong>g calorimetry (DSC). Investigated compounds<br />
exhibit nematic, smectic A and smectic B mesophases. We will discuss the <strong>in</strong>fluence<br />
of an alkyl cha<strong>in</strong> length on the mesophase sequence.<br />
244 Saturday 9:00 - 11:30 Poster 187
Synthesis and structure of the first vanadium complex with<br />
the Schiff base of salicylaldehyde and am<strong>in</strong>oguanid<strong>in</strong>e<br />
Mirjana Lalović, Marko Rodić, Ljiljana Voj<strong>in</strong>ović-Ješić, Vukad<strong>in</strong> Leovac<br />
Faculty of Sciences – University of Novi Sad – Trg Dositeja Obradovića 3 – Novi Sad –<br />
SRB<br />
mirjana.lalovic@dh.uns.ac.rs<br />
The great <strong>in</strong>terest <strong>in</strong> vanadium coord<strong>in</strong>ation chemistry <strong>in</strong> the context of medical<br />
applications has arisen from the ability of vanadium complexes to promote the <strong>in</strong>sul<strong>in</strong><br />
mimetic activity <strong>in</strong> the treatment of human Diabetes mellitus. Despite the fact<br />
that am<strong>in</strong>oguanid<strong>in</strong>e (AG) shows wide range of pharmacological activity, vanadium<br />
complexes with its Schiff bases are still unknown. Besides, only a few complexes of<br />
salicylidene-am<strong>in</strong>oguanid<strong>in</strong>e (SalAG) have been synthesized, so it seems worthwhile<br />
to exam<strong>in</strong>e the synthesis and characteristics of the new ones.<br />
Here we present the synthesis and structure of the ligand SalAG·HNO3 and its complex<br />
with dioxidovanadium(V). S<strong>in</strong>gle crystals of the ligand are obta<strong>in</strong>ed <strong>in</strong> the reaction<br />
of the ethanolic solutions of the am<strong>in</strong>oguanid<strong>in</strong>e hydrogennitrate and salicylaldehyde<br />
<strong>in</strong> the presence of the acetic acid, while the reaction of ammoniacal solutions<br />
of the ligand and NH4VO3 resulted <strong>in</strong> formation of s<strong>in</strong>gle crystals of the complex<br />
[VO2(SalAG−H)]. In this complex, SalAG is coord<strong>in</strong>ated, as a monoanion, <strong>in</strong> a tridentate<br />
ONN mode, via oxygen atom of phenolic hydroxyl and nitrogen atoms of<br />
azometh<strong>in</strong>e and im<strong>in</strong>o groups of the am<strong>in</strong>oguanid<strong>in</strong>e fragment. Vanadium atom is<br />
situated <strong>in</strong> almost ideal square-pyramidal environment (τ = 0.032), with the anion of<br />
the chelate ligand and one oxido-ligand <strong>in</strong> the basal plane and the other oxido-ligand<br />
<strong>in</strong> the apical position.<br />
Molecular structure of the ligand and the complex<br />
Poster 188 Saturday 9:00 - 11:30 245
Synthesis and Photophysical Properties of Some<br />
Tetraalkynylpyrid<strong>in</strong>es<br />
Andranik Petrosyan †,∗ , Peter Ehlers ∗ , Tariel Ghochikyan † , Ashot Saghyan † ,<br />
Peter Langer ∗<br />
∗ Leibniz-Institut für Katalyse an der Universität Rostock e.V. –<br />
Albert E<strong>in</strong>ste<strong>in</strong> Str. 29a – Rostock – GER<br />
† Faculty of Chemistry – Yerevan State University – Alex Manoogian 1 – Yerevan – ARM<br />
andranik.petrosyan@catalysis.de<br />
Both <strong>in</strong> materials science and organic chemistry, polyethynylated carbon-rich molecules<br />
are of particular <strong>in</strong>terest because of their extended conjugated structure. Those k<strong>in</strong>d<br />
of molecules have potential as liquid crystals, nonl<strong>in</strong>ear optical materials as well as<br />
build<strong>in</strong>g blocks for robust graphite-like carbon networks. [1]<br />
Encouraged by <strong>in</strong>terest<strong>in</strong>g structural, and potential properties of such compounds,<br />
and based on the work done on polyhalogenated pyrid<strong>in</strong>es before, [2] a series of new<br />
tetraalkynylpyrid<strong>in</strong>es were efficiently synthesized us<strong>in</strong>g multiple Sonogashira reaction<br />
protocol.<br />
After symmetrical tertraalkynyl compounds 1 were obta<strong>in</strong>ed via tetrafold Sonogashira<br />
coupl<strong>in</strong>g, we optimized reaction conditions <strong>in</strong> order to reach selectivity. As a result,<br />
dialkynylpyrid<strong>in</strong>e derivatives 2 were easily synthesized, which <strong>in</strong> fact, served as important<br />
start<strong>in</strong>g po<strong>in</strong>t for mak<strong>in</strong>g molecules 3 with mixed acetylene moieties.<br />
In order to get <strong>in</strong>sights <strong>in</strong>to the impact of substituents <strong>in</strong> 4-position of the pyrid<strong>in</strong>e<br />
core, we studied the absorption and emission properties of the synthesized<br />
tetraalkynylpyrid<strong>in</strong>es and already reported pentaalkynylpyrid<strong>in</strong>es. [2]<br />
Pentaalkynylpyrid<strong>in</strong>es absorb and emit at lower energies and possess higher quantum<br />
yields than tetraalkynylpyrid<strong>in</strong>es. While a sterically demand<strong>in</strong>g isopropoxygroup <strong>in</strong><br />
the 4-position leads to the highest blue shift of the absorption and emission bands as<br />
well as low quantum yields. This effect is based on a poorer conjugation caused by<br />
steric repulsion of the functional groups.<br />
Figure 1. Synthesis of products 1-3.<br />
[1] (a) U. H. F. Bunz, Y. Rub<strong>in</strong>, Y. Tobe, Chem. Soc. Rev. 1999, 28, 107; (b) F. Diederich,<br />
Nature 1994, 369, 199. (with the references cited there<strong>in</strong>)<br />
[2] (a) P. Ehlers, A. Neubauer, S. Lochbrunner, A. Vill<strong>in</strong>ger, P. Langer, Org. Lett. 2011, 13,<br />
1618-1621; (b) V. Engelhardt, J. G. Garcia, A. A. Hubaud, K. A. Lyssenko, S. Spyroudis, T. V.<br />
Timofeeva, P. Tongwa, K. P. C. Vollhardt, SYNLETT 2011, 2, 0280-0284.<br />
246 Saturday 9:00 - 11:30 Poster 189
Solventless selective phosgene-free N-carbonylation of<br />
N-heteroaromatics (pyrrole, <strong>in</strong>dole, carbazole) under mild<br />
conditions<br />
Francesco Iannone, Marianna Carafa, Valent<strong>in</strong>a Mele, Eugenio Quaranta<br />
Dipartimento di Chimica – Università degli Studi di Bari – Via E. Orabona 4 – Bari –<br />
ITA<br />
francesco.iannone@uniba.it<br />
Organic carbonates (RO)2CO (R = alkyl, aryl), nowadays available through phosgeneless<br />
routes even on an <strong>in</strong>dustrial scale, [1] are arous<strong>in</strong>g greater <strong>in</strong>terest as environmentally<br />
friendly carbonylat<strong>in</strong>g agents. [2] Very little is known about their utilization<br />
<strong>in</strong> carbonylation reactions of N-heteroaromatic compounds HetNH to HetNCO2R<br />
(R = alkyl, aryl) derivatives (eqn (1)), which are important synthetic <strong>in</strong>termediates<br />
for the preparation of a variety of chemicals, [3] <strong>in</strong>clud<strong>in</strong>g pharmaceutically relevant<br />
substances and biologically active compounds.<br />
HetNH + (RO)2CO → HetNCO2R + ROH (1)<br />
In this report we present a selective method for N-carbonylation of N-heteroaromatics<br />
HetNH, such as pyrrole (1), <strong>in</strong>dole (2) and carbazole (3), by a direct reaction with<br />
diphenyl carbonate (DPC; eqn (1), R = Ph), used as environmental friendly carbonyl<br />
active species <strong>in</strong> place of toxic and hazardous phosgene. [4]<br />
The carbonylation reaction can be effectively catalyzed by 1,8-diazabicyclo[5.4.0]undec-<br />
7-ene (DBU), which can act as a base catalyst by activat<strong>in</strong>g the HetNH substrate to<br />
the more nucleophilic HetN − anion, and as a nucleophile catalyst by activat<strong>in</strong>g the organic<br />
carbonate trough the formation of ketene am<strong>in</strong>al phenyl 1,8-diazabicyclo[5.4.0]<br />
undec-6-ene-8-carboxylate. [5]<br />
The <strong>in</strong>fluence of reaction parameters (temperature, reaction time, DBU load,<br />
DPC/HetNH molar ratio) on the productivity of the process has been also <strong>in</strong>vestigated.<br />
The synthetic methodology does not require severe temperature conditions, is<br />
solventless, simple (only one step), efficient (high yield) and selective, and offers a new<br />
solution to the synthesis of synthetically versatile HetNCO2Ph derivatives through a<br />
route alternative to the current traditional phosgenation methods.<br />
[1] (a) D. Delledonne, F. Rivetti, U. Romano, Appl. Catal. A 2001, 221, 241-251.<br />
[2] (a) M. Carafa, E. Quaranta, M<strong>in</strong>i-Rev. Org. Chem. 2009, 6, 168-183 and references there<strong>in</strong>;<br />
(b) E. Quaranta, M. Carafa, F. Trani, Appl. Catal. B 2009, 91, 380-388; (c) M. Distaso, E.<br />
Quaranta, Appl. Catal. B 2006, 66, 72-80; (d) M. Distaso, E. Quaranta, J. Catal. 2008, 253,<br />
278-288.<br />
[3] M. Carafa, V. Mele, E. Quaranta, Green Chem. 2012, 14, 217-225.<br />
[4] M. Carafa, F.Iannone, V. Mele, E. Quaranta, Green Chem. 2012, 14, 3377-3385.<br />
[5] M. Carafa, E. Mesto, E. Quaranta, Eur. J. Org. Chem. 2011, 2458-2465.<br />
Poster 190 Saturday 9:00 - 11:30 247
Porphyraz<strong>in</strong>es conta<strong>in</strong><strong>in</strong>g styryldiazep<strong>in</strong>e r<strong>in</strong>gs and their<br />
liposomal formulations: preparation, photochemical<br />
properties and photodynamic activity aga<strong>in</strong>st oral cancer cell<br />
l<strong>in</strong>es<br />
Jaroslaw Piskorz ∗ , Krystyna Konopka † , Nejat Düzgünes † , Tomasz Gosl<strong>in</strong>ski ‡ ,<br />
Jadwiga Mielcarek ∗<br />
∗ Department of Inorganic and Analytical Chemistry –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
† Department of Biomedical Sciences – University of the Pacific, School of Dentistry –<br />
2155 Webster Street – San Francisco – USA<br />
‡ Department of Chemical Technology of Drugs –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
piskorz.jaroslaw@onet.eu<br />
Photodynamic therapy (PDT) is a novel, alternative, anticancer treatment, which<br />
has also been used to cure cardiovascular, dermatological, and ophthalmic diseases<br />
as well as various microbial <strong>in</strong>fections. PDT consists of three factors: compound<br />
(photosensitizer), oxygen, and light. Upon irradiation with light of specific wavelength<br />
the photosensitizer undergoes activation and produces reactive oxygen species such<br />
as s<strong>in</strong>glet oxygen. As a consequence, it leads to the death of the treated tissue. [1]<br />
Here we present our data on the synthesis of porphyraz<strong>in</strong>es and tribenzoporphyraz<strong>in</strong>es<br />
conta<strong>in</strong><strong>in</strong>g styryldiazep<strong>in</strong>e r<strong>in</strong>gs. Condensation reactions of known dicyanodiazep<strong>in</strong>s<br />
with 3,4,5-trimetoxybenzaldehyde and 1-methyl-2-imidazolecarbaldehyde led to the<br />
novel 1,4-diazep<strong>in</strong>e-2,3-dicarbonitriles conta<strong>in</strong><strong>in</strong>g arylv<strong>in</strong>yl substituents. However,<br />
only diazep<strong>in</strong>es with 3,4,5-trimetoxyphenyl groups subjected to macrocyclization reactions<br />
gave the desired macrocycles of sufficient stability. [2,3] Novel macrocyclic<br />
compounds were characterized us<strong>in</strong>g various spectroscopic methods and extensively<br />
<strong>in</strong>vestigated <strong>in</strong> photochemical studies. Moreover, their photodynamic activity was<br />
exam<strong>in</strong>ed <strong>in</strong> vitro us<strong>in</strong>g two human oral squamous cell carc<strong>in</strong>oma cell l<strong>in</strong>es, HSC-3<br />
cells derived from the tongue and H413 cells from the buccal mucosa. Magnesium<br />
tribenzoporphyraz<strong>in</strong>e (Pz1) revealed high activity aga<strong>in</strong>st cancer cells even at low<br />
concentrations and low light dose. Moreover, significantly higher cytotoxicity of Pz1<br />
was observed after its <strong>in</strong>corporation <strong>in</strong>to negatively charged liposomes (figure).<br />
[1]<br />
R.R. Allison, C.H. Sibata, Photodiagn. Photodyn. Ther. 2010, 7, 61.<br />
[2]<br />
T. Gosl<strong>in</strong>ski, J. Piskorz, D. Brudnicki, A.J.P. White, M. Gdaniec, W. Szczolko, E. Tykarska.<br />
Polyhedron 2011 30, 1004.<br />
[3]<br />
J. Piskorz, E. Tykarska, M. Gdaniec, T. Gosliński, J. Mielcarek, Inorg. Chem. Commun. 20<br />
(2012) 13.<br />
This study was supported by the Polish M<strong>in</strong>istry of Science and Higher Education Grant No. N401<br />
067238 and funds from the University of the Pacific, Arthur A. Dugoni School of Dentistry.<br />
248 Saturday 9:00 - 11:30 Poster 191
Reactivity of InVO4 towards SrO <strong>in</strong> the solid state<br />
Agnieszka Pacześna, Elżbieta Filipek<br />
Department of Inorganic and Analytical Chemistry –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – Al. Piastów 42 – Szczec<strong>in</strong> – POL<br />
agnieszka.paczesna@zut.edu.pl<br />
The literature review has shown that InVO4–SrO system and reactions tak<strong>in</strong>g place<br />
<strong>in</strong> this system <strong>in</strong> the solid state <strong>in</strong> air have not been subject of research before our<br />
<strong>in</strong>vestigations. The properties of the components of the InVO4–SrO system are well<br />
known. [1, 2] The compound InVO4 is formed <strong>in</strong> the V2O5–In2O3 system and it melts<br />
<strong>in</strong>congruently deposit<strong>in</strong>g solid In2O3 at 1135 ◦ C. [3] The <strong>in</strong>dium(III) ortovanadate(V)<br />
crystallizes <strong>in</strong> the orthorhombic system, space group Cmcm. [4] There exist three polymorphic<br />
forms of InVO4. [5] InVO4 was found to be a visible light driven photocatalyst<br />
for H2 evolution from pure water. [1] Strontium oxide crystallizes <strong>in</strong> the cubic system,<br />
space group Fm3m. [6] SrO is promis<strong>in</strong>g as catalyst for the transesterification of soybean<br />
oil to biodiesel. [2]<br />
The aim of this research was, first of all, to <strong>in</strong>vestigate whether the reaction between<br />
InVO4 and SrO yields new phase. For the experiments were prepared eight samples<br />
with their compositions represent<strong>in</strong>g the whole components concentrations range of<br />
the system under consideration. Weighed <strong>in</strong> suitable proportions reactants were homogenized<br />
and calc<strong>in</strong>ated <strong>in</strong> the temperature range from 450 to 900 ◦ C <strong>in</strong> 24 h stages.<br />
After each heat<strong>in</strong>g stage XRD exam<strong>in</strong>ation was performed and selected samples were<br />
additionally subjected to DTA/TG <strong>in</strong>vestigation.<br />
The phase compositions of samples after the f<strong>in</strong>al heat<strong>in</strong>g stage have shown that<br />
InVO4 with SrO react <strong>in</strong> the solid state <strong>in</strong> air giv<strong>in</strong>g among other a new compound.<br />
However, they <strong>in</strong>dicated that the SrO content <strong>in</strong> the new compound is ∼ 50.00 mol%.<br />
On the base of XRD phase analysis of the all <strong>in</strong>vestigated samples, the two component<br />
system InVO4–SrO was divided <strong>in</strong>to five subsidiary subsystems.<br />
The <strong>in</strong>vestigations are cont<strong>in</strong>ued, first of all, <strong>in</strong> order to establish the formula of new<br />
compound.<br />
[1]<br />
J. Ye, Z. Zou, M. Oshikiri, A. Matsushita, M. Shimoda, M. Imai, T. Shisido, Chem. Phys.<br />
Lett. 2002, 356, 221-226.<br />
[2]<br />
X. Liu, H. He, Y. Wang, S. Zhu, Catal. Commun. 2007, 8, 1107-1111.<br />
[3]<br />
M. Touboul, A. Popot, J. Therm. Anal. 1986, 31, 117-124.<br />
[4]<br />
M. Touboul, P. Tolédano, Acta Cryst. 1980, B36, 240-245.<br />
[5]<br />
M. Touboul, K. Melghit, P. Bénard, Eur. J. Solid State Inorg. Chem. 1994, 31, 151-161.<br />
[6]<br />
W. Primak, H. Kaufman, R. Ward, J. Am. Chem. Soc. 1948, 70, 2043-2046.<br />
Poster 192 Saturday 9:00 - 11:30 249
Model<strong>in</strong>g the CO Oxidation Site of Nickel Conta<strong>in</strong><strong>in</strong>g<br />
Carbon Monoxide Dehydrogenase - Carbonyl Ligand<br />
Oxidation <strong>in</strong> a β-Diketim<strong>in</strong>ato Nickel Complex by N2O or O2<br />
Bett<strong>in</strong>a Horn, Christian Limberg, Christian Herwig, Michael Feist, Stefan Mebs<br />
Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Straße 2 – Berl<strong>in</strong> –<br />
GER<br />
BettiHorn@gmx.de<br />
Although carbon monoxide is an important substrate <strong>in</strong> many <strong>in</strong>dustrial processes<br />
such as hydroformylation, methanol synthesis, the Fischer-Tropsch and Monsanto<br />
processes, or for the production of dihydrogen <strong>in</strong> the water gas shift reaction, CO<br />
impurities <strong>in</strong> gases are often unwarranted, as they can poison catalysts employed to<br />
convert respective gases, for <strong>in</strong>stance H2. Hence, catalysts have been developed to<br />
selectively oxidize CO to the less harmful CO2, and these are often based on noble<br />
metals like gold. [1] In nature enzymatic systems do exist which utilize nickel centers<br />
for the reversible conversion of CO to CO2, namely carbon monoxide dehydrogenases<br />
(CODH). Here water serves as the oxygen source, and dur<strong>in</strong>g the reaction electrons<br />
as well as protons are produced concomitantly.<br />
Sett<strong>in</strong>g out with low coord<strong>in</strong>ated β-diketim<strong>in</strong>ato nickel carbonyl compounds [2] and<br />
bear<strong>in</strong>g the CODH reactivity <strong>in</strong> m<strong>in</strong>d we were <strong>in</strong>terested to <strong>in</strong>vestigate the reactivity<br />
of a nickel(0) carbonyl complex aga<strong>in</strong>st oxidiz<strong>in</strong>g reagents. As this complex is highly<br />
sensitive towards hydrolysis, experiments employ<strong>in</strong>g water as the oxygen source (as<br />
the enzyme) excluded themselves, though. Consider<strong>in</strong>g that CO oxidation requires<br />
one O atom (formally H2O → [O] + 2e − + 2H + ) we have chosen N2O as the O<br />
atom source, which has received <strong>in</strong>creas<strong>in</strong>g attention as an <strong>in</strong>trigu<strong>in</strong>g reagent for<br />
oxidations dur<strong>in</strong>g the last decades. [3] As an alternative oxidant O2 has been employed<br />
successfully, too. Here we describe the first precedent case of an oxidation of carbonyl<br />
ligands bound to low oxidation state nickel centers by both, N2O and O2, under<br />
formation of a unique carbonate compound, K6[L tBu Ni(CO3)]6, which was fully<br />
characterized. [4]<br />
[1] H.-J. Freund, G. Meijer, M. Scheffler, R. Schlögl, M. Wolf, Angew. Chem. 2011, 123, 10242;<br />
Angew. Chem. Int. Ed. 2011, 50, 10064.<br />
[2] B. Horn, S. Pfirrmann, C. Limberg, C. Herwig, B. Braun, S. Mebs, R. Metz<strong>in</strong>ger, Z. Anorg.<br />
Allg. Chem. 2011, 637, 1169.<br />
[3] V. N. Parmon, G. I. Panov, A. Uriarte, A. S. Noskov, Catal. Today 2005, 100, 115.<br />
[4] B. Horn , C. Limberg , C. Herwig , M. Feist, S. Mebs, Chem. Commun. 2012, 48, 8243.<br />
250 Saturday 9:00 - 11:30 Poster 193
Application of ’Click’ Cycloaddition for Synthesis of Sulfur<br />
and Oxygen Conta<strong>in</strong><strong>in</strong>g Oligomeric System<br />
Monika Stefaniak, Marc<strong>in</strong> Jasiński, Jarosław Romański<br />
Department of Organic and Applied Chemistry – University of Łódź – Tamka 12 –<br />
Łódź – POL<br />
monika_stefaniak@o2.pl<br />
Macrocyclic system, for example crown ethers or cryptands conta<strong>in</strong><strong>in</strong>g the heteroaromatic<br />
moiety, such imidazole, pyrid<strong>in</strong>e etc., are well known and play very important<br />
role <strong>in</strong> supramolecular chemistry and coord<strong>in</strong>ation chemistry as a complex<strong>in</strong>g<br />
agents. [1] In last decade, <strong>in</strong>dependently of each other, Meldal and Sharpless turned<br />
their attention to the <strong>in</strong>troduction of Cu(I) as catalyst <strong>in</strong> the Huisgen 1,3-dipolar cycloaddition.<br />
In this reaction very stable 1,2,3-triazole r<strong>in</strong>g is formed, which have very<br />
<strong>in</strong>terest<strong>in</strong>g application <strong>in</strong> medic<strong>in</strong>e or biotechnology. [2] We applied ’click’ approach to<br />
prepare sulfur and oxygen conta<strong>in</strong><strong>in</strong>g macrocyclic systems with built-<strong>in</strong> 1,2,3-triazole<br />
r<strong>in</strong>gs. We obta<strong>in</strong>ed compounds A, B, C with very good yields. The oligomer C<br />
conta<strong>in</strong>s the Cookson’s ’birdcage’ moiety which <strong>in</strong>creases its lipophilicity. It might be<br />
<strong>in</strong>terest<strong>in</strong>g to test possibility of our compounds to complex ions of metals of group I<br />
and II periodic table or also ions of metals of transitional groups.<br />
[1]<br />
J. L. Atwood, J. W. Steed, “Encyclopedia of Supramolecular Chemistry”, Taylor & Francis<br />
Group, 2004.<br />
[2]<br />
M. Meldal, Ch. W. Tornoe, Chem. Rev., 2008, 108, 2952-3015.<br />
Poster 194 Saturday 9:00 - 11:30 251
Ferrocenyl analogs of pl<strong>in</strong>abul<strong>in</strong> as organometallic <strong>in</strong>hibitors<br />
of tubul<strong>in</strong> polimerization<br />
Anna Wieczorek ∗ , Damian Plażuk ∗ , Andrzej Błauż † , Błażej Rychlik † ,<br />
Janusz Zakrzewski ∗<br />
∗ Department of Organic Chemistry – University of Łódź – 12 Tamka St. –<br />
91-403 Łódź – POL<br />
† Department of Molecular Biophysics – University of Łódź – 12/16 Banacha St. –<br />
90-237 Łódź – POL<br />
aniwie9@wp.pl<br />
Organometallic compounds are among the promis<strong>in</strong>g drug candidates with strongly<br />
enhanced anticancer activities. Ferrocene, one of the metallocenes, is the most widely<br />
<strong>in</strong>vestigated organometallic compound. It is a redox active, stable <strong>in</strong> biological media<br />
and nontoxic molecule. Ferrocene has shown only slight cytotoxic activity, whereas<br />
when conjugated with biologically active compounds it provides some promis<strong>in</strong>g anticancer<br />
agents. In recent years many ferrocenyl compounds have been prepared which<br />
have exhibited significant cytotoxicity [1,2] and anti-malarial activities [3] .<br />
Microtubules are noncovalent polymers of the prote<strong>in</strong> tubul<strong>in</strong> that are found <strong>in</strong> all<br />
divid<strong>in</strong>g eucariotic cells and <strong>in</strong> most differentiated cell types. Chemicals that target<br />
microtubules distrupt and suppreses the function by <strong>in</strong>hibit<strong>in</strong>g or promot<strong>in</strong>g microtubule<br />
polimerization. [4]<br />
Pl<strong>in</strong>abul<strong>in</strong> 1 is a potent microtubule-target<strong>in</strong>g agent derived from the natural diketopiperaz<strong>in</strong>e<br />
“phenylahist<strong>in</strong>” 2. Pl<strong>in</strong>abul<strong>in</strong> is now under phase II cl<strong>in</strong>ical trials as an<br />
anticancer drug. [5]<br />
We have synthesized ferrocenyl analogs of pl<strong>in</strong>abul<strong>in</strong> (e.g. 3 and 4) of exhibit<strong>in</strong>g<br />
potent microtubule depolymerization and highly cytotoxic.<br />
Acknowledgments: The authors are grateful for the f<strong>in</strong>ancial support of Polish<br />
National Science Centre (grant 2011/01/B/ST5/03933 years 2011-2014).<br />
Figure A 1 pl<strong>in</strong>abul<strong>in</strong>, 2 phenylahist<strong>in</strong>, 3-4 ferrocenyl analogs of pl<strong>in</strong>abul<strong>in</strong><br />
[1]<br />
S. Top, J. Tang, A. Vessières, D. Carrez, C. Provot, G. Jaouen, Chem.Commun., 955.<br />
[2]<br />
G. Gasser, I. Ott, N. Metzler-Nolte, J.Med.Chem. 2011, 54, 3.<br />
[3]<br />
M. Patra, M. G. Gassler, N. Metzler-Nolte, Dalton Trans. 2012, 41, 6350-6358.<br />
[4]<br />
A. Desai, T. J. Mitchison, Annu. Rev. Cell Dev. Biol. 1997, 13, 83.<br />
[5]<br />
Y. Yamazaki, K. Tanka, B. Nicholson, G. Deyanat-Yazdi, B. Potts, J.Med.Chem. 2012, 55,<br />
1056-1071.<br />
252 Saturday 9:00 - 11:30 Poster 195
Triazolopyrid<strong>in</strong>es: Reactions with dipolarophiles<br />
Rosa Adam, Shamim Alom, Belen Abarca, Rafael Ballesteros<br />
Organic Chemistry department – Universidad de Valencia –<br />
Avda Vicent Andrés Estellés s/n Facultat de Farmacia – Burjassot (Valencia) – ESP<br />
rosa.adam@uv.es<br />
[1,2,3]Triazolo[1,5-a]pyrid<strong>in</strong>es 1 are simple heterocycles present<strong>in</strong>g <strong>in</strong> solution an equilibrium<br />
with its open form, which can be considered a diazo compound. [1,2] The aim of<br />
this work has been to check if triazolopyrid<strong>in</strong>es are able to react as diazo compounds<br />
<strong>in</strong> the presence of several diporalophiles. To achieve our objective we performed<br />
reactions of triazolopyrid<strong>in</strong>es 1 with dipolarophiles (ethyl acrilate, ethyl propiolate<br />
and DMAD) (Scheme 1). In the case of ethyl acrilate reactions we obta<strong>in</strong>ed the<br />
correspond<strong>in</strong>g pyridyl ciclopropanes 2 by the formation of the correspond<strong>in</strong>g pyridyl<br />
carbene. [3] However, <strong>in</strong> the cases of ethyl propiolate and DMAD, pirazoyl pyrid<strong>in</strong>es 3<br />
were obta<strong>in</strong>ed demonstrat<strong>in</strong>g that a 1,3-dipolar cycloaddition reaction from the open<br />
form of triazolopyrid<strong>in</strong>e can take place.<br />
Scheme 1<br />
[1]<br />
C. Wentrup, Helv. Chim. Acta 1978, 1755.<br />
[2]<br />
F. Blanco, I. Alkorta, J. Elguero, V. Cruz, B. Abarca, R. Ballesteros, Tetrahedron 2008, 64,<br />
11150.<br />
[3]<br />
B. Abarca, R. Ballesteros, F. Blanco, Arkivoc 2007, (iv), 297.<br />
Poster 196 Saturday 9:00 - 11:30 253
Microwave and ultrasound assisted etherification of some<br />
biphenols<br />
Aleksandra Walczak, Magdalena Marc<strong>in</strong>kowska, Danuta Rasala<br />
Intitute of Chemistry – Jan Kochanowski University – Swietokrzyska 15G – Kielce – POL<br />
walczako@<strong>in</strong>teria.pl<br />
In the last few years there has been a grow<strong>in</strong>g <strong>in</strong>terest <strong>in</strong> the use of new techniques<br />
to improve classical organic synthesis. Thus, the obta<strong>in</strong> good yields with<strong>in</strong> shorter<br />
reaction time as well as higher selectivity both microwave irradiation and ultrasound<br />
assisted procedures were used <strong>in</strong> the preparation of mono- and disubstituted ethers<br />
of 4,4-biphenol and 4,4’-thiobiphenol. [1]<br />
In conclusion, we hope that the application microwaves and ultrasound irradiation is<br />
a very promis<strong>in</strong>g <strong>in</strong>novation and may stimulate further progress <strong>in</strong> the etherification<br />
of biphenols <strong>in</strong> comparison to conventional methodologies. [2] Moreover, it should be<br />
mentioned that a number of compounds under study show liquid crystall<strong>in</strong>e properties.<br />
[1] M. Marc<strong>in</strong>kowska, D. Rasała, A. Puchała, A. Gałuszka, Heterocycl. Commun. 2011, 17, 191.<br />
[2] B. Orzeszko, D. Melon-Ksyta, A. Orzeszko, Synthetic Commun. 2002, 32, 3425.<br />
254 Saturday 9:00 - 11:30 Poster 197
Enantioselective Additions of<br />
(Trifluoromethyl)Trimethylsilane to α-Im<strong>in</strong>o Ketones<br />
Derived from Arylglyoxals<br />
Emilia Obijalska, Alice Six, Grzegorz Mlostoń<br />
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 Street –<br />
91-403 Lodz – POL<br />
emilkaobijalska@gmail.com<br />
Synthesis of fluor<strong>in</strong>ated compounds is an attractive topic <strong>in</strong> the synthetic chemistry. [1]<br />
Special attention is focused on derivatives conta<strong>in</strong><strong>in</strong>g CF3 moiety because of their<br />
potential applications. [1] One of the most popular reagents applied for <strong>in</strong>corporation<br />
of CF3 group <strong>in</strong>to organic molecules is (trifluoromethyl)trimethylsilane (Ruppert’s-<br />
Prakash reagent, RPR). [2] The aim of present study was the elaboration of an new,<br />
enantioselective method for preparation β-am<strong>in</strong>o-α-(trifluoromethyl) alcohols which<br />
are known as useful build<strong>in</strong>g blocks for synthesis of fluor<strong>in</strong>ated derivatives. To the best<br />
of our knowledge there is only one paper <strong>in</strong> which enantioselective method for preparation<br />
of such compounds is described. [3] In our prelim<strong>in</strong>ary studies we developed a simple<br />
method for synthesis of rac-β-NHR-α-CF3 alcohols 2 start<strong>in</strong>g with α-im<strong>in</strong>oketones<br />
1. [4] In crucial step, the chemoselective addition of RPR to the C=O, followed by simultaneous<br />
reduction of C=N bond and desilylation, is performed. Some successful<br />
attempts of enantioselective reactions of Ruppert’s reagents with aldehydes and ketones<br />
are already reported. [5] Additions of RPR to 1 were carried out <strong>in</strong> the presence<br />
of catalytic system (8R,9S)- or (8S,9R)-3/KF or K2CO3 and they led chemoselectively<br />
to trimethylsilylethers. The latter compounds were converted <strong>in</strong>to f<strong>in</strong>al products 2<br />
<strong>in</strong> high overall yields (80-90%). However, the observed ee values rema<strong>in</strong>ed low to<br />
moderate (30-70%). The ee values were determ<strong>in</strong>ed based on the 1H or 19F NMR<br />
spectra registered for products 3 <strong>in</strong> the presence of (S)-(t-butyl)phenylthiophosph<strong>in</strong>ic<br />
acid ((S)-4) used as chiral solvat<strong>in</strong>g agent.<br />
[1]<br />
(a) Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, We<strong>in</strong>heim, 2004; (b) J.-P. Bégué,<br />
D. Bonnet-Delpon, Bioorganic and Medic<strong>in</strong>al Chemistry of Fluor<strong>in</strong>e, Wiley, Hoboken, New<br />
Jersey, 2008.<br />
[2]<br />
G. K. S. Prakash, M. Mandal, J. Fluor<strong>in</strong>e Chem. 2001, 112, 123.<br />
[3]<br />
F. Tur, J. M. Saá, Org. Lett. 2007, 9, 5079.<br />
[4]<br />
G. Mlostoń, E. Obijalska, A. Tafelska-Kaczmarek, M. Zaidlewicz, Journal of Fluor<strong>in</strong>e Chem.<br />
2010, 131, 1289.<br />
[5]<br />
(a) S. Mizuta, N. Shibata, M. Hib<strong>in</strong>o, S. Nagano, S. Nakamura, T. Toru, Tetrahedron 2007,<br />
63, 8521; (b) S. Mizuta, N. Shibata, S. Akiti, H. Fujimoto, Org. Lett. 2007, 9, 3707; (c) X. Hu,<br />
J. Wang, W. Li, L. L<strong>in</strong>, X. Liu, X. Feng, Tetrahedron Lett. 2009, 50, 4378.<br />
Research were f<strong>in</strong>anced by the National Science Center <strong>in</strong> Poland (Grant ‘SONATA’ # DEC-<br />
2011/03/D/ST5/05231)<br />
Poster 198 Saturday 9:00 - 11:30 255
Synthesis and characterization of sandwich-type europium<br />
(III) phthalocyan<strong>in</strong>es with different substitutent<br />
Ibrahim Erden, Merve Özdemir, Göknur Yasa, Fatma Aytan Kılıçarslan, Ali Erdogmus<br />
Chemistry Department – Yildiz Technical University – Esenler-34210 – İstanbul – TUR<br />
ierden@yildiz.edu.tr<br />
Phthalocynan<strong>in</strong>es are usually synthesized start<strong>in</strong>g from the appropriate phthalonitriles<br />
and their derivatives or their substitution yield as metal-free phthalociyan<strong>in</strong>e<br />
and metallophthalocyan<strong>in</strong>es which obta<strong>in</strong>ed especially <strong>in</strong> high temperatures with the<br />
presence of a suitable anhydrous metal salt. Sandwich-type porphyr<strong>in</strong>ato and/or phthalocyan<strong>in</strong>ato<br />
complexes, <strong>in</strong> which two planar and parallel conjugated p-systems are<br />
held <strong>in</strong> close proximity by lanthanide metal cation between the two macro-tetrapyrrole<br />
r<strong>in</strong>gs, have been <strong>in</strong>tensively studied over several decades <strong>in</strong> both fundamental academic<br />
and applied fields. [1,2]<br />
They are extensively used <strong>in</strong> pr<strong>in</strong>t<strong>in</strong>g <strong>in</strong>ks, coat<strong>in</strong>gs, pa<strong>in</strong>ts and plastics as blues and<br />
greens pigments. The phthalocyan<strong>in</strong>es f<strong>in</strong>d use also <strong>in</strong> catalyst for control of sulfur<br />
effluents, lasers, lubricants, photography reagents for cancer therapy, optical <strong>in</strong>formation<br />
storage systems, photography and xerography, high energy density batteries,<br />
chemical sensors, electrochoromic display devices and liquid crystal colour display<br />
applications. [3-5]<br />
In this study, we report the synthesis and characterization of different substituted phthalocyan<strong>in</strong>ato<br />
sandwich-type rare earth complexes. The new compounds have been<br />
characterized by elemental analysis, UV, FT-IR, 1H-NMR spectroscopy and mass<br />
spectra. The effect of the solvents and metal on the photophysical and photochemical<br />
parameters of the metallophthalocyan<strong>in</strong>es are also reported.<br />
[1] C. C. Leznoff, A. B. P. Lever (Eds.), Phthalocyan<strong>in</strong>es -Properties and Applications, vols.<br />
1-4, VCH, New York, 1989-1996.<br />
[2] N. B. McKeown, Phthalocyan<strong>in</strong>e Materials-Synthesis, Structure and Function, Cambridge<br />
University Press, New York, 1998.<br />
[3] G. Yaşa, A. Erdoğmuş, A. L. Uğur, M. K. Şener, U. Avcıata, T. Nyokong, “Photophysical<br />
andphotochemical properties of novel phthalocyan<strong>in</strong>es bear<strong>in</strong>g non-peripherally substituted mercaptoqu<strong>in</strong>ol<strong>in</strong>e<br />
moiety”, Journal of Porphyr<strong>in</strong>s and Phthalocyan<strong>in</strong>es 2012, 16, 845-854.<br />
[4] B. Bosnich, C. K. Poon, M. L. ve Tobe, Inorg. Chem. 1965, 4, 1102.<br />
[5] R.P. L<strong>in</strong>stead, “Phthalocyan<strong>in</strong>es”, J. Chem. Soc. 1934, 1016-1031.<br />
256 Saturday 9:00 - 11:30 Poster 199
Substituent Influence on Charge Transfer Interactions <strong>in</strong><br />
α,α-Diferrocenylthiophenes<br />
Matthäus Speck, He<strong>in</strong>rich Lang<br />
Inorganic Chemistry – Chemnitz University of Technology, Institute of Chemistry –<br />
Strasse der Nationen 62 – D-09111 Chemnitz – GER<br />
matthaeus.speck@chemie.tu-chemnitz.de<br />
There is an endur<strong>in</strong>g <strong>in</strong>terest <strong>in</strong> the chemistry of ferrocenyl-substituted homo- and<br />
hetero-aromatics, because such molecules can be regarded as model species for study<strong>in</strong>g<br />
metal-metal electronic <strong>in</strong>teraction. Furthermore, these π-conjugated organometallic<br />
compounds are qualified to design <strong>in</strong>novative electro-active materials like semiconduct<strong>in</strong>g<br />
polymers or molecular wires. The ferrocenyl moiety is a very promis<strong>in</strong>g<br />
candidate for us<strong>in</strong>g it as a redox-active group with a good stability <strong>in</strong> the neutral<br />
and <strong>in</strong> the oxidized state, enabl<strong>in</strong>g electrochemical reversible one-electron transfer<br />
processes. [1,2] With<strong>in</strong> this presentation, the synthesis, properties and spectroelectrochemical<br />
studies of ferrocenyl-substituted thiophenes (type A and B molecules) are<br />
reported. The <strong>in</strong>fluence of substituents on charge transfer <strong>in</strong>teractions between the<br />
iron centers will be discussed.<br />
[1] a) J. K. R. Thomas, J. T. L<strong>in</strong>, J. Organomet. Chem. 2001, 637, 139; b) S. Ogawa, H.<br />
Muraoka, R. Sato, Tetrahedron Lett. 2006, 47, 2479; c) F. Paul, S. Goeb, F. Justaud, G.<br />
Argouarch, L. Toupet, R. F. Ziessel, C. Lap<strong>in</strong>te, Inorg. Chem. 2007, 46, 9036; d) R. Packheiser,<br />
M. Lohan, B. Bräuer, F. Justaud, C. Lap<strong>in</strong>te, H. Lang, J. Org. Chem. 2008, 693, 2898; e) R.<br />
Packheiser, P. Ecorchard, B. Walfort, H. Lang, J. Organomet. Chem. 2008, 693, 933; f) D.<br />
E. Richardson, H. Taube, Coord. Chem. Rev. 1984, 60, 107. g) W. Kaim, B. Sarkar, Coord.<br />
Chem. Rev. 2007, 251, 584.<br />
[2] a) S. C. Jones, S. Barlow, D. O’Hare, Chem. Eur. J. 2005, 11, 4473; b) S. Barlow, D.<br />
O’Hare, Chem. Rev. 1997, 97, 637; c) I. M. Bruce, Coord. Chem. Rev. 1997, 166, 91; d) A.<br />
Hildebrandt, D. Schaarschmidt, H. Lang, Organometallics 2011, 30, 556; e) A. Hildebrandt, U.<br />
Pfaff, H. Lang, Rev. Inorg. Chem. 2011, 31, 111; f) A. Hildebrandt, H. Lang, Dalton Trans.<br />
2011, 40, 11831; g) J. M. Speck, R. Claus, A. Hildebrandt, T. Rüffer, E. Erasmus, L. van As, J.<br />
C. Swarts, H. Lang, Organometallics 2012, 31, 6373.<br />
Poster 200 Saturday 9:00 - 11:30 257
Novel term<strong>in</strong>alalkynyl-substituted asymmetric z<strong>in</strong>c<br />
phthalocyan<strong>in</strong>e and its polymers via click reaction<br />
Betul Nur Sen ∗ , Hatice D<strong>in</strong>cer ∗ , S<strong>in</strong>em Bayraktar † , Humeyra Mert Balaban †<br />
∗ Chemistry – Istanbul Technical University – 34469 – Istanbul – TUR<br />
† Chemical Eng<strong>in</strong>eer<strong>in</strong>g – Hitit University – Uctutlar street number:10 – Corum – TUR<br />
betulnursen_@hotmail.com<br />
Phthalocyan<strong>in</strong>es (Pcs) have been an area of <strong>in</strong>creas<strong>in</strong>g research for several years, due<br />
to their applicability <strong>in</strong> a variety of fields, such as liquid crystals, semiconductors,<br />
non-l<strong>in</strong>ear optics and electron transfer, among others.<br />
Synthetic routes to symmetrical Pcs are relatively straightforward, start<strong>in</strong>g from the<br />
appropriately substituted phthalonitrile. However, unsymmetrical Pcs conta<strong>in</strong><strong>in</strong>g different<br />
substituents <strong>in</strong> the benzo r<strong>in</strong>gs are more difficult to obta<strong>in</strong>. In addition these<br />
compounds provide the properties that can be used <strong>in</strong> advanced materials’ applications<br />
such as <strong>in</strong> particular non-l<strong>in</strong>ear optical properties. [1,2] Then the enormous<br />
diversity of phthalocyan<strong>in</strong>e - conta<strong>in</strong><strong>in</strong>g polymers, developed over thirty years of research,<br />
and offers the prospect of readily processed materials. [3] Recently, 1,3-dipolar<br />
cycloadditions, from the reactions between alkynes and azides known as, “click reactions”,<br />
have been recognized as a useful synthetic methodology due to their be<strong>in</strong>g fast,<br />
quantitative, reproducible, resistant to side reactions and highly tolerant to reaction<br />
conditions.<br />
In this study we aimed that the synthesis of asymmetric phthalocyan<strong>in</strong>e-conta<strong>in</strong><strong>in</strong>g<br />
polymers. For this purpose, firstly novel unsymmetrical term<strong>in</strong>alalkynyl substituted<br />
z<strong>in</strong>c phthalocyan<strong>in</strong>e will be synthesized from new 4-pent-4-ynyloxy-phthalonitrile and<br />
4-tert-butylphthalonitrile us<strong>in</strong>g statistical condensation method. Then, ‘click’ reactions<br />
between azido-term<strong>in</strong>ated polystyrene (PS) or poly(tert-butyl acrylate) (PtBA)<br />
and alkynyl-term<strong>in</strong>ated z<strong>in</strong>c phthalocyan<strong>in</strong>e will yield Pc functional polymers. All<br />
compounds will be characterized by 1 H NMR, 13 C NMR, FT-IR, UV-Vis, GPC and<br />
elemental analysis.<br />
[1] F. Matemadombo, M. Durmus, C. Togo, J. Limson, T. Nyokong, “Characterization of manganese<br />
tetraarylthiosubstituted phthalocyan<strong>in</strong>es self assembled monolayers”, Electrochim. Acta 2009, 54<br />
(23), 5557-5565.<br />
[2] Y. Q. Liu, Y. Xu, D. B. Zhu, T. Wada, H. Sasabe, X. S. Zhao, X. M. Xie, “Optical 2ndharmonic<br />
generation from langmuir-blodgett-films of an asymmetrically substituted phthalocyan<strong>in</strong>e”,<br />
J. Phys. Chem. 1995, 99 (18), 6957-6960.<br />
[3] N.B. Mc Keown, J. Mater. Chem. 2000, 10 (9), 1979.<br />
258 Saturday 9:00 - 11:30 Poster 201
Chemoselective additions of (trifluoromethyl)trimethylsilane<br />
to C=N bond <strong>in</strong> α-im<strong>in</strong>o ketones derived from arylglyoxals<br />
Marc<strong>in</strong> Kowalski, Emilia Obijalska, Grzegorz Mlostoń<br />
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 Street –<br />
Lodz – POL<br />
Johny616@gmail.com<br />
Synthesis of fluoroorganic compounds is a challeng<strong>in</strong>g topic of modern organic chemistry.<br />
Incorporation of fluor<strong>in</strong>e atoms or perfluoroalkyl groups <strong>in</strong>to the structure of organic<br />
molecules results <strong>in</strong> significant changes <strong>in</strong> their physical, chemical and biological<br />
properties. [1] (Trifluoromethyl)trimethylsilane (so-called Ruppert’s-Prakash Reagent,<br />
RPR) is one of the most convenient reagent used to nucleophilic trifluoromethylation<br />
of electrophilic subtrates. [2] The goal of presented study is to elaborate new,<br />
simple procedure for synthesis of β-am<strong>in</strong>o-β-(trifluoromethyl) alcohols of type 2 us<strong>in</strong>g<br />
easily available α-im<strong>in</strong>oketones 1 and (trifluoromethyl)trimethylsilane. There are<br />
described <strong>in</strong> literature many methods for preparation of β-am<strong>in</strong>o-α-(trifluoromethyl)<br />
alcohols. [3] Relatively less papers concern preparation of β-am<strong>in</strong>o-α-(trifluoromethyl)<br />
alcohols. They are based on exploration of difficult available trifluoronitroethane or<br />
N,S-ketals of trifluoropyruvaldehydes. [4] In the key step of our procedure additions<br />
of RPR to 1 were performed <strong>in</strong> the presence of <strong>in</strong> situ generated HF (from KF or<br />
KHF2) what allowed for activation of C=N bond. In optimised conditions adducts 2<br />
were the ma<strong>in</strong> products. Further reduction of 2 led to desired am<strong>in</strong>oalcohols 3 with<br />
very good diastereoselectivity.<br />
Research were f<strong>in</strong>anced by the National Science Center <strong>in</strong> Poland (Grant ’SONATA’<br />
# DEC-2011/03/D/ST5/05231)<br />
[1] (a) Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, We<strong>in</strong>heim, 2004; (b) J.-P. Bégué,<br />
D. Bonnet-Delpon, Bioorganic and Medic<strong>in</strong>al Chemistry of Fluor<strong>in</strong>e, Wiley, Hoboken, New<br />
Jersey, 2008.<br />
[2] G. K. S. Prakash, M. Mandal, J. Fluor<strong>in</strong>e Chem. 2001, 112, 123.<br />
[3] G. Mlostoń, E. Obijalska, H. Heimgartner, Journal of Fluor<strong>in</strong>e Chem. 2010, 131, 830.<br />
[4] (a) A. K. Beck, D. Seebach, Chem. Ber. 1991, 124, 2897; (b) R. E. Marti, J. He<strong>in</strong>zer, D.<br />
Seebach, Liebigs Ann. 1995, 1193; (c) P. Bravo, M. Crucianelli, T. Ono, M. Zanda, Journal of<br />
Fluor<strong>in</strong>e Chemistry 1999, 97, 27.<br />
Poster 202 Saturday 9:00 - 11:30 259
Reactivity of palladium carboxylate complexes towards<br />
acetonitrile<br />
Oleg Shishilov ∗ , Nailya Akhmadull<strong>in</strong>a † , Andrei Churakov ∗ , Inessa Efimenko ∗<br />
∗ Kurnakov Institute of General and Inorganic Chemistry of RAS – Len<strong>in</strong>sky pr., 31 –<br />
Moscow – RUS<br />
† Baikov Institute of Metallurgy and Material Science of RAS – Len<strong>in</strong>sky pr., 49 –<br />
Moscow – RUS<br />
oshishilov@gmail.com<br />
It’s well-known that nitriles undergo catalytic transformations, <strong>in</strong>clud<strong>in</strong>g C-C, C-N<br />
and C-O coupl<strong>in</strong>g reactions with rearrangement of nitriles or dimerization of products<br />
form<strong>in</strong>g nitrogen-conta<strong>in</strong><strong>in</strong>g compounds of different types <strong>in</strong> the presence of complexes<br />
of transition metals and especially plat<strong>in</strong>um metals. We studied reactions of two<br />
classes of palladium carboxylate compounds - b<strong>in</strong>ary carboxylates [P d(RCO2)2]n and<br />
nitrosyl carboxylates P d4(NO)2(RCO2)6 - with acetonitrile <strong>in</strong> some common organic<br />
solvents. B<strong>in</strong>ary carboxylates are a basic class of palladium carboxylate complexes<br />
and nitrosyl carboxylates were chosen due to potential multifunctionality of nitrosyl<br />
groups. For <strong>in</strong>stance, earlier it was shown that NOx-species promote transfer of<br />
oxygen and reoxidation of palladium <strong>in</strong> catalytic processes.<br />
It was found that reaction of palladium acetate P d3(µ-CH3CO2)6 with acetonitrile<br />
<strong>in</strong> benzene leads to formation of b<strong>in</strong>uclear complex of palladium(II) P d2(C6H4-o-<br />
C(CH3)=NH)2(µ-CH3CO2)2, which conta<strong>in</strong>s coord<strong>in</strong>ated 1-phenylethanim<strong>in</strong>e that<br />
forms as a result of C-C-coupl<strong>in</strong>g between nitrile and arene molecules. Reactions of<br />
polynuclear nitrosyl carboxylate complexes P d4(NO)2(RCO2)6 of palladium(II) with<br />
acetonitrile <strong>in</strong> acetone <strong>in</strong> the presence of water lead to formation of complexes P d5(µ-<br />
NO)(µ-C6H11CO2)7(µ, µ-CH3C(=N)OC(=N)CH3) and P d5(µ-NO)(µ-NO2) (µ-<br />
CMe3CO2)6(µ, µ-CH3C(=N)OC(=N)CH3), which are the first palladium complexes<br />
conta<strong>in</strong><strong>in</strong>g coord<strong>in</strong>ated acetimidic anhydride. The complexes belong to a new<br />
topological type of carboxylate palladium compounds with 5-nuclear cyclic metalcore.<br />
Acetimidic anhydride forms as a result of complicate hydration process conjugated<br />
with C-O-coupl<strong>in</strong>g. Also complex P d5(µ-NO)(µ-NO2)(µ-CMe3CO2)6(µ, µ-<br />
CH3C(=N)OC(=N)CH3) is the first fully characterized palladium carboxylate compound<br />
conta<strong>in</strong><strong>in</strong>g nitrosyl and nitrite groups together.<br />
We are grateful to the Council of the President of the Russian Federation for young<br />
scientists for f<strong>in</strong>ancial support (project 966.2012.3).<br />
Molecular structure of<br />
P d5(µ-NO)(µ-NO2)(µ-CMe3CO2)6(µ, µ-CH3C(=N)OC(=N)CH3)<br />
260 Saturday 9:00 - 11:30 Poster 203
Didecyldimethylammonium salts of am<strong>in</strong>o acids - the<br />
characteristics and application directions<br />
Paula Ossowicz ∗ , Zbigniew Rozwadowski ∗ , Ewa Janus † , Ryszard Pilawka ‡<br />
∗ Department of Inorganic and Analytical Chemistry –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – 42 Piastów Ave. – Szczec<strong>in</strong> – POL<br />
† Institute of Organic Chemical Technology –<br />
West Pomeranian University of Technology, Szczec<strong>in</strong> – Pulaski Str. 10 – Szczec<strong>in</strong> – POL<br />
‡ Institute of Polymers – West Pomeranian University of Technology, Szczec<strong>in</strong> –<br />
Pulaski Str. 10 – Szczec<strong>in</strong> – POL<br />
possowicz@zut.edu.pl<br />
Currently, the attention is focused on a new generation of ionic liquids, which are<br />
derived from natural raw materials such as am<strong>in</strong>o acids. Am<strong>in</strong>o acid ionic liquids are<br />
an alternative to ionic liquids, based solely on petrochemical raw materials. Am<strong>in</strong>o<br />
Acid Ionic Liquids derived from biorenewable raw materials are more biocompatible,<br />
because of greater biodegradability <strong>in</strong> the environment and lower toxicity (ecotoxicity<br />
and cytotoxicity).<br />
The synthesis, identification and physical properties of didecyldimethylammonium<br />
salts of L am<strong>in</strong>o acids were presented. Identification was based on 1 H NMR, 13 C<br />
NMR, FT-IR, UV-VIS analyses. The physical properties of new chiral ionic liquids,<br />
for example the density, viscosity, surface tension, specific rotation, water content,<br />
thermal stability (TG) and phase transformations (DSC) were determ<strong>in</strong>ed. Didecyldimethylammonium<br />
salts of L-am<strong>in</strong>o acids salts were soluble <strong>in</strong> water and were<br />
also characterized by surface tension, critical micelle concentration and stabillity <strong>in</strong><br />
alkal<strong>in</strong>e and acid solution.<br />
Synthesis of didecyldimethylammonium salts of am<strong>in</strong>o acids<br />
Poster 204 Saturday 9:00 - 11:30 261
Design and Synthesis of a new Galantham<strong>in</strong>e Delivery<br />
System<br />
Mihaela-Liliana Țînțaş, Lénaig Foucout, Sylva<strong>in</strong> Petit, Sylva<strong>in</strong> Oudeyer,<br />
Cyril Papamicaël, V<strong>in</strong>cent Levacher<br />
UMR CNRS 6014, IRCOF Rouen, INSA de Rouen – Rue Tesniere 1 –<br />
Mont-Sa<strong>in</strong>t-Aignan – FRA<br />
mihaela_t<strong>in</strong>tas@yahoo.com<br />
Galantham<strong>in</strong>e is one of the acetylchol<strong>in</strong>esterase <strong>in</strong>hibitors (AChEIs) prescribed as<br />
anti-Alzheimer Disease (AD) drug. It has a dist<strong>in</strong>ct mode of action, not observed for<br />
the other <strong>in</strong>hibitors, be<strong>in</strong>g a competitive and reversible AChEI; an allosteric modulator<br />
of nicot<strong>in</strong>ic acetylchol<strong>in</strong>e receptors improv<strong>in</strong>g their function<strong>in</strong>g by help<strong>in</strong>g the<br />
release of ACh; and modulates the levels of other neurotransmitters <strong>in</strong>volved <strong>in</strong> dementia:<br />
glutamate, seroton<strong>in</strong> and GABA. The <strong>in</strong>hibit<strong>in</strong>g properties of galantham<strong>in</strong>e<br />
are considered quite modest, but its multiple actions make it one of the most efficient<br />
AD therapy drug. It was observed <strong>in</strong> numerous cases that long treatment with<br />
galantham<strong>in</strong>e produces many side effects (eg. nausea, vomit<strong>in</strong>g, diarrhea, dizz<strong>in</strong>ess,<br />
etc.) caus<strong>in</strong>g treatment disruption. AD patients are dependent of cont<strong>in</strong>uous adm<strong>in</strong>istration<br />
of AChEI to have day-to-day function<strong>in</strong>g and maximize their quality of life<br />
as much as possible. A way to overcome the side-effects of a neuroactive drug is to<br />
ensure a bra<strong>in</strong> targeted transport to the active site mediated by a carrier. One such<br />
chemical delivery system towards bra<strong>in</strong> was developed by Bodor [1] and is based on dihydropyrid<strong>in</strong>e–pyrid<strong>in</strong>ium<br />
redox couple. The neuroactive drug is covalently l<strong>in</strong>ked to<br />
a dihydropyrid<strong>in</strong>e moiety that plays the role of a lipoidal carrier towards bra<strong>in</strong>. Dihydropyrid<strong>in</strong>e<br />
is an unstable and chemically fragile moiety. We developed a new stable<br />
and assertive chemical delivery system based on a dihydroqu<strong>in</strong>ol<strong>in</strong>e–qu<strong>in</strong>ol<strong>in</strong>ium redox<br />
couple. [2,3] We applied this system to galantham<strong>in</strong>e, as schematically represented<br />
below. This transformation represents a valuable drug modification strategy which<br />
<strong>in</strong>creases the chances of a site-specific and susta<strong>in</strong>ed delivery of galantham<strong>in</strong>e <strong>in</strong>side<br />
bra<strong>in</strong>. Dihydroqu<strong>in</strong>ol<strong>in</strong>e moiety will ensure the transport of the drug to the central<br />
nervous system through the lipophilic blood bra<strong>in</strong> barrier (BBB) by passive diffusion.<br />
Then oxidation <strong>in</strong>to a charged qu<strong>in</strong>ol<strong>in</strong>ium salt will prevent the system to cross back<br />
the BBB aga<strong>in</strong>. Enzymatic cleavage will liberate galantham<strong>in</strong>e to target directly the<br />
AChE implied <strong>in</strong> AD followed by its normal metabolism and clearance. Liberation of<br />
the drug just <strong>in</strong>side the bra<strong>in</strong> will lead to lower drug doses and less undesirable side<br />
effects.<br />
[1] L. Prokai, K. Prokai-Tatrai, N. Bodor, Med. Res. Rev. 2000, 20, 367-416.<br />
[2] L. Foucout, F. Gourand, M. Dhilly, P. Bohn, G. Dupas, J. Costent<strong>in</strong>, A. Abbas, F. Marsais, L.<br />
Barré, V. Levacher, Org. Biomol. Chem. 2009, 7, 3666-3673.<br />
[3] P. Bohn, N. Le Fur, G. Hagues, J. Costent<strong>in</strong>, N. Torquet, C. Papamicael, F. Marsais, V.<br />
Levacher, Org. Biomol. Chem. 2009, 7, 2612-2618.<br />
262 Saturday 9:00 - 11:30 Poster 205
Optical Anisotropy of Pb Nanowires on Si(557)<br />
Arne Baumann ∗ , Jochen Räthel ∗ , Eugen Speiser ∗ , Daniel Lükermann † ,<br />
Christopher Krich † , Christoph Tegenkamp † , Norbert Esser ∗<br />
∗ Nanostrukturen – Leibniz-Institut für Analytische Wissenschaften - ISAS - e. V. –<br />
Albert-E<strong>in</strong>ste<strong>in</strong>-Straße 9 – 12489 Berl<strong>in</strong> – GER<br />
† Institut für Festkörperphysik – Leibniz Universität Hannover – Appelstraße 2 –<br />
30167 Hannover – GER<br />
arne.baumann@isas.de<br />
Reduc<strong>in</strong>g the dimensionality of metal films on semi-conductor surfaces can lead to the<br />
appearance of <strong>in</strong>terest<strong>in</strong>g physical phenomena. Due to the high electron correlation it<br />
could be not longer accurate to describe the electron gas by traditional Fermi liquid<br />
theory. For example, the <strong>in</strong>herent <strong>in</strong>stabilities of 1D electronic systems, like Peierls<br />
<strong>in</strong>stabilities, can entail the formation of charge and sp<strong>in</strong> density waves, moreover the<br />
systems may exhibit Lutt<strong>in</strong>ger liquid behavior. The goal of our work is to elucidate<br />
these phenomena by the means of optical methods, such as reflectance anisotropy<br />
spectroscopy (RAS).<br />
Metal nanowire model systems <strong>in</strong>volve noble metal, In or Pb nanowires on vic<strong>in</strong>al<br />
Si or Ge surfaces. One particular <strong>in</strong>terest<strong>in</strong>g system is Pb on Si(557), where the<br />
adsorption of approximately 1.3 monolayers of Pb onto the clean Si(557) surface<br />
<strong>in</strong>duces a reorganization of the surface structure. The clean Si(557) surface consists<br />
of (111) oriented terraces and (112) oriented steps. After the adsorption of Pb low<br />
energy electron dispersion patterns and scann<strong>in</strong>g tunnel<strong>in</strong>g microscopy measurements<br />
show an evenly stepped surface decorated with distant Pb nanowires.<br />
At low temperatures (< 78 K) this system shows almost exclusively electronic conductivity<br />
parallel to the steps. Increas<strong>in</strong>g the temperature above this temperature<br />
causes a phase transition and enables conductivity perpendicular to the wires. A reorder<strong>in</strong>g<br />
of the surface <strong>in</strong>duces a change <strong>in</strong> the electronic properties and with this also<br />
<strong>in</strong> the dielectric function. Hence, <strong>in</strong> this clearly anisotropic system it is possible to<br />
apply RAS, <strong>in</strong> connection with density functional theory based calculations, to study<br />
the anisotropic optical transitions <strong>in</strong> the surface band structure. By compar<strong>in</strong>g the<br />
RAS spectra of the clean Si(557) surface with the Pb covered surface it is possible<br />
to identify signals belong<strong>in</strong>g to adsorption <strong>in</strong>duced states. Furthermore, by carry<strong>in</strong>g<br />
out temperature dependant measurements it can be possible to observe the appearance<br />
of new anisotropic transitions below 78 K, <strong>in</strong>dicat<strong>in</strong>g a change <strong>in</strong> the surface<br />
band structure of the system, as well as changes <strong>in</strong> the optical conductance behavior<br />
accompany<strong>in</strong>g the phase transition.<br />
Poster 206 Saturday 9:00 - 11:30 263
Micelle Formation<br />
Marta Cybulak<br />
Faculty of Chemistry – Maria Curie-Sklodowska University <strong>in</strong> Lubl<strong>in</strong> –<br />
pl. Marii Curie-Sklodowskiej 2 – Lubl<strong>in</strong> – POL – Lubl<strong>in</strong> – POL<br />
marta.cybulak@wp.pl<br />
The structure and thermodynamics of formation of mixed micelles is of great theoretical<br />
<strong>in</strong>terest. Micelles are also often present and often <strong>in</strong>tegrally <strong>in</strong>volved <strong>in</strong> practical<br />
processes. For example, <strong>in</strong> a small pore volume surfactant flood<strong>in</strong>g process (sometimes<br />
called micellar flod<strong>in</strong>g), the solution <strong>in</strong>jected <strong>in</strong>to an oil field generally conta<strong>in</strong>s 5-12<br />
weight % surfactant and the surfactant is predom<strong>in</strong>ately <strong>in</strong> micellar form <strong>in</strong> the reservoir<br />
water. In detergency, solubilization can be important, so micelles are generally<br />
present <strong>in</strong> the detergent solution. In micellar – enhanced ultrafiltration, a separation<br />
technique to remove dissolved organic from water, micelles effect the separation.<br />
The Critical Micelle Concentration (CMC) is the lowest surfactant concentration at<br />
which micelles form – the lower the CMC, the greater the tendency of a system to<br />
form micelles. When the total fraction of surfactant equals the CMC, an <strong>in</strong>f<strong>in</strong>itesimal<br />
fraction of surfactant is present as micelles.<br />
[1]<br />
W.B. Gogarty, J. Pet. Technol. 1983, 35, 1581.<br />
[2]<br />
K. Sh<strong>in</strong>oda <strong>in</strong> “Colloidal Surfactants”, K. Sh<strong>in</strong>oda, T. Tanamushi, T. Nakagawa, T. Isemura,<br />
Academic Press: New York, 1963, Chapter 1.<br />
[3]<br />
R.F. Kamrath, E.I. Frances, J. Phys. Chem. 1984, 88, 1642.<br />
[4]<br />
K. Sh<strong>in</strong>oda, J. Phys. Chem. 1954, 58, 541.<br />
[5]<br />
K.J. Mysels, R.J. Otter, J. Colloid Sci. 1961, 16, 474.<br />
[6]<br />
B.W. Barry, J.C. Morrison, G.F. Russel, J. Colloid Interface Sci. 1970, 33, 554.<br />
264 Saturday 9:00 - 11:30 Poster 207
Shear-<strong>in</strong>duced structure formation <strong>in</strong> a mixture of a nonionic<br />
associative polymer and anionic surfactant<br />
Alena Tomsik, Jaroslav Katona, Sandra Njaradi<br />
Department of Biotechnology and Pharmaceutical Eng<strong>in</strong>eer<strong>in</strong>g –<br />
University of Novi Sad, Faculty of Technology –<br />
Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia – Novi Sad – SRB<br />
alena.tomsik@gmail.com<br />
Mixtures of polymers and surfactants are commonly found <strong>in</strong> a wide range of consumer<br />
products. Interaction between polymers and surfactants <strong>in</strong>fluence different<br />
properties of these products, e.g. stability, flow properties, phase behavior etc. [1-3] In<br />
this work, <strong>in</strong>fluence of shear rate on flow properties of a mixture of hydroxypropylmethyl<br />
cellulose (HPMC), a nonionic associative polymer, and sodium dodecylsulfate<br />
(SDS), an anionic surfactant was <strong>in</strong>vestigated. B<strong>in</strong>ary mixtures composed of 0.70%<br />
wt. HPMC and SDS concentration rang<strong>in</strong>g from 0.00% to 2.00% wt. were prepared<br />
<strong>in</strong> deionized water and <strong>in</strong> 0.01M NaCl. Rheological properties of the mixtures were<br />
exam<strong>in</strong>ed by determ<strong>in</strong><strong>in</strong>g the steady state viscosity under different shear rates. At<br />
low shear rates, HPMC and SDS mixtures show Newtonian plateau where viscosity is<br />
<strong>in</strong>dependent on shear rate. On further <strong>in</strong>crease <strong>in</strong> shear rate, a typical shear th<strong>in</strong>n<strong>in</strong>g<br />
behavior with a power low decrease <strong>in</strong> viscosity takes place. However, <strong>in</strong> mixtures<br />
with SDS concentration higher than 0.15% SDS, above a critical shear rate an <strong>in</strong>crease<br />
<strong>in</strong> viscosity accompanied with an <strong>in</strong>crease <strong>in</strong> the first normal stress difference<br />
occurs. The shear thicken<strong>in</strong>g behavior <strong>in</strong>dicates shear <strong>in</strong>duced structure formation<br />
due to HPMC-SDS <strong>in</strong>teraction. The shear thicken<strong>in</strong>g flow takes place <strong>in</strong> both water<br />
and 0.01M NaCl b<strong>in</strong>ary mixtures. The critical shear rate is lower, while the viscosity<br />
<strong>in</strong>crease is more pronounced <strong>in</strong> the 0.01M NaCl mixtures than <strong>in</strong> the correspond<strong>in</strong>g<br />
deionised water mixtures. This is attributed to a stronger HPMC-SDS <strong>in</strong>teraction<br />
due to charge screen<strong>in</strong>g effect <strong>in</strong> HPMC-SDS complex by sodium cations. When<br />
SDS concentration is higher than 1.50% wt. no shear thicken<strong>in</strong>g is observed <strong>in</strong> the<br />
<strong>in</strong>vestigated shear rate range.<br />
[1] B. Nystrom, A.-L. Kjoniksen, B. L<strong>in</strong>dman, “Effect of temperature, surfactant, and salt on the<br />
rheological behavior <strong>in</strong> semidilute aqueous systems of a nonionic cellulose ether”, Langmuir 1996,<br />
12, 3233-3240.<br />
[2] J. M. Katona, V. J. Sovilj “Rheological <strong>in</strong>vestigation on dynamics and structure of separated<br />
phases <strong>in</strong> polymer-mixture - ionic surfactant ternary mixtures”, Carbohydrate Polymers 2008,<br />
74, 193-200.<br />
[3] J.M. Katona, V.J. Sovilj, L.B. Petrović, “Microencapsulation of oil by polymer mixture ionic<br />
surfactant <strong>in</strong>teraction <strong>in</strong>duced coacervation”, Carbohydrate Polymers 2010, 79, 563-570.<br />
Poster 208 Saturday 9:00 - 11:30 265
Studies of Dodecane/Water Interfaces by<br />
Polarization-Dependent and Time-Resolved Second<br />
Harmonic Generation<br />
Michal Hamkalo, Piotr Fita<br />
Faculty of Physics – Institute of Experimental Physics, University of Warsaw – Hoza 69 –<br />
Warsaw – POL<br />
michalhamkalo@student.uw.edu.pl<br />
Properties of organic dyes: eos<strong>in</strong> B, Rhodam<strong>in</strong>e 640, Rhodam<strong>in</strong>e 6G, Malachite<br />
Green, and Sulforhodam<strong>in</strong>e 101, at dodecane/water <strong>in</strong>terfaces have been <strong>in</strong>vestigated<br />
with polarization-dependent and time-resolved surface second harmonic generation<br />
(SHG). [1,2] In this experimental technique an <strong>in</strong>terface under study is illum<strong>in</strong>ated<br />
(probed) with a beam of femtosecond pulses and the second harmonic of the probe<br />
beam is detected us<strong>in</strong>g a sensitive photodetector. Due to symmetry the second harmonic<br />
is generated only <strong>in</strong> a very th<strong>in</strong> layer separat<strong>in</strong>g two different phases, which<br />
ensures high spatial selectivity.<br />
This study was focused on polarization-dependent SHG, <strong>in</strong> which the probe beam is<br />
l<strong>in</strong>early polarized and the plane of polarization can be cont<strong>in</strong>uously rotated us<strong>in</strong>g a<br />
halfwave plate. Polarization of the detected second harmonic is selected by a polarizer<br />
located after the sample and can be either parallel or perpendicular to the plane of<br />
<strong>in</strong>cidence. For both polarizations of the detected light its <strong>in</strong>tensity is measured as a<br />
function of the direction of polarization of the probe beam.<br />
The <strong>in</strong>vestigation aims to describe the behavior of organic molecules at <strong>in</strong>terfaces<br />
between 2 non-mix<strong>in</strong>g liquids. In polarization-dependent measurements 3 parameters<br />
were varied: the dye concentration, the <strong>in</strong>tensity of the laser beam and the age of<br />
the sample. It has been found that both, the dye concentration and - surpris<strong>in</strong>gly,<br />
the probe beam <strong>in</strong>tensity affect the polarization dependence of the second harmonic<br />
<strong>in</strong>tensity. Comparison of the results obta<strong>in</strong>ed for different conditions suggests that<br />
the state of molecules at the surface changes and aggregates are formed at higher<br />
dye concentrations. Nevertheless aggregation alone cannot expla<strong>in</strong> all the observed<br />
phenomena, therefore we will carry out additional time-resolved measurements which<br />
should help to identify the processes occurr<strong>in</strong>g <strong>in</strong> molecules adsorbed at the <strong>in</strong>terface.<br />
[1] K. B. Eisenthal, J. Phys. Chem. 1996, 100, 12997-13006.<br />
[2] J. C. Conboy, J. L. Daschbach, G. L. Richmond, J. Phys. Chem. 1994, 98, 9688-9692.<br />
266 Saturday 9:00 - 11:30 Poster 209
Emission Properties of Quantum Dots Affected by the<br />
Ligand Shell – Theory and Experiment<br />
Susanne Leubner ∗ , Soheil Hatami † , Tommy Lorenz ∗ , Jan-Ole Joswig ∗ ,<br />
Nikolai Gaponik ∗ , Ute Resch-Genger † , Alexander Eychmüller ∗<br />
∗ Physical Chemistry – TU Dresden – Dresden – GER<br />
† BAM Federal Institute for Materials Research and Test<strong>in</strong>g – Berl<strong>in</strong> – GER<br />
susanne.leubner@chemie.tu-dresden.de<br />
In recent years semiconductor quantum dots (QDs) have drawn a broad <strong>in</strong>terdiscipl<strong>in</strong>ary<br />
attention as an attractive choice for the use <strong>in</strong> light-emitt<strong>in</strong>g devices and<br />
imag<strong>in</strong>g techniques. This is strongly related to their superior optical properties compared<br />
to other classes of functional dyes, such as high photostability, large ext<strong>in</strong>ction<br />
coefficient, tunable and narrow band gap lum<strong>in</strong>escence and high photolum<strong>in</strong>escence<br />
(PL) quantum yields.<br />
Especially the PL quantum yield is a significant characteristic for the emission quality<br />
and is often cited <strong>in</strong> literature. However, for valuable data on one hand a proper<br />
determ<strong>in</strong>ation procedure is crucial and on the other hand the understand<strong>in</strong>g of particle<br />
properties <strong>in</strong>fluenc<strong>in</strong>g the emission is of great importance. In detail, the optical<br />
properties of the nanocrystals are affected by both the core material and the ligand<br />
shell. As the surface chemistry of QDs can still be tuned after the synthesis, a complete<br />
understand<strong>in</strong>g of the impact of the stabiliz<strong>in</strong>g shell on the emission properties is<br />
promis<strong>in</strong>g for the design of highly emitt<strong>in</strong>g materials.<br />
Hence, this study discusses the proper experimental PL quantum yield determ<strong>in</strong>ation<br />
as well as the analytical study of the nanoparticle surface and its relation to the<br />
PL quantum yield for the model system of aqueous synthesized CdTe nanocrystals<br />
capped with thiols. The <strong>in</strong>vestigation of the ligand shell <strong>in</strong>cludes analytical techniques<br />
together with theoretical calculations.<br />
Poster 210 Saturday 9:00 - 11:30 267
N -Am<strong>in</strong>oalkylation of heterocycles with α-amidosulfones<br />
Marc Montes<strong>in</strong>os Magraner, Gonzalo Blay, Rosa María Girón, José Ramón Pedro<br />
Departament de Química Orgànica – Universitat de València – Dr. Mol<strong>in</strong>er, 50 –<br />
Burjassot – ESP<br />
marc.montes<strong>in</strong>os@uv.es<br />
Nitrogen conta<strong>in</strong><strong>in</strong>g heterocycles are present <strong>in</strong> a vast number of natural products<br />
and biologically active molecules. [1] So, the functionalization of these compounds is<br />
an important goal <strong>in</strong> organic chemistry. However, the <strong>in</strong>troduction of an am<strong>in</strong>oalkyl<br />
group is less developed due to the low reactivity of im<strong>in</strong>es as electrophiles. [2]<br />
Recently, we have carried out the first regioselective am<strong>in</strong>oalkylation of <strong>in</strong>doles 1 with<br />
α-amidosulfones (7) <strong>in</strong> either the C -3 or N -1 position under basic conditions. Both<br />
methods are also useful to <strong>in</strong>troduce different am<strong>in</strong>oalkyl moieties <strong>in</strong> other nitrogen<br />
conta<strong>in</strong><strong>in</strong>g heterocycles.<br />
In this communication we present an extension of the scope of the reaction of am<strong>in</strong>oalkylation<br />
on the nitrogen us<strong>in</strong>g different heterocycles as 7-aza<strong>in</strong>doles 2, pur<strong>in</strong>es 3, pyrrole<br />
(4), benzimidazole (5) or <strong>in</strong>dazole (6). Our method afforded heterocycles functionalized<br />
with an am<strong>in</strong>omethyl group bear<strong>in</strong>g aryl, heteroaryl or alkyl substituents.<br />
F<strong>in</strong>ancial support from the M<strong>in</strong>isterio de Ciencia e Innovación and FEDER (CTQ 2009-<br />
13083) and from Generalitat Valenciana (ACOMP/2012/212 and ISIC/2012/001) is acknowledged.<br />
M.M. thanks the Universitat de València for a pre-doctoral grant.<br />
[1] (a) I. S. Young, P. D. Thorntonb, A. Thompson, Nat. Prod. Rep. 2010, 27, 1801; (b) K.<br />
Kumar, H. Waldmann, Angew. Chem. Int. Ed. 2009, 48, 3224; (c) R. Garg, S. P. Gupta, H.<br />
Gao, M. S. Babu, A. K. Debnath, C. Hansch, Chem. Rev. 1999, 99, 3525.<br />
[2] (a) H. Zhang, C.-X. Lian, W.-C. Yuan, X.-M. Zhang, Synlett 2012, 23, 1339; X. (b) Mi, S.<br />
Luo, J. Hea, J.-P. Chen, Tetrahedron Lett. 2004, 45, 4567; (c) W. Xie, K. M. Bloomfield, Y. J<strong>in</strong>,<br />
N. Dolney, P. G. Wang, Synlett 1999, 498.<br />
268 Saturday 9:00 - 11:30 Poster 211
Surface modification of segmented copolymers via hydrolysis<br />
and am<strong>in</strong>olysis<br />
Agata Niemczyk, Zygmunt Staniszewski, Mirosława El Fray<br />
Polymer Institute – West Pomeranian University of Technology, Szczec<strong>in</strong> –<br />
10 Pułaski Street – Szczec<strong>in</strong> – POL<br />
aniemczyk@zut.edu.pl<br />
Polymeric implants are an important class of biomaterials, which have facilitated the<br />
development of numerous prostheses and implants for orthopedic and cardiovascular<br />
applications, which are exposed to prolonged contact with tissue. However, <strong>in</strong>fections<br />
are a common complication aris<strong>in</strong>g from the tissue-biomaterial <strong>in</strong>teraction, lead<strong>in</strong>g to<br />
cl<strong>in</strong>ically significant problems. The major role of implant susceptibility to <strong>in</strong>fections<br />
is associated with the adhesion of a pathogen to the implant surface, therefore one<br />
of the strategies to obta<strong>in</strong> better surface resistance to microbial colonization is their<br />
modification.<br />
Poly(aliphatic/aromatic-ester) (PED) multiblock copolymers with different concentration<br />
of hard segment (poly(ethylene terephthalate) (PET)) and soft segments (dil<strong>in</strong>oleic<br />
acid (DLA)), namely 50, 55, 60, 65 and 70% wt. were modified to <strong>in</strong>duce surface<br />
hydrolysis and am<strong>in</strong>olysis, respectively. The chemical structure of the neat PET/DLA<br />
is shown <strong>in</strong> Figure 1.<br />
Hydrolysis of PET/DLA copolymers <strong>in</strong> concentrated alkal<strong>in</strong>e solution produced a<br />
carboxyl-enriched surface, and am<strong>in</strong>olysis <strong>in</strong> 1,6-hexanediam<strong>in</strong>e /propanol solution<br />
<strong>in</strong>troduced am<strong>in</strong>o groups. That surface functionalization leads to the negative (COO-<br />
) or positive (NH3+) charges on copolymer surface thus provid<strong>in</strong>g activated groups<br />
capable anchor<strong>in</strong>g polyelectrolytes <strong>in</strong> a layer-by-layer process. The changes of surface<br />
chemistry were monitored and verified ma<strong>in</strong>ly by FTIR spectroscopy.<br />
Figure 1. Chemical structure of PET/DLA copolymers<br />
Poster 212 Saturday 9:00 - 11:30 269
DFT-Study of the adsorption process of GaP-precursors on<br />
Si(001)(2x1) <strong>in</strong> Metal Organic Vapour Phase Epitaxy<br />
Phil Rosenow, Ralf Tonner<br />
Fachbereich Chemie – Philipps-Universität Marburg – Hans-Meerwe<strong>in</strong>-Straße 4 –<br />
Marburg – GER<br />
Rosenowp@students.uni-marburg.de<br />
Lasers on silicon are of particular <strong>in</strong>terest <strong>in</strong> optoelectronics and chip design. A system<br />
of great <strong>in</strong>terest is the quarternary III/V-semiconductor Ga(NAsP). In order to<br />
avoid lattice mismatches GaP is used as an <strong>in</strong>termediate layer. [1,2] The electronic<br />
properties depend highly on the <strong>in</strong>itial structure of the GaP-adlayer. Thus a DFTstudy<br />
has been started <strong>in</strong> order to ga<strong>in</strong> a better understand<strong>in</strong>g of the process us<strong>in</strong>g<br />
the VASP code.<br />
Calculations on gas-phase decomposition reactions suggest that hardly any decomposition<br />
occurs <strong>in</strong> the gas phase. Therefore surface reactions are supposed to play<br />
an important role <strong>in</strong> the adsorption process. The reactivity of the surface is determ<strong>in</strong>ed<br />
by the degree of hydration. Experimental studies of the silicon surface show<br />
that under high temperature MOVPE reactions the surface is clean whereas at low<br />
temperature conditions it is hydrated. [3]<br />
Adsorption reactions at the hydrated are possible under <strong>in</strong>sertion <strong>in</strong> Si-H or Si-Si<br />
bonds or under release of dihydrogen or hydrocarbon ligands. Adsorption is preceded<br />
by physisorption accompanied by activation of Si-H bonds.<br />
Layer growth depends on residues attached to the adsorbed atoms. t-Butyl groups<br />
block neighbour<strong>in</strong>g adsorption sites whereas mere hydrogen atoms have hardly any<br />
<strong>in</strong>fluence on adsorption. A notable exception is the case of gallium hydride species<br />
where a borane-like species occurs which leads to strongly stabilized structures.<br />
[1] B. Kunert, K. Volz, J. Koch, W. Stolz, Appl. Phys. Lett., 2006, 88, 182108.<br />
[2] I. Németh, B. Kunert, W. Stolz, K. Volz, J. Cryst. Growth, 2008, 310, 1595.<br />
[3] U. Höfer, L. Li, T. F. He<strong>in</strong>z, Phys. Rev. B, 1992, 45, 9485.<br />
270 Saturday 9:00 - 11:30 Poster 213
Rapid Preparation of 15 N3-labeled Enniat<strong>in</strong>s<br />
Svenja Schloß ∗ , Matthias Proske ∗ , Irmtraut Zaspel ∗ , Matthias Koch ∗ , Ronald Maul ∗<br />
∗ 1.7 Lebensmittelanalytik – Bundesanstalt für Materialforschung und -prüfung (BAM) –<br />
Richard-Willstätter-Straße 11 – Berl<strong>in</strong> – GER<br />
† Institut für Forstgenetik – Johann He<strong>in</strong>rich von Thünen-Institut –<br />
Eberswalder Chaussee 3a – Waldsieversdorf – GER<br />
svenja.schloss@bam.de<br />
In the class of depsipeptides, the enniat<strong>in</strong>s (ENN) are becom<strong>in</strong>g <strong>in</strong>creas<strong>in</strong>gly significant.<br />
As secondary metabolites of various Fusarium species, they represent a common<br />
source of food and feed contam<strong>in</strong>ation ma<strong>in</strong>ly affect<strong>in</strong>g cereal products. [1] Due to the<br />
limited data on the toxicity, occurrence, and contam<strong>in</strong>ation levels ENN are also referred<br />
to as “emerg<strong>in</strong>g mycotox<strong>in</strong>s”. [2] The detection of the analytes by means of mass<br />
spectrometry has been found as a suitable method. However, coelution of matrix components<br />
may lead to ion suppression or ion enhancement effects <strong>in</strong> LC-MS-analysis.<br />
Thus, for a reliable quantitation the use of isotope-labeled <strong>in</strong>ternal standards is advisable.<br />
All matrix effects <strong>in</strong>fluence the <strong>in</strong>ternal standard and the analyte <strong>in</strong> the same<br />
way. Also losses dur<strong>in</strong>g sample process<strong>in</strong>g can be compensated by addition of the<br />
isotope labeled <strong>in</strong>ternal standard at the beg<strong>in</strong>n<strong>in</strong>g of the sample extraction.<br />
The cultivation of Fusarium cultures and the isolation of unmarked ENN have been<br />
successfully carried out. Accord<strong>in</strong>g to Hu et al., the four ma<strong>in</strong> compounds ENN A,<br />
A1, B and B1 can be replaced with their 15 N3-labeled versions by grow<strong>in</strong>g a stra<strong>in</strong><br />
of Fusarium <strong>in</strong> an artificial culture medium with Na 15 NO3 as sole nitrogen source. [3]<br />
In variation from this, the labeled ENN were isolated by a modified rapid cleanup of<br />
the mycelium.<br />
After a solid-liquid extraction of the ENN from the homogenized fungal mycelium of<br />
Fusarium avenaceum, a fractionation and purification was carried out on a normal<br />
phase silica gel column with cyclohexane, ethyl acetate and methanol as eluents. The<br />
fractions conta<strong>in</strong><strong>in</strong>g the target analytes were identified by subsequent LC-MS analysis<br />
and evaporated to dryness. The residue was dissolved <strong>in</strong> methanol.<br />
The pattern of the native ENN and the 15 N-ENN (s<strong>in</strong>gle, double and triple labeled)<br />
and the accurate masses were determ<strong>in</strong>ed by LC-QToF-MS. Less than 2 percent of<br />
unlabeled ENN was detected <strong>in</strong> the isolated standard. Hence, the obta<strong>in</strong>ed isotope<br />
labeled ENN will be suitable for follow<strong>in</strong>g quantitative LC-MS based ENN analyses<br />
<strong>in</strong> food and feed.<br />
[1] Malachova et al., J. Agric. Food Chem. 2011, 28, 59(24), 12990-12997.<br />
[2] M. Jestoi, Crit Rev Food Sci Nutr. 2008, 48(1), 21-49.<br />
[3] Hu et al., J. Agric. Food Chem. 2012, 25, 60(29), 7129-36,<br />
Poster 214 Saturday 9:00 - 11:30 271
Novel phthalocyan<strong>in</strong>e derivatives possess<strong>in</strong>g dietheroxy<br />
substituents at non-peripheral positions as s<strong>in</strong>glet oxygen<br />
generators<br />
Lukasz Sobotta ∗ , Marc<strong>in</strong> Wierzchowski † , Tomasz Gosl<strong>in</strong>ski † , Jadwiga Mielcarek ∗<br />
∗ Department of Inorganic and Analytical Chemistry –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
† Department of Chemical Technology of Drugs –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL<br />
lsobotta@wp.eu<br />
Photodynamic therapy (PDT) is a novel promis<strong>in</strong>g treatment of cancer and precancer<br />
diseases, and of potential utility <strong>in</strong> bacterial and viral <strong>in</strong>fections. In PDT<br />
three components are necessary, such as photosensitizer, molecular oxygen and light<br />
of an appropriate wavelength. Interest<strong>in</strong>gly, an excited form of a drug <strong>in</strong>teracts with<br />
molecular oxygen <strong>in</strong> its tryplet state generat<strong>in</strong>g s<strong>in</strong>glet oxygen. S<strong>in</strong>glet oxygen can<br />
react with many biological cell components caus<strong>in</strong>g their destruction. [1] The photodynamic<br />
efficacy of three phthalocyan<strong>in</strong>es (Pc-1, Pc-2, Pc-3) was studied and their<br />
potential usefulness <strong>in</strong> photodynamic therapy was evaluated (Fig.1). The generation<br />
of s<strong>in</strong>glet oxygen by Pc-1 – Pc-3 was studied. 1,3-Diphenyloisobenzofuran (DPBF)<br />
was used as a s<strong>in</strong>glet oxygen quencher. The photooxidation process was <strong>in</strong>vestigated<br />
<strong>in</strong> aerobic conditions and <strong>in</strong> an environment with limited access of oxygen (Fig.1). [1]<br />
Accord<strong>in</strong>g to these studies, phthalocyan<strong>in</strong>es Pc-1 and Pc-2 generate s<strong>in</strong>glet oxygen,<br />
but <strong>in</strong> the environment with limited access of oxygen this process occurs to a much<br />
lesser extent. The quantum yield of s<strong>in</strong>glet oxygen generation was estimated by compar<strong>in</strong>g<br />
with the reference macrocycle (z<strong>in</strong>c phthalocyan<strong>in</strong>e). Moreover, Pc-2 appeared<br />
to be the most efficient photosensitizer among the series of macrocycles studied. The<br />
follow<strong>in</strong>g values of the quantum yield of s<strong>in</strong>glet oxygen generation <strong>in</strong> DMF and DMSO<br />
were found 0.32 and 0.30 for Pc-1, 0.46 and 0.34 for Pc-2, respectively.<br />
Fig.1 S<strong>in</strong>glet oxygen assessment spectra of Pc-1 were plotted dur<strong>in</strong>g measurement, <strong>in</strong>set<br />
presents process of DPBF oxidation)<br />
[1]<br />
R. R. Allison, G. H. Downie, R. Cuenca, X. Hu, C. J. H. Childs, C. H. Sibata, Photodiagn<br />
[2]<br />
Photodyn 2004, 1, 27-42. W. Szczolko, L. Sobotta, P. Fita, T. Koczorowski, M. Mikus, M.<br />
Gdaniec, A. Orzechowska, K. Burda, S. Sobiak, M. Wierzchowski, J. Mielcarek, E. Tykarska, T.<br />
Gośliński, Tetrahedron Lett. 2012, 53, 2040-44.<br />
This study was supported by the National Science Centre under Grant No. N N401 067238.<br />
272 Saturday 9:00 - 11:30 Poster 215
Incorporation and Organization of β-Peptides <strong>in</strong> Lipid<br />
Membranes<br />
Diana Petersen, Tatjana Polupanow, Ulf Diederichsen<br />
Institute of Organic and Biomolecular Chemistry – Georg-August-University Gött<strong>in</strong>gen –<br />
Tammannstr. 2 – 37077 Gött<strong>in</strong>gen – GER<br />
dpeters2@gwdg.de<br />
Transmembrane prote<strong>in</strong>s are spann<strong>in</strong>g the lipid bilayer and act<strong>in</strong>g as gateways for a<br />
selective transport of small molecules across the membranes. [1] The structural similarities<br />
of one or more hydrophobic regions <strong>in</strong> terms of α-helices or α-helical aggregates<br />
are common <strong>in</strong> transmembrane prote<strong>in</strong>s. [2] Properties like fold<strong>in</strong>g, channel formation<br />
and transmembrane signall<strong>in</strong>g are essentially affected by the non-covalent <strong>in</strong>teractions<br />
between the helix-motifs. Moreover, important are also the surround<strong>in</strong>g lipids<br />
and their orientation <strong>in</strong> the membrane (Scheme 1). [3] In order to better understand<br />
<strong>in</strong>termolecular <strong>in</strong>teractions and organization of transmembrane prote<strong>in</strong>s, we have chosen<br />
β-peptides as novel model system to study membrane assembly. β-Peptides are<br />
promis<strong>in</strong>g motifs to show various secondary structures with high helical content. [4,5]<br />
Therefore, various β-peptides with different hydrophobic side cha<strong>in</strong>s will be synthesized<br />
and exam<strong>in</strong>ed regard<strong>in</strong>g helix topology and membrane <strong>in</strong>corporation.<br />
Scheme 1: Schematic illustration of potential peptide assembly based on molecular<br />
recognition of helix side cha<strong>in</strong>s <strong>in</strong>side the membrane bilayer. Left: Aggregation via<br />
electrostatic attraction between a positive charged lys<strong>in</strong>e residue and a negative charged<br />
glutamic acid side cha<strong>in</strong>. Right: Helical assembly obta<strong>in</strong>ed by hydrogen bond<strong>in</strong>g of two<br />
asparag<strong>in</strong>e residues.<br />
[1]<br />
K. Murata, K. Mitsuoka, T. Hirai, T. Walz, P. Agre, J. B. Heyman, A. Engel, Y. Fujiyoshi,<br />
Nature 2000, 407, 599-605.<br />
[2]<br />
O.S. Andersen, R. E. Koeppe, Annu. Rev. Biophys. Biomol. Struct. 2007, 36, 107-130.<br />
[3]<br />
J. U. Bowie, Nature 2005, 438, 581-589.<br />
[4]<br />
D. Seebach, A. K. Beck, D. J. Bierbaum, Chem. Biodivers. 2004, 1, 1111-1239.<br />
[5] S. H. Gellman, Acc. Chem. Rev. 1998, 31, 173-180.<br />
Poster 216 Saturday 9:00 - 11:30 273
Chromatographic retention parameters as predictors of the<br />
biological activity of some aldopentose and aldohexose<br />
derivatives<br />
Strah<strong>in</strong>ja Kovacevic, Lidija Jevric, Sanja Podunavac Kuzmanovic, Natasa Kalajdzija,<br />
Eva Loncar<br />
Department of Applied and Eng<strong>in</strong>eer<strong>in</strong>g Chemistry –<br />
University of Novi Sad, Faculty of Technology – Bulevar cara Lazara 1 – Novi Sad – SRB<br />
strah<strong>in</strong>jakovacevic@hotmail.com<br />
Chromatographic retention parameters, R 0 M and C0, have been used to form mathematical<br />
models for prediction of the biological behavior of 1,2-O-izopropylidene<br />
derivatives of aldohexoses and 1,2-O-cyclohexylidene derivatives of aldopentoses. The<br />
biological activity of these molecules was confirmed <strong>in</strong> several scientific papers. [1−3]<br />
In silico biological descriptors of the exam<strong>in</strong>ed molecules, such as enzyme <strong>in</strong>hibition<br />
(EI), nuclear receptor ligand b<strong>in</strong>d<strong>in</strong>g (NRL), k<strong>in</strong>ase <strong>in</strong>hibition (KI), protease<br />
<strong>in</strong>hibition (PI), ion channel modulation (ICM), G prote<strong>in</strong>-coupled receptors b<strong>in</strong>d<strong>in</strong>g<br />
(GPCR), and Caco-2 cells permeability (Caco-2), were calculated by PreADMET [4]<br />
and Mol<strong>in</strong>spiration [5] software. The retention factors R 0 M and C0 were determ<strong>in</strong>ed by<br />
normal-phase th<strong>in</strong>-layer chromatography <strong>in</strong> the solvent systems cyclohexane : ethylacetate,<br />
cyclohexane : acetone, cyclohexane : dioxane, cyclohexane : tetrahydrofuran<br />
and benzene : acetone, and silica gel as stationary phase.<br />
The correlations between def<strong>in</strong>ed biological descriptors and retention parameters were<br />
determ<strong>in</strong>ed by statistical software Statistica 8. [6] Quadratic equations that relate R 0 M<br />
and C0 with EI, PI, KI, NRL, ICM, GPCR and Caco-2 were established. The validity<br />
of the generated mathematical models was confirmed by standard statistical measures<br />
(correlation coefficient (r), the standard error of estimation (s), Fisher’s value (F)),<br />
and cross-validation parameters (PRESS value, TSS value, Spress value, r 2 cv, r 2 adj ).[7]<br />
Optimal values of the cross-validation parameters confirm predictive ability of the<br />
estimated equations.<br />
On the basis of the obta<strong>in</strong>ed results it can be concluded that etablished mathematical<br />
models can be used for prediction of the biological behavior of the exam<strong>in</strong>ed molecules.<br />
It <strong>in</strong>dicates that retention parameters obta<strong>in</strong>ed by normal-phase chromatography can<br />
successfully predict some biological characteristics of the exam<strong>in</strong>ed aldopentose and<br />
aldohexose derivatives.<br />
[1]<br />
G. Catelani, F. D’Andrea, M. Landi, C. Zuccato, N. Bianchi, R. Gambari, Carbohydr. Res.<br />
2006, 341, 538.<br />
[2]<br />
G. Catelani, F. D’Andrea, E. Mastrorilli, N. Bianchi, C. Chiarabelli, M. Borgatti, D. Martello,<br />
R. Gambari, Bioorg. Med. Chem. 2002, 10, 347.<br />
[3]<br />
R. Trivedi, E. R. Reddy, Ch. Kiran Kumar, B. Sridhar, K. Pranay Kumar, M. Sr<strong>in</strong>ivasa Rao,<br />
Bioorg. Med. Chem. Lett. 2011, 21, 3890.<br />
[4]<br />
preadmet.bmdrc.org<br />
[5]<br />
www.mol<strong>in</strong>spiration.com<br />
[6]<br />
www.statsoft.com<br />
[7]<br />
S. Podunavac Kuzmanovic, D. Cvetkovic, S. Gadzuric, APTEFF 2011, 42, 251.<br />
274 Saturday 9:00 - 11:30 Poster 217
Selective Oxidation of Methane over VOX Catalysts: Effect<br />
of CO2 admixtures on formaldehyde selectivity<br />
Enno Schönborn, Philipp Wallis, Claudio Pirovano, Narayana Kalevaru, Andreas Mart<strong>in</strong>,<br />
Sebastian Wohlrab<br />
Leibniz-Institut für Katalyse e.V. – A.-E<strong>in</strong>ste<strong>in</strong>-Str. 29a – Rostock – GER<br />
enno.schoenborn@catalysis.de<br />
The selective oxidation of methane to oxygenates is one of the challeng<strong>in</strong>g tasks <strong>in</strong><br />
catalysis. Promis<strong>in</strong>g catalytic systems with enhanced selectivity for formaldehyde are<br />
based on vanadium oxide species supported on mesoporous silicas. [1, 2] In the present<br />
work, we compare properties of differently prepared VOX catalysts supported on<br />
mesoporous silicas (MCM-41, SBA-15) us<strong>in</strong>g different analytical methods. In addition,<br />
we show the <strong>in</strong>fluence of CO2 -admixtures on the catalytic performance of these<br />
catalysts for the selective oxidation of methane to formaldehyde.<br />
Isolated low-molecular VOX species are assumed to be the active sites <strong>in</strong> the selective<br />
oxidation of methane. [3] However, analytic <strong>in</strong>vestigations of the catalysts prepared under<br />
different conditions showed concise differences related to preparation method as<br />
well as supports used. [4] The catalytic oxidation experiments are congruent with the<br />
analytical results. Besides such preparative developments, the process can be further<br />
positively <strong>in</strong>fluenced by technological variations. Primarily, the total oxidation can<br />
be suppressed by CO2 admixtures to the reactant feed. Fig. 1 shows such effect over<br />
VOX /SBA-15 catalyst prepared by IWI method. Start<strong>in</strong>g from a feed mixture of<br />
7.5:1:4:7.5 (CH4: O2:N2:CO2) methane conversion xCH4 was 5.6%. The formaldehyde<br />
selectivity SHCHO was found to be 19.6%. After 3 h the CO2 was substituted<br />
by N2 and xCH4 <strong>in</strong>creased while SHCHO decreased tremendously. If a cont<strong>in</strong>uous<br />
flow of CO2 was used for the whole reaction time we observed only a slight <strong>in</strong>crease of<br />
xCH4 and appreciably lower decrease of SHCHO. It can be concluded that CO2 <strong>in</strong> the<br />
feed reduces the overall conversion of methane while the selectivity to formaldehyde<br />
is <strong>in</strong>creased.<br />
From this, we can conclude that CO2 admixtures to the reactant feed have a positive<br />
<strong>in</strong>fluence on the methane oxidation reaction which leads to enhancement of the<br />
formaldehyde selectivity. Together with methods <strong>in</strong>clud<strong>in</strong>g rapid formaldehyde isolation<br />
from the reaction zone such CO2 admixtures to the feed help to reduce total<br />
oxidation of methane to carbon dioxide.<br />
Fig. 1. Influence of CO2 admixtures on the performance of VOX catalyst (T = 923 K;<br />
cat. amount = 100 mg; GHSV = 180,000 lkg −1 h −1 , CH4:O2:N2:admixture =<br />
7.5:1:4:7.5, 6 h), left: xCH4 , right: SHCHO .<br />
[1] H. Berndt et al., J. Catal. 2000, 191, 384.<br />
[2] L.D. Nguyen et al., J. Catal. 2006, 237, 38.<br />
[3] V. Fornés et al., Appl. Catal. A: Gen. 2003, 249, 345.<br />
[4] C. Pirovano et al., Catal. Today 2012, 192, 20.<br />
Poster 218 Saturday 9:00 - 11:30 275
One-step synthesis of tetrazolo[1,5-a]pyrid<strong>in</strong>es from pyrid<strong>in</strong>e<br />
N -oxides<br />
Shanshan Liu, Christoph Tzschucke<br />
Department of Chemistry and Biochemistry – Freie Universität Berl<strong>in</strong> – Takustr. 3 –<br />
D- 14195 Berl<strong>in</strong> – GER<br />
liushan329@126.com<br />
Organic azides are important functional groups, they are used as precursors to primary<br />
am<strong>in</strong>es [1] , nitrenes [2] , and triazoles [3] . Tetrazole is the predom<strong>in</strong>ant species <strong>in</strong><br />
the azide/tetrazole equilibrium of 2-azidopyrid<strong>in</strong>es. We seek an practical and convenient<br />
manufactur<strong>in</strong>g route to <strong>in</strong>troduce azides us<strong>in</strong>g cost efficient reagents. Different<br />
sulfonyl and phosphoryl reagents and various solvents were compared <strong>in</strong> this reaction.<br />
Various substituted tetrazolopyrid<strong>in</strong>es were prepared <strong>in</strong> good to excellent yield from<br />
the correspond<strong>in</strong>g pyrid<strong>in</strong>e-N -oxides. Reaction optimization and substrate scope will<br />
be discussed.<br />
Synthesis of tetrazolo[1,5-a]pyrid<strong>in</strong>es from pyrid<strong>in</strong>e N -oxides.<br />
[1] (a) A. Boruah, M. Baruah, D. Prajapati, J. S. Sandhu, Synlett 1997, 1253-1254; (b) M.<br />
Vaultier, N. Knouzi, R. Carrie, Tetrahedron Lett. 1983, 24, 763-764; (c) H. J. Boyer, J. Am.<br />
Chem. Soc. 1951, 73, 5865-5866.<br />
[2] (a) M.-L. Tsao, M. S. Platz, J. Am. Chem. Soc. 2003, 125, 12014-12025; (b) S. Murata, R.<br />
Yoshidome, Y. Satoh, N. Kato, H. Tomioka, J. Org. Chem. 1995, 60, 1428-1434; (c) A. Alb<strong>in</strong>i,<br />
G. Bett<strong>in</strong>etti, G. M<strong>in</strong>oli, J. Am. Chem. Soc. 1991, 113, 6928-6934.<br />
[3] (a) W. G. Lewis, L. G. Green, F. Grynszpan, Z. Radic, P. R. Carlier, P. R. Taylor, M. G. F<strong>in</strong>n,<br />
K. B. Sharpless, Angew. Chem., Int. Ed. 2002, 41, 1053-1057; (b) Y. Angell, K. Burgess, J.<br />
Org. Chem. 2005, 70, 9595-9598; (c) A. F. Brigas, Sci. Synth. 2004, 13, 861-915.<br />
276 Saturday 9:00 - 11:30 Poster 219
Qu<strong>in</strong>ol<strong>in</strong>ium based Dyes <strong>in</strong> Ionic Liquids - Synthesis,<br />
Theoretical Calculations and Photophysical Properties<br />
Stella Schmode ∗ , Sebastian Reimann ∗ , Nikolaus P. Ernst<strong>in</strong>g † , Ralf Ludwig ∗<br />
∗ Theoretical and Physical Chemistry – University of Rostock – Dr.-Lorenz-Weg/1 –<br />
Rostock – GER<br />
† Physical Chemistry – Humboldt Universität zu Berl<strong>in</strong> – Brook-Taylor-Str./2 –<br />
Berl<strong>in</strong> – GER<br />
stella.schmode@uni-rostock.de<br />
Ionic Liquids have attracted much attention <strong>in</strong> science and technology over the past<br />
decades. First <strong>in</strong>novative applications are already established <strong>in</strong> the fields of chemical<br />
synthesis, catalysis, biochemical and pharmaceutical research as well as material<br />
science. [1,2] Despite the impressive enhancements, the reasons of fundamental chemical<br />
properties like solvation behavior and acidity are often not completely understood.<br />
Different spectroscopic methods can be used to probe <strong>in</strong>ter- and <strong>in</strong>tramolecular <strong>in</strong>teractions<br />
<strong>in</strong> ionic liquids. [3]<br />
Here we present a comb<strong>in</strong>ation of spectroscopy with synthesis of new low melt<strong>in</strong>g salts<br />
supported by DFT calculations. The structural unit of all exam<strong>in</strong>ed compounds is<br />
qu<strong>in</strong>ol<strong>in</strong>ium. This heterocyclic molecule is substituted <strong>in</strong> N-position by alkyl groups<br />
which results <strong>in</strong> a native zwitterionic molecule with a negative charge at the oxygen<br />
and a positive one at the nitrogen atom. Low melt<strong>in</strong>g salts are formed by conversion<br />
with acids conta<strong>in</strong><strong>in</strong>g weak coord<strong>in</strong>ation anions, e.g. triflate. Structural <strong>in</strong>formation<br />
is given by NMR and MIR spectroscopy. The <strong>in</strong>fluence of different alkyl cha<strong>in</strong> length<br />
is studied by comparison of b<strong>in</strong>d<strong>in</strong>g energy <strong>in</strong> terms of measured melt<strong>in</strong>g po<strong>in</strong>ts and<br />
calculated molecular energies.<br />
[1]<br />
N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev. 2008, 37 (1), 123-150.<br />
[2]<br />
J. Stoimenovski, D. R. MacFarlane, K. Bica, R. D. Rogers, Pharmaceutical Research 2010,<br />
27 (4), 521-526.<br />
[3]<br />
A. Wulf, K. Fum<strong>in</strong>o, R. Ludwig, Angew. Chem. Int. Ed. 2010, 49, 449-453.<br />
Poster 220 Saturday 9:00 - 11:30 277
Target<strong>in</strong>g tumor cells by us<strong>in</strong>g drug-magnetic nanoparticles<br />
conjugate<br />
Anita Jarzeb<strong>in</strong>ska ∗ , Anna Maria Nowicka ∗ , Agata Kowalczyk ∗ , Mikolaj Donten ∗ ,<br />
Pawel Krys<strong>in</strong>ski ∗ , Zbigniew Stojek ∗ , Ewa August<strong>in</strong> † , Zofia Mazerska †<br />
∗ Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
† Department of Pharmaceutical Technology and Biochemistry –<br />
Gdansk University of Technology – Narutowicza 11/12 – Gdansk – POL<br />
anita.jarzeb<strong>in</strong>ska@student.uw.edu.pl<br />
A disadvantage of many drugs used <strong>in</strong> therapy of solid tumors is their cytotoxicity<br />
aga<strong>in</strong>st healthy tissues. Doxorubic<strong>in</strong> is especially toxic to the heart and the kidneys,<br />
which limits its therapeutic applications. Therefore, it is important to f<strong>in</strong>d a<br />
carrier that can deliver the drug selectively to the tumor tissue. The b<strong>in</strong>d<strong>in</strong>g of a<br />
magnetic nanoparticle with a doxorubic<strong>in</strong> and apply<strong>in</strong>g a properly directed external<br />
magnetic field might be a good alternative to such traditional forms of the drug like<br />
liposomes and micels. The improved by us synthesis of the conjugate of doxorubic<strong>in</strong><br />
with iron-oxide magnetic nanoparticles allows a substantial depression of the aggregation<br />
process of the nanoparticles and therefore the exam<strong>in</strong>ation of cytotoxicity of the<br />
modified drug. It has been shown, by perform<strong>in</strong>g the electrochemical microbalance<br />
measurements, that the use of magnetic field guarantees the efficient delivery of the<br />
drug to the requested place. The change <strong>in</strong> the synthesis led to an <strong>in</strong>crease <strong>in</strong> the<br />
number of DOX molecules attached to one magnetic particle. It has also been found<br />
that the release of the drug takes place below pH 5.8, which pH characterizes the cancer<br />
cells. We demonstrated that unmodified iron-oxide magnetic nanoparticles were<br />
not cytotoxic toward human ur<strong>in</strong>ary bladder carc<strong>in</strong>oma cells UM-UC-3. Tumor cell<br />
sensitivity of DOX-Np complex was slightly higher <strong>in</strong> comparison to identical concentration<br />
of doxorubic<strong>in</strong> alone. Therefore, the magnetic nanoparticles were shown to be<br />
a good carrier for doxorubic<strong>in</strong> <strong>in</strong>to the <strong>in</strong>vestigated tumor cells.<br />
[1]<br />
J. O’Shaughnessy, Oncologist 2003, 8, 1-2.<br />
[2]<br />
V. I. Shubayev, T. R. Pisanic II, S. J<strong>in</strong>, Advanced Drug Delivery Rev. 2009, 61, 467-477.<br />
[3]<br />
S. M. Hussa<strong>in</strong>, K. L. Hess, J. M. Gearhart, K. T. Geiss, J. J. Schlager, Toxicol.<strong>in</strong> Vitro 2005,<br />
19, 975-983.<br />
[4]<br />
A. M. Nowicka, A. Kowalczyk, M. Donten, P. Krys<strong>in</strong>ski, Z. Stojek, Anal. Chem. 2009, 81,<br />
7474-7483.<br />
278 Saturday 9:00 - 11:30 Poster 221
Synthesis and biological activity of novel phthalocyan<strong>in</strong>es<br />
with dietheroxy and nitroimidazolylethoxy moieties<br />
Marc<strong>in</strong> Wierzchowski ∗ , Sebastian Lijewski ∗ , Lukasz Sobotta † , Krystyna Konopka ‡ ,<br />
Michael Lee ‡ , Nejat Düzgünes ‡ , Ewa Tykarska ∗ , Jadwiga Mielcarek † , Tomasz Gosl<strong>in</strong>ski ∗<br />
∗ Department of Chemical Technology of Drugs –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – 60-780 Poznan – POL<br />
† Department of Inorganic and Analytical Chemistry –<br />
Poznan University of Medical Sciences – Grunwaldzka 6 – 60-780 Poznan – POL<br />
‡ Department of Biomedical Sciences – University of the Pacific – 2155 Webster Street –<br />
San Francisco, 94115 CA – USA<br />
sebastianlijewski@o2.pl<br />
Phthalocyan<strong>in</strong>es (Pcs) are aromatic macrocyclic compounds consist<strong>in</strong>g of four iso<strong>in</strong>dole<br />
fragments l<strong>in</strong>ked together with azometh<strong>in</strong>e groups. These synthetic analogues<br />
of natural porphyr<strong>in</strong>oids are known to possess wide applications <strong>in</strong> dyes <strong>in</strong>dustry,<br />
<strong>in</strong> materials chemistry as sensors, molecular semiconductors and non-l<strong>in</strong>ear optical<br />
materials, and as photosensitizers <strong>in</strong> photodynamic therapy. Medical applications<br />
of phthalocyan<strong>in</strong>es impose good solubility <strong>in</strong> water and <strong>in</strong>creased accumulation <strong>in</strong><br />
pathologic tissues. The structure of Pcs may be modified by <strong>in</strong>troduc<strong>in</strong>g substituents<br />
at their peripheral and non-peripheral positions, as well as various metal ions <strong>in</strong>to the<br />
central cavity of a macrocycle. Good solubility <strong>in</strong> water can be reached by <strong>in</strong>troduc<strong>in</strong>g<br />
polyetheric substituents [1] <strong>in</strong> non-peripheral positions. Increased accumulation<br />
<strong>in</strong> hypoxic tissues such as cancer tissue can be reached by <strong>in</strong>corporat<strong>in</strong>g nitroimidazole<br />
moieties to the structure. [2] New compounds were synthesized accord<strong>in</strong>g to the<br />
procedure shown on Figure 1.<br />
Newly synthesized phthalocyan<strong>in</strong>es Pc-1, Pc-2, Pc-3, Pc-4 as well as the precursor<br />
d<strong>in</strong>itriles 1 and 2 were fully characterized by NMR, UV-Vis, MS, HPLC. Additionally,<br />
new d<strong>in</strong>itryles were characterized by combustion analysis and crystallographic data.<br />
New phthalocyan<strong>in</strong>es were tested for photodynamic activity aga<strong>in</strong>st human oral squamous<br />
carc<strong>in</strong>oma cells HSC-3. The best activity was revealed by compound Pc-3<br />
possess<strong>in</strong>g two types of substituents – dietheroxy and nitroimidazolylethoxy. Pc-3<br />
showed photocytotoxicity at the level of IC50 0.10 µM. Z<strong>in</strong>c compound Pc-2 was three<br />
times more active than the magnesium Pc-1 and seems to be a promis<strong>in</strong>g compound<br />
for further research.<br />
This study was supported by the National Science Centre under Grant No. N401<br />
067238.<br />
Fig. 1<br />
[1] F. Lv, B. Cao, Y. Cui, T. Liu, Molecules 2012, 17, 6349-6361.<br />
[2] R. J. Abdel-Jalil, M. Übele, W. Ehrlichmann, W. Voelter, H. J. Machulla, J. Radioanal. Nucl.<br />
Chem. 2006, 267, 557-560.<br />
Poster 222 Saturday 9:00 - 11:30 279
Highly Chemoselective Metal-free Reduction of Phosph<strong>in</strong>e<br />
Oxides to Phosph<strong>in</strong>es<br />
Yuehui Li, Liang-Qiu Lu, Kathr<strong>in</strong> Junge, Matthias Beller<br />
Leibniz-Institut für Katalyse – Albert-E<strong>in</strong>ste<strong>in</strong>-Str. 29a – Rostock – GER<br />
yuehui.li@catalysis.de<br />
Chemoselective reductions of unsaturated compounds constitute an important tool<br />
box for more benign organic synthesis. Little is known on the catalytic reduction<br />
of related P=O bonds, which are thermodynamically highly stable. With a bond<br />
energy of around 502 kJ/mol they are significantly more stable compared to typical<br />
organic functional groups and the general order of bond energy stability is: P-O ><br />
C-H > C-O > C-C > C-N). [1,2] Therefore, it is not surpris<strong>in</strong>g that highly chemoselective<br />
reductions of phosph<strong>in</strong>e oxides until today represent an unsolved problem<br />
although the result<strong>in</strong>g organophosph<strong>in</strong>es represent valuable <strong>in</strong>termediates and ligands<br />
for transition-metal catalysis. [3] For the first time, unprecedented chemoselective<br />
reductions of phosph<strong>in</strong>e oxides to phosph<strong>in</strong>es proceed smoothly <strong>in</strong> the presence of<br />
catalytic amounts of specific Brønsted acids. Utiliz<strong>in</strong>g <strong>in</strong>expensive silanes, e.g. PMHS<br />
or (EtO)2MeSiH, other reducible functional groups such ketones, aldehydes, olef<strong>in</strong>s,<br />
nitriles, and esters are well tolerated under optimized conditions. [4]<br />
Chemoselective reduction of phosph<strong>in</strong>e oxides.<br />
[1]<br />
S. B. Hartley, W. S. Holmes, J. K. Jacques, M. F. Mole, J. C. McCoubrey, Quart. Rev. 1963,<br />
17, 204-223.<br />
[2]<br />
Y. Li, S. Das, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc. 2012, 134, 9727-9732.<br />
[3]<br />
K. D<strong>in</strong>g, Z. Han, Z. Wang, Chem. Asian. J. 2009, 4, 32-41.<br />
[4]<br />
Y. Li, L.-Q. Lu, S. Das, S. Pisiewicz, K. Junge, M. Beller, J. Am. Chem. Soc. 2012, 134,<br />
18325-18329.<br />
280 Saturday 9:00 - 11:30 Poster 223
Determ<strong>in</strong>ation of orig<strong>in</strong>ality of fruit brandies us<strong>in</strong>g l<strong>in</strong>ear<br />
regression analysis<br />
Natasa Kalajdzija ∗ , Sanja Podunavac Kuzmanovic ∗ , Lidija Jevric ∗ ,<br />
Strah<strong>in</strong>ja Kovacevic ∗ , Biljana Marosanovic † , Maja Lojovic †<br />
∗ Department of Applied and Eng<strong>in</strong>eer<strong>in</strong>g Chemistry –<br />
University of Novi Sad, Faculty of Technology – Bulevar cara Lazara 1 – Novi Sad – SRB<br />
† Department of Instrumental Analysis – SP Laboratory – Industrijska zona bb –<br />
Becej – SRB<br />
natasa.ns@live.com<br />
Production of fruit brandy should be based on the use of fruit from which fermentable<br />
sugars are transformed <strong>in</strong>to ethanol dur<strong>in</strong>g fermentation. However, due to the manufacturers<br />
aim to achieve higher profits, they are <strong>in</strong>creas<strong>in</strong>gly resort<strong>in</strong>g to the use of<br />
sugar produced from sugar beet due to much lower purchase prices of raw materials.<br />
Given that sugar beet belongs to the C3-plants as well as fruit (apples, pears), the<br />
addition of sugar that comes from sugar beet can be confirmed through isotope ratio<br />
mass spectrometry analysis (IRMS) of stable isotopes of hydrogen <strong>in</strong> the molecule<br />
of ethanol. [1] On average, 85% of deuterium orig<strong>in</strong>at<strong>in</strong>g from sugar dur<strong>in</strong>g the fermentation<br />
process is be<strong>in</strong>g <strong>in</strong>corporated <strong>in</strong> the methyl-group, and 75% of deuterium<br />
orig<strong>in</strong>at<strong>in</strong>g from water <strong>in</strong>to methylene-group of ethanol molecules. [2] If alcoholic beverages<br />
are sweetened with sugar beet, analysis of ethanol will obta<strong>in</strong> δD values that<br />
are significantly lower compared to the values obta<strong>in</strong>ed for the ethanol molecule that<br />
is derived exclusively from fruit. [3]<br />
The exam<strong>in</strong>ation of apple and pear brandies that orig<strong>in</strong>ate from the areas of the Republic<br />
of Serbia, confirmed the existence of dependence between the amount of added<br />
sugar derived from sugar cane and the value of the stable isotopes of hydrogen <strong>in</strong><br />
ethanol molecule (δD). We analyzed six samples of brandy, and for each sample, by<br />
us<strong>in</strong>g a l<strong>in</strong>ear regression analysis, a mathematical formulation was derived that describes<br />
the given l<strong>in</strong>ear dependence. Statistical parameters that prove the validation<br />
of the model equations (Pearson’s correlation coefficients (r), the standard error of<br />
estimation (s), Fisher’s value (F) and parameters of cross validation (PRESS value,<br />
r2 cv and r2 adj )) were calculated us<strong>in</strong>g the software package Statistical System Number<br />
Cruncher-NCSS 2007. The practical application of the equations is reflected <strong>in</strong> the<br />
calculation of the amount of added sugar derived from sugar beets dur<strong>in</strong>g the production<br />
of brandy on the basis of δD values, and it is necessary to know the type and<br />
variety of fruit from which it is produced.<br />
[1] N. Christop, A. Rossmann, S. Voerkelius, Mitt. Klosterneuburg 2003, 53, 23.<br />
[2] M. Guček, J. Marsel, N. Ogr<strong>in</strong>c, S. Lojen, Acta Chim. Slov. 1998, 45, 217.<br />
[3] K. Ishida-Fujii, S. Goto, R. Uemura, K. Yamada, M. Sato, N. Yoshida, Biosci. Biotechnol.<br />
Biochem. 2005, 69, 2193.<br />
Poster 224 Saturday 9:00 - 11:30 281
Photogeneration of charge carriers <strong>in</strong> poly(N-v<strong>in</strong>ylcarbazole)<br />
doped with 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole and<br />
tris(2-phenylpyrid<strong>in</strong>e) iridium<br />
Anna Stefaniuk, Jarosław Jung, Ireneusz Głowacki<br />
Department of Molecular Physics, Faculty of Chemistry –<br />
Łódź University of Technology – Żeromskiego/116, 90-924 Łódź – Łódź – POL<br />
anna.stefaniuk@hotmail.com<br />
Poly(N-v<strong>in</strong>ylcarbazole) (PVK) and a mixture of PVK with 40 wt. % of 2-(4-diphenyl)-<br />
5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PVK - PBD) are commonly used as an electrolum<strong>in</strong>escent<br />
matrix. [1] PVK-PBD system is characterized by comparable transport<br />
of holes and electrons. The high level of triplet excitons’ energy of carbazole groups<br />
allows the effective energy transfer from the matrix to the phosphorescent dopant. [2]<br />
Analysis of the spectral distribution of thermolum<strong>in</strong>escence spectrum confirms the<br />
presence of the deep traps for holes and efficient recomb<strong>in</strong>ation centers which are<br />
located on the tris(2-phenylpyrid<strong>in</strong>e) iridium (Ir(ppy)3) particles. The addition of a<br />
small amount (2 wt. %) of Ir(ppy)3 effectively quenches the excited states of PVK<br />
and PBD-PVK. [3] A similar value of the triplet energy levels (∼ 3.2 eV) and the ability<br />
of the formation of triplet excitons <strong>in</strong> PVK and Ir(ppy)3 has a significant impact<br />
on the generation of electron-hole pairs and their dissociation <strong>in</strong> a high electric field<br />
<strong>in</strong> PVK-PBD systems doped with tris(2-phenylpyrid<strong>in</strong>e) iridium.<br />
The aim of this work was to determ<strong>in</strong>e the quantum yield of photogeneration of<br />
charge carriers by xerographic discharge method. Samples of PVK and PVK-PBD<br />
doped with iridium complex (2 wt. %) with a thickness from 1,5 to 6 µm was obta<strong>in</strong>ed<br />
by drop-cast<strong>in</strong>g method. Based on the analysis of the results of quantum efficiency of<br />
photogeneration of charge carriers depend<strong>in</strong>g on the <strong>in</strong>tensity of the electric field and<br />
the excitation wavelength the photoconductivity of exam<strong>in</strong>ed systems PVK and PVK-<br />
PBD doped with iridium complex was rated. The results obta<strong>in</strong>ed for the samples<br />
doped with Ir(ppy)3 show that the quantum efficiency of photogeneration of charge<br />
carriers is significantly reduced <strong>in</strong> comparison with pure PVK. This is associated with<br />
the effective capture of holes by Ir(ppy)3 particles. Addition of 40 wt. % of PBD<br />
(which is characterized by a high mobility of electrons) to the PVK + Ir(ppy)3 system<br />
results <strong>in</strong> an appearance of photoconductivity <strong>in</strong> the electric field from −4 · 10 5 V/m<br />
to −3 · 10 7 V/m.<br />
[1] I. Glowacki, and Z. szamel, J. Phys. D: Appl. Phys. 2010, 43, 295101.<br />
[2] D.F. Prepichka, N. Meng, M.-M. L<strong>in</strong>g, “Phosphorescent polymer light-emitt<strong>in</strong>g diodes, Organic<br />
light-emitt<strong>in</strong>g materials and devices”, Z. Li, H. Meng, Tylor Francis, Boca Raton 2007, 413-449.<br />
[3] Z. Szamel “Trapp<strong>in</strong>g and recomb<strong>in</strong>ation of charge carriers <strong>in</strong> polymer electrophosphorescent<br />
systems”, Ph.D. Thesis, Lodz University of technology, 2007.<br />
282 Saturday 9:00 - 11:30 Poster 225
Detection of the Cyanotox<strong>in</strong> Cyl<strong>in</strong>drospermops<strong>in</strong> <strong>in</strong> Brassica<br />
Species<br />
Katr<strong>in</strong> Kittler ∗ , Monika Schre<strong>in</strong>er † , Angelika Krumbe<strong>in</strong> † , Matthias Koch ∗ ,<br />
Sascha Rohn ‡ , Ronald Maul ∗<br />
∗ Analytical Chemistry; Reference Materials –<br />
Federal Institute for Materials Research and Test<strong>in</strong>g – Richard-Willstätter-Straße 11 –<br />
Berl<strong>in</strong> – GER<br />
† Department of Quality Research –<br />
Leibniz-Institute of Vegetable and Ornamental Crops – Theodor-Echtermeyer-Weg 1 –<br />
Großbeeren – GER<br />
‡ Institute of Food Chemistry – University of Hamburg – Gr<strong>in</strong>delallee 117 –<br />
Hamburg – GER<br />
katr<strong>in</strong>.kittler@bam.de<br />
Cyl<strong>in</strong>drospermops<strong>in</strong> (CYN), a potent cyanobacterial hepatotox<strong>in</strong>, occurs <strong>in</strong> freshwater<br />
bodies worldwide. Humans or animals get exposed to this tox<strong>in</strong> by <strong>in</strong>gestion,<br />
sk<strong>in</strong> contact, or <strong>in</strong>halation predom<strong>in</strong>antly when swimm<strong>in</strong>g <strong>in</strong> contam<strong>in</strong>ated water.<br />
Another known exposure route is the uptake of CYN conta<strong>in</strong><strong>in</strong>g seafood. [1] In many<br />
countries it is common to use surface water for crop irrigation also from potentially<br />
cyanotox<strong>in</strong>-contam<strong>in</strong>ated resources. [2] Therefore, an exposure to CYN by eat<strong>in</strong>g contam<strong>in</strong>ated<br />
crops seems possible. The aim of this study was to clarify whether CYN is<br />
taken up by plants and transported from the roots to the leaves. Different Brassica<br />
species served as model crops, which were irrigated with CYN conta<strong>in</strong><strong>in</strong>g water.<br />
In experiment 1 the roots of two leaf stage Brassica oleracea var. sabellica and<br />
Brassica juncea plants were irrigated with a nutrient solution <strong>in</strong> an aeroponic system<br />
for 30 days. The water conta<strong>in</strong>ed pure CYN and CYN from an unpurified APH<br />
extract (cCY N = 18-35 µg L −1 ). In experiment 2 S<strong>in</strong>apis alba seedl<strong>in</strong>gs were used to<br />
exam<strong>in</strong>e the concentration dependency for CYN uptake. Therefore, the plants were<br />
exposed to concentrations <strong>in</strong> the range of 20 to 445 µg L −1 CYN for a growth period<br />
of 3 days. The plant material from the two different experiments was freeze-dried,<br />
extracted, and analyzed by HPLC-MS/MS. [3]<br />
In all experiments performed, a significant uptake of CYN by the test plants was<br />
observed. The CYN concentrations <strong>in</strong> the leaves reached up to 21 % of the concentration<br />
<strong>in</strong>itially applied to the roots. Furthermore, a l<strong>in</strong>ear concentration dependency<br />
of the CYN absorption <strong>in</strong> the selected concentration range was determ<strong>in</strong>ed for<br />
S<strong>in</strong>apia alba seedl<strong>in</strong>gs. The results <strong>in</strong>dicate that CYN is systemically available to the<br />
exam<strong>in</strong>ed Brassica species. Thus, it seems possible that crop plants irrigated with<br />
CYN-conta<strong>in</strong><strong>in</strong>g surface water may represent a significant source of this tox<strong>in</strong> with<strong>in</strong><br />
the food cha<strong>in</strong>. [3]<br />
[1] S. K<strong>in</strong>near, Mar. Drugs. 2010, 8(3), 542–564.<br />
[2] A. Peuthert, Environ. Toxicol. 2007, 22(4), 436-442.<br />
[3] K. Kittler, Food Chem. 2012, 133(3), 875-879.<br />
Poster 226 Saturday 9:00 - 11:30 283
Characterization Anthocyan<strong>in</strong> by UV-Vis Spectroscopy and<br />
HPLC Detection <strong>in</strong> Chokeberry<br />
Jelena M. Brcanović, Aleksandra N. Pavlović, Snežana S. Mitić, Jovana N. Veljković,<br />
Milan N. Mitić, Jovana Lj. Pavlović<br />
Department of Chemistry – Faculty of Sciences and Mathematics, University of Niš –<br />
Višegradska 33 – Niš – SRB<br />
djolejeca97@gmail.com<br />
Aronia melanocarpa, native to eastern North America, is a member of the Rasaceae<br />
family. Chokeberries are rich <strong>in</strong> phenolic compounds and have been reported to<br />
have antioxidative effects <strong>in</strong> vitro and <strong>in</strong> vivo. It has been applied as a natural<br />
antihypertensive and anti-atherosclerotic drug, ma<strong>in</strong>ly by the polyphenols and anthocyan<strong>in</strong>s.<br />
The anthocyan<strong>in</strong>s are water-soluble plant pigments with antioxidant, anti<strong>in</strong>flammatory,<br />
antimicrobial, anticancer, hepatoprotective, gastroprotective. In the<br />
fruit, chlorogenic and neochlorogenic acids are dom<strong>in</strong>ant among the aromatic acids.<br />
High contents of cyanid<strong>in</strong>-3-arab<strong>in</strong>oside, cyanid<strong>in</strong>-3-galactoside and (-)-epicatech<strong>in</strong><br />
are also typical of chokeberries.<br />
In this study we have determ<strong>in</strong>ed the total content of anthocyan<strong>in</strong>s by the pHdifferential<br />
spectrophotometric method <strong>in</strong> five different samples (syrup, juice, berry,<br />
dried tea and chokebbery tea <strong>in</strong>fusions). Two dilutions were prepared, one with<br />
potassium chloride buffer (pH 1.0) and the other with sodium acetate buffer (pH<br />
4.5). Absorbance was measured simultaneously at 510 nm and 700 nm. The content<br />
of total anthocyan<strong>in</strong>s was expressed <strong>in</strong> mg of cyanid<strong>in</strong>-3-O-glucoside equivalents per<br />
100 g of chokeberry or liter of juice (mg C3GE/g or mg C3GE/L). Total anthocyan<strong>in</strong>s<br />
content from different samples ranged from 1055.68 mg/100 g (<strong>in</strong>fusion tea) to 56.757<br />
mg/100 g (chokeberry). Total anthocyan<strong>in</strong>s content from different solvents <strong>in</strong> chokeberry<br />
from 101.2 mg/100 g (solvent methanol 60%) to 28.71 mg/100 g (solvent water).<br />
Total anthocyan<strong>in</strong>s content from different samples <strong>in</strong> one solvent methanol 60% from<br />
715.65 mg/100 g (dried tea) to 96.52 mg/100 g (chokeberry). Qualitative and quantitative<br />
determ<strong>in</strong>ation of the content of anthocyan<strong>in</strong>s and phenolic compounds was<br />
measured by HPLC.<br />
This research was supported by the M<strong>in</strong>istry of Education, Science and Technological<br />
Development, grand number BI172047.<br />
Key words: anthocyan<strong>in</strong>s, chokeberry, HPLC, phenolic compounds<br />
284 Saturday 9:00 - 11:30 Poster 227
Taylor Dispersion Analysis (TDA) for Liquid Diffusivity<br />
Measurements<br />
Bianka Sieredz<strong>in</strong>ska ∗ , Magdalena Ligia Naurecka † , Anna Lewandrowska ‡ ,<br />
Aldona Majcher ‡<br />
∗ Faculty of Chemistry – the University of Warsaw – Pasteura 1 – Warsaw – POL<br />
† Faculty of Chemistry – Maria Curie-Sklodowska University <strong>in</strong> Lubl<strong>in</strong> –<br />
pl. Marii Curie-Sklodowskiej 2 – Lubl<strong>in</strong> – POL<br />
‡ Institute of Physical Chemistry – the Polish Academy of Sciences – Kasprzaka 44/52 –<br />
Warsaw – POL<br />
madamebianca@gmail.com - magda_naurecka@wp.pl<br />
Taylor Dispersion Analysis is a method for the study of diffusion coefficient, which<br />
was first described by Taylor (1953) and further developed by Aris (1954). It is based<br />
on the measurements of effective molecular diffusion coefficient dur<strong>in</strong>g flow through a<br />
long, th<strong>in</strong> capillary with and without selector. [1,2,7] The analysis demonstrates that<br />
it is possible to design an <strong>in</strong>strument that operates very nearly <strong>in</strong> accordance with<br />
the simplest mathematical description of the dispersion of a solute pulse <strong>in</strong> a fluid<br />
<strong>in</strong> lam<strong>in</strong>ar flow with<strong>in</strong> a straight, circular cross-section tube. The small departures<br />
of a practical <strong>in</strong>strument from the ideal are evaluated as corrections by means of<br />
a general perturbation treatment that allows them to be exam<strong>in</strong>ed one at a time.<br />
The corrections considered <strong>in</strong>clude the effects of the f<strong>in</strong>ite volume of the <strong>in</strong>jection<br />
pulse, the f<strong>in</strong>ite volume of the concentration monitor, the coil<strong>in</strong>g of the tube, and the<br />
nonuniformity and noncircularity of the cross section, as well as the variation of the<br />
fluid properties with composition. [3]<br />
TDA is a typical chromatographic method, where the chromatographic column is<br />
replaced by a capillary filled with an appropriate eluent (Tris-phosphate buffer, Tris-<br />
HCl buffer). A small <strong>in</strong>jection of the sample is applied to the system and the diffusion<br />
coefficients of the free ligand and the free selector (l-phenylalan<strong>in</strong>e, ribonuclease and<br />
warfar<strong>in</strong>) is determ<strong>in</strong>ed by TDA. The concentration of the ligand is the same as <strong>in</strong><br />
the experiment without selector. The concentration of the selector is the same as an<br />
eluent. The effective diffusion coefficient of the ligand dur<strong>in</strong>g the flow <strong>in</strong> the presence<br />
of the selector depends on the diffusion coefficient of free and complexed ligand, and<br />
also stability contact of the ligand-selector complex. [4] A method we used <strong>in</strong> our experiment<br />
was, ultrahigh pressure liquid chromatography (UHPLC). However, around<br />
the world there are several other methods used to determ<strong>in</strong>e dispersion coefficient,<br />
e.g. dynamic light scatter<strong>in</strong>g, [5] and nuclear resonance spectroscopy. [6]<br />
TDA might be useful <strong>in</strong> the study of biological substances. There is a large group<br />
of <strong>in</strong>dustrial processes that may f<strong>in</strong>d the dispersion coefficient parameter to be useful<br />
<strong>in</strong> designat<strong>in</strong>g and analyz<strong>in</strong>g new technological solutions. Furthermore, dispersion<br />
coefficient along with hydrodynamic properties can deliver <strong>in</strong>formation both about<br />
size and shape of macromolecules such as prote<strong>in</strong>s.<br />
[1]<br />
R. Aris, Proc. Soc. Lond. A 1956, 235, 67-77.<br />
[2]<br />
A. Bielejewska, A. Byl<strong>in</strong>a, K. Duszczyk, M. Fialkowski, R. Holyst, Anal.<br />
5463-5469.<br />
Chem. 2010, 82,<br />
[3]<br />
A. Alizadeh, C. A. Nieto de Castro, W. A. Wakeham, Int. J. Thermophys. 1980, 1, 243-284.<br />
[4] M. Zuo, Y. Han, L. Qi, Y. Chen, Ch<strong>in</strong>. Sci. Bull. 2007, 52, 3325-3332.<br />
[5] C. Yang, W. Li, Vu. Ch, J. Physic. Chem. 2004, 108, 11866-11870.<br />
[6] E. O. Stejskal, J. E. Tanner, J. Chem. Physics 1965, 42, 288-292.<br />
[7] M. Johnson, R. D. Kamm, J. Fluid Mech. 1986, 172, 329.<br />
Poster 228 Saturday 9:00 - 11:30 285
Influence of substituent effect on structure of imidazole<br />
N-oxide derivatives<br />
Marlena Lukomska ∗ , Agnieszka Rybarczyk-Pirek ∗ , Krzysztof Ejsmont † ,<br />
Marc<strong>in</strong> Palusiak ∗<br />
∗ Structural Chemistry and Crystallography Group – University of Lodz –<br />
Pomorska 163/165 – Lodz – POL<br />
† Crystallography Group – University of Opole – Oleska 48 – Opole – POL<br />
mlukomska@uni.lodz.pl<br />
Imidazole derivatives occur <strong>in</strong> biologically important systems and are used <strong>in</strong> agriculture<br />
and medic<strong>in</strong>e. [1-4] Various medicaments based on imidazole and benzimidazole<br />
derivatives are applied <strong>in</strong> treatment of parasitic diseases like trichomoniasis or<br />
Chang disease which are caused by protozoa Trichomonas vag<strong>in</strong>alis and Trypansoma<br />
cruzi. [5,6] S<strong>in</strong>ce currently used drugs cause serious side effects, chemists are look<strong>in</strong>g<br />
for new more effective chemicals which <strong>in</strong> the same time could be less toxic. In that<br />
light it is worth mention<strong>in</strong>g that some imidazole N–oxide derivatives were tested <strong>in</strong><br />
vitro aga<strong>in</strong>st the mentioned protozoa [7] with positive results.<br />
As cont<strong>in</strong>uation of broad studies on novel imidazole N-oxide derivatives the crystal<br />
structures of six new compounds were determ<strong>in</strong>ed by X–ray method. The analysis<br />
of structural properties of <strong>in</strong>dividual molecules as well as <strong>in</strong>termolecular contacts <strong>in</strong><br />
crystals was performed. The <strong>in</strong>fluence of substituent effect on selected geometrical<br />
parameters <strong>in</strong>clud<strong>in</strong>g parameters of <strong>in</strong>tramolecular N − H · · · O (−) charge assisted<br />
hydrogen bond will be discussed <strong>in</strong> this presentation.<br />
Acknowledgment: Authors thank dr Marc<strong>in</strong> Jasiński (Department of Organic and<br />
Applied Chemistry, University of Łódź) for crystal samples.<br />
Fig.1:Molecular structure of the <strong>in</strong>vestigated compounds(R=H, CN, OCH3, NO2, CF3, F)<br />
[1]<br />
M. R. Grimmett, Adv. Heterocycl. Chem. 1970, 12, 103.<br />
[2]<br />
M. R. Grimmett, Adv. Heterocycl. Chem. 1980, 27, 241.<br />
[3]<br />
M. R. Grimmett, <strong>in</strong> Comprehensive Heterocyclic Chemistry, Ed. K. T. Potts, Pergamon<br />
Press, Oxford 1984, 5, 374.<br />
[4]<br />
K. Ebel, <strong>in</strong> Methoden der organischen Chemie (Houben-Weyl), Band E8c, Teil III, Ed. E.<br />
Schaumann, G. Thieme, Stuttgart, 1994, 1.<br />
[5]<br />
H. Cerecetto, M. González, Current Topic Med. Chem. 2002, 2, 1185<br />
[6]<br />
C. Cosar, P. Ganter, L. Jolou, Presse Med. 1961, 69, 1069.<br />
[7]<br />
G. Aguirre, M. Boiani, H. Cerecetto, A. Gerpe, M. González, F. Sa<strong>in</strong>z, A. Denicola, C. Ochoa<br />
de Ocáriz, J. Nogal, D. Montero, J. A. Escario, Arch. Pharm. Pharm. Med. Chem. 2004, 337,<br />
259.<br />
286 Saturday 9:00 - 11:30 Poster 229
Crystallographic Description of Crystall<strong>in</strong>e Nanostructures<br />
Virg<strong>in</strong>ia Ramona Bucila ∗ , Davide M. Proserpio † , Mircea V. Diudea ∗ ,<br />
Miranda Petronella Vlad ‡<br />
∗ Department of Organic Chemistry –<br />
Babes-Bolyai University, Faculty of Chemistry and Chemical Eng<strong>in</strong>eer<strong>in</strong>g Cluj-Napoca –<br />
Arany Janos Str.11 – Cluj-Napoca – ROU<br />
† Dipartimento di Chimica – Universita’ degli Studi di Milano –<br />
Via Golgi, 19 - <strong>2013</strong>3 Milano, Italy – Milano – ITA<br />
‡ Department of F<strong>in</strong>ance and Account<strong>in</strong>g –<br />
“Dimitrie Cantemir” Christian University Bucharest Fac. of Eco. Sci. of Cluj-Napoca –<br />
56. Teodor Mihaly Street Cluj Napoca – Cluj-Napoca – ROU<br />
virg<strong>in</strong>iabucila@yahoo.com<br />
The present work is dedicated to present<strong>in</strong>g the crystallographic description of some<br />
studied nano crystall<strong>in</strong>e networks as 3-periodic structures. For each structure, we determ<strong>in</strong>e<br />
the category to which it belongs (3-c net, 4-c net, 3,4-c net or other nets), its<br />
po<strong>in</strong>t symbol, stoichiometry, vertex symbol, topos parameters and identify whether<br />
the structure has a known or new topology, with the help of the TOPOS program<br />
(a program package for multipurpose crystallochemical analysis) and additional programs<br />
we developed.<br />
We also used a program called Systre designed to analyze periodic nets as they arise<br />
<strong>in</strong> the study of extended crystal structures (as opposed to molecular crystals). Systre<br />
uses a method called barycentric placement to determ<strong>in</strong>e the ideal symmetry of the<br />
crystal net (optimal embedd<strong>in</strong>g) and to analyze its topological structure.<br />
Poster 230 Saturday 9:00 - 11:30 287
Terahertz-Time-Doma<strong>in</strong>-Spectroscopy (THz-TDS) as<br />
Method for the Analysis of the Polymorphism <strong>in</strong> Aspir<strong>in</strong><br />
Sebastian Reimann, Christian Roth, Stella Schmode, Ralf Ludwig<br />
Physical and Theoretical Chemistry – University of Rostock / Institute of Chemistry –<br />
Dr.-Lorenz-Weg 1 – Rostock – GER<br />
basti.reimann@googlemail.com<br />
Nowadays, terahertz time doma<strong>in</strong> spectroscopy (THz-TDS) has ga<strong>in</strong>ed remarkable importance<br />
for characterization of materials, s<strong>in</strong>ce THz spectroscopy has high sensitivity<br />
to the conformation and structure of molecules as well as its adjacent environment. [1]<br />
Especially lattice vibrations of molecular crystals occur at THz frequencies be<strong>in</strong>g <strong>in</strong>credibly<br />
sensitive to the <strong>in</strong>termolecular contacts of the crystal system. [2] Thus, variations<br />
<strong>in</strong> crystall<strong>in</strong>e materials composed of identical molecules, such as polymorphs,<br />
typically show unique THz vibrational spectra due to their dist<strong>in</strong>ct three-dimensional<br />
structures.<br />
Aspir<strong>in</strong> exhibits a fasc<strong>in</strong>at<strong>in</strong>g and perplex<strong>in</strong>g structural chemistry possess<strong>in</strong>g two<br />
polymorphs (form I and form II). [3] Exemplarily, we have chosen this ubiquitous<br />
compound to develop a new procedure prob<strong>in</strong>g the phenomenon of polymorphism by<br />
THz-TDS spectroscopy. Both, form I and form II, were synthesized and def<strong>in</strong>ed by Xray<br />
powder diffraction. [3] Subsequently, THz-TDS has been applied to identify both<br />
polymorphs of Aspir<strong>in</strong> provid<strong>in</strong>g structural <strong>in</strong>formation of the molecules as well. The<br />
observed THz features were compared to far-IR measurements and the f<strong>in</strong>al results<br />
were verified theoretically by DFT calculations.<br />
Scheme 1. Elucidat<strong>in</strong>g the polymorphism of Aspir<strong>in</strong> us<strong>in</strong>g THz spectroscopy.<br />
[1]<br />
a) S. L. Dexheimer (Ed.), Terahertz Spectroscopy - Pr<strong>in</strong>ciples and Applications, Taylor<br />
Francis Ltd., Boca Raton, Florida, 2008; b) Y.-C. Shen, Int. J. Pharm. 2011, 417, 48-60; c) R.<br />
M. Smith, M. A. Arnold, Appl. Spec. Rev. 2011, 46(8), 636-679.<br />
[2]<br />
M. D. K<strong>in</strong>g, E. A. Davis, T. M. Smith, T. M. Korter, J. Phys. Chem. A 2011, 115, 11039-<br />
11044.<br />
[3]<br />
a) A. D. Bond, CrystEngComm 2012, 14, 2363-2366; b) A. D. Bond, K. A. Solanko, S.<br />
Parsons, S. Redder, R. Boese, CrystEngComm 2011, 13, 399-401; c) A. D. Bond, R. Boese, G.<br />
R. Desiraju, Angew. Chem. 2007, 119, 625-630.<br />
288 Saturday 9:00 - 11:30 Poster 231
The <strong>in</strong>fluence of the reactants flow through the<br />
reaction-stripp<strong>in</strong>g column on the 1,3-dichloropropan-2-ol<br />
dehydrochlor<strong>in</strong>ation process<br />
Anna Krzyżanowska, Eugeniusz Milchert<br />
Institute of Organic Chemical Technology –<br />
West Pomeranian University Of Technology – Pułaski Str. 10 – Szczec<strong>in</strong> – POL<br />
akrzyzanowska@zut.edu.pl<br />
As a result of 1,3-dichloropropan-2-ol dehydrochlor<strong>in</strong>ation reaction epichlorohydr<strong>in</strong> is<br />
obta<strong>in</strong>ed. Epichlorohydr<strong>in</strong> is an important <strong>in</strong>termediate ma<strong>in</strong>ly use <strong>in</strong> the production<br />
of epoxy res<strong>in</strong>s. [1]<br />
Commercially epichlorohydr<strong>in</strong> is manufactured by react<strong>in</strong>g allyl chloride with chlor<strong>in</strong>e–water<br />
to obta<strong>in</strong> a mixture of chlorohydr<strong>in</strong>s, which are then treated with milk<br />
of lime to produce epichlorohyd<strong>in</strong>. [2] Nowadays, last for research on the receipt of<br />
epichlorohydr<strong>in</strong> from glycerol. This process based on the conversion of glycerol to<br />
dichlorohydr<strong>in</strong>s (ma<strong>in</strong>ly 1,3-dichloropropan-2-ol), and then dehydrochlor<strong>in</strong>ation to<br />
epichlorohydr<strong>in</strong> (the GTE process). [3] In the literature, there are no reports concern<strong>in</strong>g<br />
the process parameters of production of epichlorohydr<strong>in</strong> from 1,3-dichloropropan-<br />
2-ol and the methods of realization of technological process itself.<br />
The aim of doctoral thesis is study on the <strong>in</strong>fluence of technological parameters on<br />
the cont<strong>in</strong>uously dehydrochlor<strong>in</strong>ation process <strong>in</strong> the reaction-stripp<strong>in</strong>g column. One<br />
of this parameters is flow of 88 wt % aqueous solution of 1,3-dichloropropan-2-ol and<br />
10 wt % milk of lime. The total reactants flow was changed (from 12.1 cm 3 /m<strong>in</strong><br />
to 70.0 cm 3 /m<strong>in</strong>) and the <strong>in</strong>fluence on the selectivity to the epichlorohydr<strong>in</strong> and<br />
1,3-dichloropropan-2-ol conversion was studied.<br />
Increas<strong>in</strong>g the summary flow rate of reactants <strong>in</strong> the range of 12.1 to 70.0 cm 3 /m<strong>in</strong>, at<br />
a constant flow of steam (4.3 dm 3 /m<strong>in</strong>), reduces the conversion of 1,3-dichloropropan-<br />
2-ol from about 90% to 80%. The selectivity of epichlorohydr<strong>in</strong> is constant and is<br />
approximately 99%. At summary total flow of reactants which is 70.0 cm 3 /m<strong>in</strong>, the<br />
flood<strong>in</strong>g of column is occur.<br />
[1]<br />
P. Czub, Z. Bończa-Tomaszewski, P. Penczek, J. Pielichowski.<br />
epoksydowych. PWN, Warsaw, 2002, 24-25.<br />
Chemia i technologia żywic<br />
[2]<br />
E. Grzywa, J. Molenda.<br />
2008, 278-280.<br />
Technologia podstawowych syntez organicznych. WNT, Warsaw,<br />
[3]<br />
B.M Bell, J.R. Briggs, Clean Journal, 2008, 36(8), 657-661.<br />
Poster 232 Saturday 9:00 - 11:30 289
Determ<strong>in</strong>ation of folic acid and its major derivatives by<br />
capillary electrophoresis<br />
Justyna Stachniuk, Radoslaw Dalkowski, Barbara Krawczyk, Dom<strong>in</strong>ik Szczukocki,<br />
Robert Zakrzewski<br />
Inorganic and Analytical Chemistry – University of Lodz, Faculty of Chemistry –<br />
Tamka 12 – Lodz – POL<br />
stachniuk.justyna@wp.pl<br />
Folic acid (FA) is the simplest naturally occurr<strong>in</strong>g water soluble vitam<strong>in</strong> and most<br />
stable form of folate, which is essential for humans. Mammals cannot synthesize folate<br />
by themselves so it should be supplied with food. Folic acid has different important<br />
functions <strong>in</strong> the human body while it is not biologically active. All the biological<br />
functions of FA are performed by tetrahydrofolic acid (FH4) and other derivatives<br />
which are generated <strong>in</strong> the presence of dihydrofolate reductase (DHFR). This FH4<br />
is the ma<strong>in</strong> circulat<strong>in</strong>g form of folate which plays a major role <strong>in</strong> the red blood cells<br />
synthesis and tissue development. This compound also facilitates the s<strong>in</strong>gle carbon<br />
transfer reaction for the synthesis of basic constituents of DNA and RNA and the<br />
production of methion<strong>in</strong>e from homocyste<strong>in</strong>e. The supplementation of FA prevents<br />
sp<strong>in</strong>a bifida and related neural tube birth defects.<br />
Methotrexate (MTX) is an analog of folic acid. It is a potent FA antagonist which<br />
acts as an <strong>in</strong>hibitor of DHFR lead<strong>in</strong>g to DNA damage and cell death. Dur<strong>in</strong>g the<br />
last-half century MTX has been widely used <strong>in</strong> large doses for the treatment of acute<br />
lymphoblastic leukemia, as an anti-<strong>in</strong>flammatory and immunosuppressive drug, <strong>in</strong><br />
low doses <strong>in</strong> the treatment of rheumatoid arthritis and other diseases. Today, due<br />
to its antiproliferate activity, MTX is ma<strong>in</strong>ly used <strong>in</strong> the treatment of leukemia,<br />
lymphomas as well as certa<strong>in</strong> solid tumors. As a chemotherapeutic drug for tumors,<br />
methotrexate is usually used <strong>in</strong> high doses, which causes same side effects such as<br />
vomit<strong>in</strong>g, myelosuppression, hepatotoxicity, nephrotoxicity and neurotoxicity. That<br />
is why, high doses of MTX are always followed by fol<strong>in</strong>ic acid (FNA) rescue lead<strong>in</strong>g<br />
to an <strong>in</strong>crease of reduced folates <strong>in</strong> the cellular concentration.<br />
Due to the importance of FA, toxic side effects of MTX and rescue value of FNA, their<br />
concentration <strong>in</strong> nutrition supplements, pharmaceutical preparations and plasma or<br />
ur<strong>in</strong>e should be regularly monitored. In literature several analytical methods, <strong>in</strong>clud<strong>in</strong>g<br />
HPLC and CE, can be found to quantify mentioned compounds separately. [1,2]<br />
These separation techniques are powerful due to their high resolution, high efficiency,<br />
rapid separation of analytes and m<strong>in</strong>imum operation cost. Thus, <strong>in</strong> this study we<br />
evaluate and validate a reliable CE method with UV detection for measur<strong>in</strong>g the<br />
concentration of FA, FNA and MTX <strong>in</strong> biological samples. The start<strong>in</strong>g conditions<br />
for the development of these compounds were calculated from the CE conditions of<br />
a validated method for some organic acids. [3] The method was optimized by test<strong>in</strong>g<br />
the follow<strong>in</strong>g parameters: the used buffer concentration and pH, time of <strong>in</strong>jection and<br />
temperature.<br />
[1]<br />
E. Decon<strong>in</strong>ck, S. Crevits, P. Baten, P. Courselle, J. De Beer, J. Pharm. Biomed. Anal. 2011,<br />
54, 995-1000.<br />
[2]<br />
S. Zhao, H. Yuan, Ch. Xie, D. Xiao, J. Chromatogr. A 2006, 1107, 290-293.<br />
[3]<br />
I. S. L. Lee, M. C. Boyce, M. C. Breadmore, Food chemistry 2011, 127, 797-801.<br />
290 Saturday 9:00 - 11:30 Poster 233
Calcium Fructoborate Influence on Inflammation<br />
Anca-Mihaela Bulearca, Andrei Bita, Romulus Ion Scorei<br />
research department –<br />
Bioboron Research Institute from Natural Research Ltd., Craiova, Dolj, Romania –<br />
Strada A.I.Cuza, nr. 15, bloc Patria, sc.B, ap.11, etaj 2, Craiova, Dolj, Romania –<br />
Craiova, Dolj County – ROU<br />
ancutabulearca@yahoo.com<br />
Several population-based cl<strong>in</strong>ical studies have shown that the level of C-reactive prote<strong>in</strong><br />
(CRP), an immune recognition prote<strong>in</strong>, is a sensitive marker of <strong>in</strong>flammation.<br />
Calcium fructoborate (CF) is a sugar-borate ester (SBE), patented complex of calcium,<br />
fructose and boron found naturally <strong>in</strong> fresh and dried fruits, vegetables and<br />
herbs, and w<strong>in</strong>e. Published cl<strong>in</strong>ical researches <strong>in</strong>dicate that CF significantly reduces<br />
serum levels of CRP <strong>in</strong> humans, suggest<strong>in</strong>g this unique plant-m<strong>in</strong>eral complex controls<br />
the <strong>in</strong>flammation.<br />
Poster 234 Saturday 9:00 - 11:30 291
Design, Synthesis and Biological Study of<br />
4-(Polyfluoroalkyl)-1,2-dihydropyrazolo[3,4-b]pyrid<strong>in</strong>-3-ones<br />
and correspond<strong>in</strong>g Nucleosides - new<br />
6-Polyfluoroalkyl-conta<strong>in</strong><strong>in</strong>g Pur<strong>in</strong>e Isosters as potential<br />
Drug-like Scaffolds<br />
L<strong>in</strong>da Supe ∗ , Robert Begunk † , Jan<strong>in</strong>e Hussner † , Henriette Meyer zu Schwabedissen † ,<br />
Katr<strong>in</strong> Sternberg † , Viktor O. Iaroshenko ∗<br />
∗ Institut für Chemie – Universität Rostock – Albert-E<strong>in</strong>ste<strong>in</strong> Str. 3a – Rostock – GER<br />
† Institut für Biomediz<strong>in</strong>ische Technik – Universität Rostock –<br />
Friedrich-Barnewitz-Straße 4 – Rostock – GER<br />
l<strong>in</strong>dasupe@gmail.com<br />
Nucleosides furnished with fluor<strong>in</strong>e functionality either <strong>in</strong> sugar or <strong>in</strong> the heterocyclic<br />
part take a special place among biologically active molecules. Development of fluor<strong>in</strong>ated<br />
nucleosides became the result of the extensive antiviral and anticancer research<br />
stimulated by emergence of acquired immunodeficiency syndrome (AIDS) and tumours.<br />
To date there are known several marketed drugs so called fluor<strong>in</strong>ated pur<strong>in</strong>e<br />
and pyrimid<strong>in</strong>e antimetabolites cl<strong>in</strong>ically broadly used for the treatment numerous of<br />
cancers and viral <strong>in</strong>fections. [1]<br />
In this work performed reactions <strong>in</strong>clude synthesis of 1H -pyrazolo[3,4-b]pyrid<strong>in</strong>-3ones<br />
3 and correspond<strong>in</strong>g nucleosides 4 (Fig.1). Besides peracylated ribofuranose,<br />
correspond<strong>in</strong>g glycose and rhamnose derivatives were used giv<strong>in</strong>g accord<strong>in</strong>g nucleosides<br />
<strong>in</strong> good to excellent yields. Catalytic reduction of pyrid<strong>in</strong>e r<strong>in</strong>g 3 was carried<br />
out successfully.<br />
Prelim<strong>in</strong>ary biological evaluation library of more than 150 compounds, and subsequent<br />
optimization by the additional hit-to-lead study resulted <strong>in</strong> the identification<br />
of several representatives with strong antagonistic action on human smooth muscle<br />
cells. Lead compounds LS 009 and LS 057 are now under study as novel, cell-selective<br />
drug-candidate for endovascular implants.<br />
Fig. 1. Synthesis of perfluoralkyl group conta<strong>in</strong><strong>in</strong>g pur<strong>in</strong>e-like scaffolds.<br />
[1] (a) K. L. J. Kirk, Fluor. Chem. 2006, 127, 1013-1029; (b) W. K. J. Hagmann, Med. Chem.<br />
2008, 4359-4369; (c) V. Gouverneur, K. Müller, Fluor<strong>in</strong>e <strong>in</strong> Pharmaceutical and Medic<strong>in</strong>al<br />
Chemistry, Imperial College Press 2012, ISBN-10: 1-84816-634-6; (d) P. Shah, A. D. J. Westwell,<br />
Enzyme Inhib. Med. Chem, 2007, 22, 527–540; (e) P. Liu, A. Sharon, C. K. J. Chu, Fluor.<br />
Chem. 2008, 129, 743-766; (f) S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc.<br />
Rev. 2008, 37, 320-330.<br />
292 Saturday 9:00 - 11:30 Poster 235
PNA/PNA Recognition Mediated Ligation Strategy<br />
Apply<strong>in</strong>g a Photosensitive L<strong>in</strong>ker<br />
Cornelia H. Panse, Stephen Middel, Ulf Diederichsen<br />
Institute of Organic and Biomolecular Chemistry – Georg-August-University Gött<strong>in</strong>gen –<br />
Tammannstr. 2 – Gött<strong>in</strong>gen – GER<br />
cpanse@gwdg.de<br />
The photochemical properties of o-nitrobenzene compounds are known for more than<br />
hundred years, [1] whereas photocleavable groups based on this concept have been<br />
<strong>in</strong>troduced <strong>in</strong> the 1960s. [2] S<strong>in</strong>ce then, photodeprotection and cleavage are well established<br />
<strong>in</strong> various fields of research. [3] Our aim is to use the photocleavable unit to<br />
cleave PNA oligomers after these oligomers served <strong>in</strong> a ligation reaction. PNA/PNA<br />
recognition facilitates nearly unlimited orthogonal ligation sites (Scheme 1). Here<strong>in</strong>,<br />
PNA covalently attached to the peptide br<strong>in</strong>gs the functionalized centres of the<br />
two peptides <strong>in</strong> close proximity by PNA/PNA base pair recognition. Follow<strong>in</strong>g the<br />
PNA-mediated peptide ligation the PNA strands need to be cleaved off us<strong>in</strong>g the onitrobenzene<br />
derivate. For this purpose a photocleavable l<strong>in</strong>ker was synthesized based<br />
on the 3,4-dimethylnitrobenzene structure, which is known to have enhanced quantum<br />
yields and photon absorption properties compared to the unsubstituted nitrobenzene<br />
derivative. [4] For functionalization with PNA an ethyne moiety was <strong>in</strong>troduced <strong>in</strong><br />
benzylic position of the nitrobenzene r<strong>in</strong>g. [5] In prelim<strong>in</strong>ary experiments it was shown<br />
that the photolabile group at the N -term<strong>in</strong>us of a peptide was uncaged with<strong>in</strong> 30 m<strong>in</strong>utes<br />
of UV exposure. Furthermore, functionalization with a res<strong>in</strong> bound PNA strand<br />
apply<strong>in</strong>g copper mediated click chemistry is possible. In near future PNA-mediated<br />
ligation experiments will be explored.<br />
Scheme 1: Strategy for the PNA/PNA mediated ligation us<strong>in</strong>g a photocleavable<br />
auxiliary.<br />
[1] P. Silber, G. Ciamician, Chem. Ber. 1901, 34, 2040.<br />
[2] A. Patchornik, B. Amit, R. B. Woodward, J. Am. Chem. Soc. 1970, 92, 6333.<br />
[3] C. Brieke, F. Rohrbach, G. Mayer, A. Heckel, Angew. Chem. Int. Ed. 2012, 51, 8446.<br />
[4] K. Schaper, M. Et<strong>in</strong>ski, T. Fleig, Photochem. Photobiol. 2009, 85, 1075.<br />
[5] J. A. Baccile, M. A. Morrell, R. M. Falotico, B. T. Milliken, D. L. Drew, F. M. Rossi,Tetrahedron<br />
Lett. 2012, 53, 1933.<br />
Poster 236 Saturday 9:00 - 11:30 293
HPLC screen<strong>in</strong>g and evaluation of antioxidative capacity of<br />
Hylotelephium spectabile (Boreau) H. Ohba x telephium (L.)<br />
H.Ohba leaf and flower extracts, fractions and their<br />
hydrolysates<br />
Snezana Jovanovic ∗ , Goran Petrovic ∗ , Bojan Zlatkovic † , Aleksandra Djordjevic ∗ ,<br />
Olga Jovanovic ∗ , Vesna Stankov-Jovanovic ∗ , Violeta Mitic ∗ , Marija Ilic ∗ ,<br />
Gordana Stojanovic ∗<br />
∗ Department of Chemistry – University of Niš, Faculty of Sciences and Mathematics –<br />
Visegradska 33 – Nis – SRB<br />
† Department of Biology and Ecology –<br />
University of Niš, Faculty of Sciences and Mathematics – Visegradska 33 – Nis – SRB<br />
snezana_chem@yahoo.com<br />
Hylotelephium genus is well-known due to a wide range of pharmacological effects<br />
(anti-<strong>in</strong>flammatory, anti-radiation, antiviral, anticancer, etc.). Leaf juice locally heals<br />
wound, sk<strong>in</strong> disease and spots, and relieves the pa<strong>in</strong> caused by cold to the ear. Investigated<br />
plant, Hylotelephium spectabile (Boreau) H. Ohba x telephium (L.) H.Ohba,<br />
a taxon of hybrid orig<strong>in</strong> is grown as an ornamental and medic<strong>in</strong>al plant across Serbia.<br />
Ch<strong>in</strong>a and Japan are natural habitats of H. spectabile (Autumn Joy, Ice plant) while<br />
H. telephium (Orp<strong>in</strong>e, Livelong, Frog’s-stomach, Midsummer-men, Witch’s Moneybags,etc.)<br />
is native to Eurasia. Wide use of plant <strong>in</strong> traditional medic<strong>in</strong>e <strong>in</strong>duced our<br />
<strong>in</strong>terests to exam<strong>in</strong>e chemical composition and antioxidative activity of plant MeOH<br />
extracts, its fractions and hydrolysates. Experimental work <strong>in</strong>cluded preparation of<br />
fresh leaves and flowers MeOH extracts and liguid-liguid partition of each extract to<br />
obta<strong>in</strong> hexane, EtOAc and BuOH fractions. Except hexane fraction, MeOH extracts<br />
and theirs fractions were hydrolysed. HPLC chromatograms showed that extracts<br />
conta<strong>in</strong> mostly quercet<strong>in</strong> and kaempferol glycosides, as confirmed by the composition<br />
of hydrolysates whose ma<strong>in</strong> components were quercet<strong>in</strong> and kaempferol. Evaluations<br />
of antioxidant activity were done by apply<strong>in</strong>g the follow<strong>in</strong>g assays: DPPH assay,<br />
ABTS assay and Total reduc<strong>in</strong>g power assay (Fe 3+ to Fe 2+ ). Additionally total<br />
flavonoid content (based on flavonoid aff<strong>in</strong>ity to form complex with AlCl3 ) and total<br />
phenols (by Fol<strong>in</strong>-Ciocalteu reagent based on reduction of Mo 6+ to Mo 5+ ) were<br />
determ<strong>in</strong>ed. Flower EtOAc fraction showed best activity for all performed assays.<br />
Leaf samples have lower activity then correspond<strong>in</strong>g flower samples. Flower samples<br />
(EtOAc, BuOH fractions and their hydrolysates) are better DPPH radical and ABTS<br />
radical cation scavengers than rut<strong>in</strong>, exclud<strong>in</strong>g BuOH fraction aga<strong>in</strong>st ABTS radical<br />
cation. In non hydrolysed samples (mgml −1 ) values for total flavonoid content,<br />
expressed as rut<strong>in</strong> equivalents, was ranged from 57.20 to 121.33 µgml −1 and <strong>in</strong> hydrolysed<br />
from 101.98 to 539.16 µgml −1 . Range values of total phenol content (gallic<br />
acid equivalents), for non hydrolysed samples was from 53.33 to 960.00 µgml −1 and<br />
for hydrolysed samples from 173.33 to 1946.67 µgml −1 .<br />
Acknowledgements: The research was supported by the Serbian M<strong>in</strong>istry of Education,<br />
Science and Technology Development (Grant no 172047).<br />
Keywords: Hylotelephium spectabile (Boreau) H. Ohba x telephium (L.) H.Ohba,<br />
flavonoids, HPLC, antioxidative activity<br />
294 Saturday 9:00 - 11:30 Poster 237
Location of tetraarylporphyr<strong>in</strong> <strong>in</strong> sterically stabilized<br />
liposomes<br />
Natalia Szydłowska, Monika Dzieciuch, Mariusz Kepczynski, Maria Nowakowska<br />
Faculty of Chemistry – University – Ingardena 3 – Krakow – POL<br />
nszydlow@wp.pl<br />
The aim of our studies was to determ<strong>in</strong>e partition<strong>in</strong>g of tetraarylporphyr<strong>in</strong> (mTHPP)<br />
to sterically stabilized liposomes (SSL). Liposomes are spherical vesicles formed by<br />
some amphiphilic compounds, e.g., phosphatidylchol<strong>in</strong>es and are considered as a<br />
model of biological membranes. Incorporation of lipids with covalently attached<br />
poly(ethylene glycol) (PEG) <strong>in</strong>to liposomal bilayer membranes causes significant stabilization<br />
of liposome suspensions, prevents their aggregation and <strong>in</strong>hibits prote<strong>in</strong><br />
and cellular <strong>in</strong>teractions with liposomes thereby considerably prolong<strong>in</strong>g their blood<br />
circulation time. These vesicles are known as pegylated or SSL liposomes and are applied<br />
as effective drug delivery supports. [1,2] The <strong>in</strong>teractions between mTHPP and<br />
SSL were studied us<strong>in</strong>g fluorescence methods. POPC liposomes conta<strong>in</strong><strong>in</strong>g one of the<br />
quenchers were prepared by sonication. [3] A series of doxyl-sp<strong>in</strong> labeled molecules:<br />
3β-doxyl-5α-cholestane (CSL), 5-doxyl stearic acid (5-SASL) or 16-doxyl stearic acid<br />
(16-SASL) was used <strong>in</strong> the measurements. The f<strong>in</strong>al concentration ratio between<br />
POPC and the quencher <strong>in</strong> the sample was 80:20. The vertical localization of the fluorophore<br />
<strong>in</strong> a membrane was calculated accord<strong>in</strong>g to the parallax method. The basic<br />
idea of parallax method is to compare the amount of fluorescence quench<strong>in</strong>g caused<br />
by quenchers which are located at two different depths <strong>in</strong> the bilayer. [4] mTHPP was<br />
quenched mostly by CSL and 16-SASL. The shallow position of mTHPP <strong>in</strong> the pegylated<br />
membrane <strong>in</strong>dicates that the porphyr<strong>in</strong> tends to escape to the PEG layer. An<br />
additional method to obta<strong>in</strong> the <strong>in</strong>formation about the relative vertical depth location<br />
of membrane-bound fluorophores <strong>in</strong> a membrane is quench<strong>in</strong>g of the porphyr<strong>in</strong><br />
fluorescence with copper ions. Fluorescence quench<strong>in</strong>g is associated with a collisional<br />
quench<strong>in</strong>g constant, KSV, which is obta<strong>in</strong>ed from the Stern–Volmer equation. The<br />
KSV value for mTHPP <strong>in</strong> non-pegylated liposomes is much lower than for mTHPP <strong>in</strong><br />
pegylated liposomes, which suggests that the porphyr<strong>in</strong> <strong>in</strong> SSL is situated superficially<br />
<strong>in</strong> the bilayer.<br />
[1] M.C. Woodle, “Controll<strong>in</strong>g liposome blood clearance by surface-grafted polymers”, Adv. Drug<br />
Deliv. Rev. 1998, 32, 139-152.<br />
[2] S. Piperoudi, D. Fatouros, P. V. Ioannou, P. Frederik, S.G. Antimisiaris, “Incorporation of<br />
PEG-lipids <strong>in</strong> arsonoliposomes results <strong>in</strong> formation of highly stable arsenic-conta<strong>in</strong><strong>in</strong>g vesicles”,<br />
Chem. Phys. Lipids 2006, 139, 96-106.<br />
[3] M. Kepczynski, M. Kumorek, M. Stepniewski, T. Róg, B. Kozik, D. Jamróz, J. Bednar, M.<br />
Nowakowska, “Behavior of 2,6-Bis(decyloxy)naphthalene Inside Lipid Bilayer”, 2010.<br />
[4] A. Chattopadhyay, E. London, Biochemistry 1987, 26, 39.<br />
Poster 238 Saturday 9:00 - 11:30 295
Total Polyphenol, Flavonoid Contents and Antioxidant<br />
Capacity of Chokeberry<br />
Jovana N. Veljković, Jelena M. Brcanovic, Aleksandra N. Pavlovic, Snezana B. Tosic,<br />
Milan M. Stojkovic, Dusan Ð. Paunovic, Branka T. Stojanovic<br />
Department of Chemistry – University of Niš, Faculty of Sciences and Mathematics –<br />
Višegradska 33, 18000 Niš, Serbia – Niš – SRB<br />
jovanaveljkovic86@gmail.com<br />
The purpose of the present study was to evaluate small and high molecular phenolics,<br />
flavonoid and antioxidant activity of Aronia melanocarpa. Small berries such as black<br />
chokeberry (Aronia melanocarpa) represent one of the important sources of potential<br />
healthpromot<strong>in</strong>g phytochemicals because these fruits are rich <strong>in</strong> compounds with<br />
high antioxidant properties.The objective of our research was to evaluate the total<br />
polyphenol and flavonoid contents as well as antioxidant activity of five different<br />
products aronia <strong>in</strong> six different solvents.<br />
Total polyphenol content was determ<strong>in</strong>ed spectrophotometrically accord<strong>in</strong>g to the<br />
Fol<strong>in</strong>-Ciocalteu method (λ=760 nm), us<strong>in</strong>g gallic acid (GA) as a standard, and ranged<br />
from 66.68 mg/g (aronia dried tea, solvent acetone) to 4.25 mg/g (juce of aronia,<br />
solvent acetone). The total flavonoid content <strong>in</strong> selected chokeberry samples was determ<strong>in</strong>ed<br />
accord<strong>in</strong>g the alum<strong>in</strong>um chloride spectrophotometric method (λ=510 nm).<br />
Catech<strong>in</strong> was chosen as a standard and the results expressed <strong>in</strong> milligram catech<strong>in</strong><br />
equivalents per gram of extract (mg CE/g). Results are ranged from 52.2 mg/g (aronia<br />
dried tea, solvent acetone) to 3.52 mg/g (syrup, solvent water). DPPH radical scaveng<strong>in</strong>g<br />
activity, 2,2’-az<strong>in</strong>o-bis(3-ethylbenzthiazol<strong>in</strong>e-6-sulphonic acid) radical cation<br />
scaveng<strong>in</strong>g activity (ABTS), ferric reduc<strong>in</strong>g-antioxidant power (FRAP) and reduc<strong>in</strong>g<br />
power assay Fe(III) to Fe(II) (RP) were used to assess the antioxidant capacity (AC)<br />
of chokeberry. These assays, based on different chemical mechanisms, were selected<br />
to take <strong>in</strong>to account the wide variety and range of action of antioxidant compounds<br />
present <strong>in</strong> selected chokeberry samples. All samples showed antioxidant power. The<br />
results obta<strong>in</strong>ed <strong>in</strong> this work are generally consistent with literature data.<br />
This research was supported by the M<strong>in</strong>istry of Education, Science and Technological<br />
Development, grant number BI172047<br />
Keywords: total phenols, flavonoids, antioxidant capacity, chokeberry.<br />
296 Saturday 9:00 - 11:30 Poster 239
A D<strong>in</strong>uclear, Molecular Iron(II) Silicate with two High-Sp<strong>in</strong>,<br />
Square Planar FeO4 Units<br />
Denise P<strong>in</strong>kert ∗ , Serhiy Demeshko † , Fabian Schax ∗ , Beatrice Braun ∗ , Franc Meyer † ,<br />
Christian Limberg ∗<br />
∗ Institut für Chemie – Humboldt-Universität zu Berl<strong>in</strong> – Brook-Taylor-Str. 2 – Berl<strong>in</strong> –<br />
GER<br />
† Institut für Anorganische Chemie – Georg-August-Universität Gött<strong>in</strong>gen –<br />
Tammannstraße 4 – Gött<strong>in</strong>gen – GER<br />
denise.p<strong>in</strong>kert@chemie.hu-berl<strong>in</strong>.de<br />
For four ligand donor atoms surround<strong>in</strong>g a metal ion, tetrahedral and square planar<br />
ligand geometries have to be considered. The comparison of the ligand field stabilization<br />
energies of high-sp<strong>in</strong> and low-sp<strong>in</strong> configurations provides a rationale, why a<br />
certa<strong>in</strong> structure and electron configuration is stable and others are not. Square planar<br />
geometry implicates a large separation of the d x 2 −y 2 orbital from the rema<strong>in</strong><strong>in</strong>g<br />
d orbitals, which is beneficial if only those are filled, <strong>in</strong> particular if the ligand field is<br />
strong. Consequently, for metal ions with more than 4 d electrons and a square planar<br />
ligand geometry low-sp<strong>in</strong> configurations are preferred and compounds with high-sp<strong>in</strong><br />
configuration are rare.<br />
Recently Klüfers [1] et al. and Doerrer [2] et al. reported the first molecular compounds<br />
conta<strong>in</strong><strong>in</strong>g high-sp<strong>in</strong>, square planar FeO4 units which are not coord<strong>in</strong>ated by<br />
a macrocyclic ligand and discussed the prerequisites for this unusual structural motif.<br />
In our work, we set out employ<strong>in</strong>g the known tripodal organotrisilanol LH3 [3] as a<br />
ligand precursor which was reacted with iron(II)-triflate after deprotonation of the<br />
Si-OH groups with sodium methanolate. The result<strong>in</strong>g product conta<strong>in</strong>s two Fe II<br />
centers <strong>in</strong> square planar coord<strong>in</strong>ation spheres spanned by two trisiloxane ligands. The<br />
rema<strong>in</strong><strong>in</strong>g two negative charges are compensated by two sodium ions (additionally<br />
b<strong>in</strong>d<strong>in</strong>g Et2O co-ligands). [4] This compound extends the sparse knowledge <strong>in</strong> this<br />
field with regard to molecular chemistry to d<strong>in</strong>uclear compounds, to 6-membered<br />
chelate r<strong>in</strong>gs and also to silanolate ligands; it thus approaches the situation <strong>in</strong> the<br />
natural iron silicate Gillespite [5] or <strong>in</strong> certa<strong>in</strong> ceramics [6] where also square planar<br />
FeO4 units have been found. Overall for the first time edge-shar<strong>in</strong>g of FeO4 units has<br />
been observed.<br />
[1]<br />
X. Wurzenberger, H. Piotrowski, P. Klüfers, Angew. Chem. Int. Ed. 2011, 50, 4974-4978.<br />
[2]<br />
S. A. Cantalupo, S. R. Fiedler, M. P. Shores, A. L. Rhe<strong>in</strong>gold, L. H. Doerrer, Angew. Chem.<br />
Int. Ed. 2012, 51, 1000-1005.<br />
[3]<br />
M. Veith, A. Rammo, O. Schütt, V. Huch, Z. Anorg. Allg. Chem. 2010, 636, 1212-1221.<br />
[4]<br />
D. P<strong>in</strong>kert, S. Demeshko, F. Schax, B. Braun, F. Meyer, C. Limberg, Angew. Chem. Int. Ed.<br />
<strong>2013</strong>, accepted.<br />
[5]<br />
A. Pabst, Am. M<strong>in</strong>eral. 1943, 28, 372–390.<br />
[6]<br />
Y. Tsujimoto, C. Tassel, N. Hayashi, T. Watanabe, H. Kageyama, K. Yoshimura, M. Takano,<br />
M. Ceretti, C. Ritter, W. Paulus, Nature 2007, 450, 1062-1065.<br />
Poster 240 Saturday 9:00 - 11:30 297
Alternative synthesis of surfactant KLE by 1,3-cycloaddition<br />
reaction<br />
Monica Violeta Cîrcu, Frank Ala<strong>in</strong> Nüesch, Dor<strong>in</strong>a Maria Opriş<br />
Functional polymers – EMPA – Ueberlandstrasse 129 – Dubendorf – SUI<br />
monica.circu@empa.ch<br />
KLE [poly(ethylene-co-butylene)-block-poly(ethylene oxide)] is an ideal surfactant for<br />
stabilization of monomer nanodroplets <strong>in</strong> <strong>in</strong>verse m<strong>in</strong>iemulsions and is commonly synthesized<br />
us<strong>in</strong>g Kraton liquid [polyethylene-co-butylene (PEB)] as macro<strong>in</strong>itiator <strong>in</strong><br />
ethylene oxide polymerization. [1] The disadvantage of this approach is that ethylene<br />
oxide is gaseous, therefor small scale experiments are not convenient to be implemented.<br />
We propose here an alternative route to synthesize KLE avoid<strong>in</strong>g use of gaseous<br />
ethylene oxide (Scheme 1). In the first step Kraton liquid (A), which represents the<br />
lipophilic part of the aimed surfactant C, was esterified with 4-pentynoic acid by us<strong>in</strong>g<br />
active ester chemistry. The hydrophilic part, B, of this surfactant was obta<strong>in</strong>ed by<br />
us<strong>in</strong>g commercial hydroxyl end functionalized polyethylene oxide (Mw = 2000 g/mol<br />
and Mw = 5000 g/mol). [2] The two build<strong>in</strong>g blocks A and B were covalently coupled<br />
together by so-called “click” chemistry.<br />
Scheme 1. Retrosynthetic scheme for obta<strong>in</strong><strong>in</strong>g KLE<br />
[1] A. Thomas, H. Schlaad, B. Smarsly, M. Antonietti, Langmuir 2003, 19, 4455-4459.<br />
[2] J. A. Opsteen, J. C. M. van Hest, Chem. Commun. 2005, 57-59.<br />
298 Saturday 9:00 - 11:30 Poster 241
Synthesis and Electrochemical Characterization of Cp*Ir<br />
Complexes Bear<strong>in</strong>g an Unsymmetrically Substituted<br />
Bipyrid<strong>in</strong>e Ligand<br />
Fanni Sypaseuth, Christoph Tzschucke<br />
Institut für Chemie und Biochemie - Organische Chemie – Freie Universität Berl<strong>in</strong> –<br />
Takustr. 3 14195 Berl<strong>in</strong> – Berl<strong>in</strong> – GER<br />
fannidaruny@gmail.com<br />
Bipyrid<strong>in</strong>es have been used as chelat<strong>in</strong>g ligands for a wide range of metal ions <strong>in</strong><br />
numerous different applications. [1] Synthesis and catalytic activity of Cp* iridium<br />
bipyrid<strong>in</strong>e complexes have been studied <strong>in</strong> the context of different reactions such<br />
as transfer hydrogenation of ketones and dehydrogenative oxidation of alcohols. [2]<br />
However, the <strong>in</strong>fluence of unsymmetrical substitution patterns on the 2-,2’-bipyrid<strong>in</strong>e<br />
ligand has not been described. We previously developed the synthesis of unsymmetrically<br />
substituted bipyrid<strong>in</strong>es by palladium catalyzed direct arylation of pyrid<strong>in</strong>e<br />
N -oxides. [3] These bipyrid<strong>in</strong>es were employed as ligands <strong>in</strong> the preparation of<br />
[Cp*Ir(bpy)Cl]Cl complexes. The redox behaviour of these complexes was characterized<br />
by cyclic voltammetry. Initial results on their catalytic activity will be presented.<br />
[1] C. Kaes, A. Katz, M. W. Hosse<strong>in</strong>i, Chemical reviews 2000, 100, 3553.<br />
[2] a) S. Ogo, N. Makihara, Y. Kaneko, Y. Watanabe, Organometallics 2001, 20, 4903; b) T.<br />
Abura, S. Ogo, Y. Watanabe, S. Fukuzumi, Journal of the American Chemical Society 2003,<br />
125, 4149; c) Y. Himeda, N. Onozawa-Komatsuzaki, S. Miyazawa, H. Sugihara, T. Hirose, K.<br />
Kasuga, Chemistry 2008, 14, 11076; d) R. Kawahara, K. Fujita, R. Yamaguchi, Journal of the<br />
American Chemical Society 2012, 134, 3643; e) R. Kawahara, K. Fujita, R. Yamaguchi, Angew.<br />
Chem. Int. Ed. 2012, 51, 12790.<br />
[3] S. Duric, C. C. Tzschucke, Organic Letters 2011, 13, 2310.<br />
Poster 242 Saturday 9:00 - 11:30 299
Synthesis of Oligomeric Lign<strong>in</strong>-Analogs<br />
Ramona Pirwerdjan, Tillmann Kle<strong>in</strong>e, Carsten Bolm<br />
Organische Chemie – RWTH Aachen – Landoltweg 1 – Aachen – GER<br />
ramona.pirwerdjan@rwth-aachen.de<br />
In the last decades the valorization of lignocellulosic biomass has become a field of<br />
<strong>in</strong>creased <strong>in</strong>terest due to its relevance as a potential feedstock for fuels, chemicals and<br />
energy. [1] Lign<strong>in</strong>-valorization, <strong>in</strong> contrast to cellulose and hemicelluloses, however is<br />
still <strong>in</strong> an <strong>in</strong>itial phase. [2,3] Because of its great structural diversity, analyses of this<br />
amorphous biopolymer and its reaction products rema<strong>in</strong> rather challeng<strong>in</strong>g. For this<br />
reason, model compounds that mimic the properties of native lign<strong>in</strong> are of prime <strong>in</strong>terest,<br />
<strong>in</strong> order to make the studies on the lign<strong>in</strong> cleavage easier and comprehensible<br />
on a molecular level. [4] In this context, substrates conta<strong>in</strong><strong>in</strong>g β-O-4 l<strong>in</strong>kages are particularly<br />
relevant, as those bonds are most abundant <strong>in</strong> lign<strong>in</strong> (30-50%, depend<strong>in</strong>g on<br />
the wood type). [2,5]<br />
Recently, we described a diastereoselective preparation of dimeric β-O-4 dilignol<br />
model compounds. [5] In 2005 and 2008, Kishimoto and coworkers developed synthetic<br />
routes for the preparation of polymeric β-O-4 mono- and dilignol model compounds. [6]<br />
Based on these previous f<strong>in</strong>d<strong>in</strong>gs, we now present a protocol which allows the synthesis<br />
of oligomeric lign<strong>in</strong> analogs. The cha<strong>in</strong> length of these lign<strong>in</strong> related mono- and<br />
dilignols could be controlled to bear two to four β-O-4 l<strong>in</strong>kages.<br />
[1]<br />
a) F. Cherub<strong>in</strong>i, Energy Convers. Manage. 2010, 51, 1412-1421; b) J. C. Serrano-Ruiz, R.<br />
Luque, A. Sepúlveda-Escribano, Chem. Soc. Rev. 2011, 40, 5266-5281.<br />
[2]<br />
J. Zakzeski, P. C. Bruijn<strong>in</strong>cx, A. L. Jongerius, B. M. Weckhuysen, Chem.<br />
3552-3599.<br />
Rev. 2010, 110,<br />
[3]<br />
a) Y.-T. Cheng, J. Jae, J. Shi, W. Fan, G. W. Huber, Angew. Chem. Int. Ed. 2012, 51,<br />
1387-1390; b) G. W. Huber, A. Corma, Angew. Chem. Int. Ed. 2007, 46, 7184-7201; c) J. B.<br />
B<strong>in</strong>der, R. T. Ra<strong>in</strong>es, J. Am. Chem. Soc. 2009, 131, 1979-1985; d) A. Corma, S. Iborra, A.<br />
Velty, Chem. Rev. 2007, 107, 2411-2502.<br />
[4]<br />
For a recent degradation study, see: T. Kle<strong>in</strong>e, J. Buendia, C. Bolm, Green Chem. <strong>2013</strong>, 15,<br />
160-166.<br />
[5]<br />
J. Buendia, J. Mottweiler, C. Bolm, Chem. Eur. J. 2011, 17, 13877-13882.<br />
[6]<br />
a) T. Kishimoto, Y. Uraki, M. Ubukata, Org. Biomol. Chem. 2005, 3, 1067-1073; b) T.<br />
Kishimoto, Y. Uraki, M. Ubukata, Org. Biomol. Chem. 2006, 4, 1343-1347; c) T. Kishimoto,<br />
Y. Uraki, M. Ubukata, Org. Biomol. Chem. 2008, 6, 2982-2987.<br />
300 Saturday 9:00 - 11:30 Poster 243
Efficient [5+1]-Synthesis of 4-Qu<strong>in</strong>olones by Dom<strong>in</strong>o<br />
Am<strong>in</strong>ation / Conjugate Addition Reactions of<br />
1-(2-Fluorophenyl)prop-2-yn-1-ones with Am<strong>in</strong>es<br />
Satenik Mkrtchyan, Viktor Iaroshenko, Aleksander Vill<strong>in</strong>ger<br />
Faculty of Chemistry – University Rostock – Albert E<strong>in</strong>ste<strong>in</strong> str. 3a, 18059 Rostock –<br />
Rostock – GER<br />
satenikmk@yahoo.co.uk<br />
Functionalized qu<strong>in</strong>ol<strong>in</strong>es are attractive compounds for drug discovery s<strong>in</strong>ce many<br />
of them have been shown to exhibit excellent biological activities. Moreover, a<br />
very special position among all drugs conta<strong>in</strong><strong>in</strong>g a qu<strong>in</strong>ol<strong>in</strong>e core is occupied by the<br />
fluoroqu<strong>in</strong>olones. [1] Recent advances <strong>in</strong> the synthesis of pyrid<strong>in</strong>es, qu<strong>in</strong>ol<strong>in</strong>es and fused<br />
pyrid<strong>in</strong>es by [5+1]-cyclization strategies <strong>in</strong>clude several efficient methods for the construct<strong>in</strong>g<br />
of such heterocyclic scaffolds. [2] Hav<strong>in</strong>g this strategy <strong>in</strong> m<strong>in</strong>d Iaroshenko’s<br />
laboratory exanimated the cyclisation reaction of fluor<strong>in</strong>ated phenylpropyn-1-one 1<br />
with different am<strong>in</strong>es 2. Compounds 1 are available from commercially available<br />
acetylenes and fluor<strong>in</strong>ated benzoylchlorides by Sonogashira reaction. Us<strong>in</strong>g Li2CO3<br />
as base <strong>in</strong> DMA, a series of tandem [5+1]-cyclizations of am<strong>in</strong>es 2 with 1 was conducted,<br />
result<strong>in</strong>g the 4-qu<strong>in</strong>olones 3 with 73-89 % yields (Figure 1). [3] When acetylenes<br />
1 conta<strong>in</strong><strong>in</strong>g a second fluor<strong>in</strong>e atom <strong>in</strong> the molecule were <strong>in</strong>vestigated, we have observed<br />
an <strong>in</strong>terest<strong>in</strong>g phenomenon. In the case when the second fluor<strong>in</strong>e was located<br />
<strong>in</strong> ortho- or para- position to the carbonyl group it was substituted by an am<strong>in</strong>e to<br />
give the am<strong>in</strong>o-substituted qu<strong>in</strong>olones 4. However, the substrates 1 with the second<br />
fluor<strong>in</strong>e <strong>in</strong> meta-position were not prone to react with am<strong>in</strong>es and <strong>in</strong> this case the<br />
reaction resulted <strong>in</strong> 4-qu<strong>in</strong>olones 3 conta<strong>in</strong><strong>in</strong>g the fluor<strong>in</strong>e group <strong>in</strong> the position-6.<br />
Nevertheless, dur<strong>in</strong>g this <strong>in</strong>vestigation we have encountered with the fact that the<br />
double-substitution occurred only with aliphatic am<strong>in</strong>es. The application of anil<strong>in</strong>es<br />
under our standard reaction conditions did not result <strong>in</strong> substitution of the second<br />
fluoride group. However, this result provided us the possibility to use some products<br />
3 to substitute the second activated fluor<strong>in</strong>e atom by aliphatic am<strong>in</strong>es to deliver different<br />
qu<strong>in</strong>olones 4. Moreover, the mechanism of this transformation was <strong>in</strong>vestigated<br />
and a number of <strong>in</strong>termediates was isolated and identified. [3]<br />
Figure 1. Synthesis of functionated 4-qu<strong>in</strong>ol<strong>in</strong>es<br />
[1]<br />
R. B. Silverman, The organic chemistry of drug design, and drug action (Second Edition),<br />
Elsevier Academic Press, 2004, 617, ISBN 0-12-643732-7.<br />
[2]<br />
a) D. Craig, G. D. Henry, Tetrahedron<br />
Lett. 2005, 46, 2559-2562; b) T. Harschneck, S. F. Kirsch, J. Org. Chem. 2011, 76,<br />
2145-2156.<br />
[3]<br />
V. O. Iaroshenko, S. Mkrtchyan, A. Vill<strong>in</strong>ger, Synthesis <strong>2013</strong>, DOI: 10.1055/s-<br />
0032-1316826.<br />
Poster 244 Saturday 9:00 - 11:30 301
Alternative method for blood alcohol determ<strong>in</strong>ation by<br />
proton -NMR – Development and validation<br />
El<strong>in</strong>a Zailer, Bernd Diehl<br />
Spectral Service AG – Spectral Service AG – Emil-Hoffmann-Straße 33 – 50996 Köln –<br />
GER<br />
el<strong>in</strong>a.zailer@googlemail.com<br />
Aims: The 50 - year - old methods of analyz<strong>in</strong>g blood alcohol (BAC) like headspace -<br />
gaschromatography and the enzymatic ADH can be supplemented by the alternative<br />
method of NMR spectroscopy us<strong>in</strong>g only one capillary blood drop with an equivalence<br />
of 20 µL. The aims of this method are the keep<strong>in</strong>g of the demands of the Guidel<strong>in</strong>es<br />
to determ<strong>in</strong>e the BAC for forensic purposes and the <strong>in</strong>troduction of a fast, precise<br />
and non - destructive BAC analysis with a m<strong>in</strong>imum volume of capillary full blood.<br />
Methods: The NMR method <strong>in</strong>volves the use of a solvent of maximum 1 mL D2O<br />
spiked with TMSP, and an <strong>in</strong>ternal standard <strong>in</strong> form of 20 µL DMS. The measurement<br />
occurs with the NMR spectroscopy (600 MHz) with fixed parameters.<br />
Results and Discussion: The volume of 20 µL capillary full blood is enough for the determ<strong>in</strong>ation<br />
of the BAC with the same accuracy like the “old” methods. The stability<br />
at different storage places, the repeatability, reproducibility, l<strong>in</strong>earity and accuracy<br />
confirmed by prepar<strong>in</strong>g calibration series with reference serum and whole blood are<br />
analyzed. Factors like personnel, chemicals, temperature, light and air humidity do<br />
not show any effects on the BAC results. A scientific dr<strong>in</strong>k<strong>in</strong>g test proves that <strong>in</strong>travenous<br />
and capillary blood shows the same BAC level.<br />
Conclusion: The dr<strong>in</strong>k<strong>in</strong>g test proves that a s<strong>in</strong>gle capillary blood drop is sufficient for<br />
a BAC determ<strong>in</strong>ation. A comparison of the BAC results of the forensic jurisprudence,<br />
measured by GC - HS and ADH, and of the alternative NMR – method demonstrates<br />
the accuracy of this method with real blood samples. A forensic usability with the<br />
specified limits can be met.<br />
Key words: blood, alcohol, BAC, NMR, spectroscopy<br />
302 Saturday 9:00 - 11:30 Poster 245
Explor<strong>in</strong>g what’s underneath -<br />
Sub-Surface AFM to locate Nanoparticles with<strong>in</strong> Polymer<br />
Soft Matter<br />
Bob-Dan Lechner ∗ , Eike-Christian Spitzner † , Adekunle Olubummo † , Matthias Schulz ‡ ,<br />
Wolfgang H. B<strong>in</strong>der ‡ , Robert Magerle † , Alfred Blume ∗<br />
∗ Physikalische Chemie – Mart<strong>in</strong>-Luther-Universität Halle-Wittenberg –<br />
Von-Danckelmann-Platz 4 – Halle an der Saale – GER<br />
† Chemische Physik – Technische Universität Chemniz – Reichenha<strong>in</strong>er Str. 70 –<br />
Chemnitz – GER<br />
‡ Makromolekulare Chemie – Mart<strong>in</strong>-Luther-Universität Halle-Wittenberg –<br />
Von-Danckelmann-Platz 4 – Halle an der Saale – GER<br />
bob-dan.lechner@chemie.uni-halle.de<br />
The <strong>in</strong>teractions of mixed systems of lipids and surface modified nanoparticles have<br />
<strong>in</strong>creased researchers <strong>in</strong>terest <strong>in</strong> the past decade. Modified nanoparticles are a valuable<br />
target system for a plenty of biological, biomedical and nano-technological issues<br />
requir<strong>in</strong>g the controllability and tunability of their mix<strong>in</strong>g abilities with<strong>in</strong> lipid membranes<br />
with focus on adsorption, b<strong>in</strong>d<strong>in</strong>g, dispersion and localization. [1] A powerful<br />
mean to <strong>in</strong>vestigate such nanoscopic systems are amplitude modulation atomic force<br />
microscopy (AM-AFM) techniques enabl<strong>in</strong>g visualization of nanostructures and characterization<br />
of key local mechanical properties, simultaneously. By <strong>in</strong>dent<strong>in</strong>g the soft<br />
material of the sample with the oscillat<strong>in</strong>g AFM tip a depth resolved map of mechanical<br />
properties can by ga<strong>in</strong>ed. Hard tissues like non-compressive CdSe nanoparticles<br />
can thus be visualized underneath the respective lipid/polymer surface. [2]<br />
The aim of this work is to ga<strong>in</strong> <strong>in</strong>sight <strong>in</strong> <strong>in</strong>teraction pr<strong>in</strong>ciples of CdSe nanoparticles<br />
with mixed lipid/polymer monolayers at the air water <strong>in</strong>terface or transferred films<br />
at solid Si substrates via AM-AFM. We focus on the organization and localization of<br />
the nanoparticles with<strong>in</strong> the monolayer thereby demonstrat<strong>in</strong>g that the nanoparticles<br />
surface modification plays a crucial role for the respective nanoparticle location with<strong>in</strong><br />
or at the <strong>in</strong>terface.<br />
Fig. 1. Location of functionalized CdSe nanoparticles with<strong>in</strong> mixed DPPC/<br />
PIB87-b-PEO17 monolayers; <strong>in</strong>teraction cartoon for hydrophobicly modified<br />
nanoparticles (left), AFM scan of a transferred layer at Si substrate (mid), localization of<br />
CdSe nanoparticle clusters with<strong>in</strong> polymer columns measured by AM-AFM (right).<br />
[1] a) A. Olubummo, M. Schulz, B.-D. Lechner, P. Scholtysek, K. Bacia, A. Blume, J. Kressler, W.<br />
H. B<strong>in</strong>der, ACS Nano 2012, 6 (10), 8713-8727; b) M. Schulz, D. Glatte, A. Meister, P. Scholtysek,<br />
A. Kerth, A. Blume, K. Bacia, W. H. B<strong>in</strong>der, Soft Matter 2011, 7, 8100.<br />
[1] E.-C. Spitzner, C. Riesch, R. Magerle, ASC Nano 2011, 5, 1, 315.<br />
Poster 246 Saturday 9:00 - 11:30 303
Composition and Chemistry of a Pd-Ni-Co alloy studied by<br />
HAXPES<br />
Julius Kühn<br />
6.8 Surface Analysis and Interfacial Chemistry – BAM – Unter den Eichen 44-46 –<br />
Berl<strong>in</strong> – GER<br />
julius.kuehn@bam.de<br />
The surface near region is very important for catalytic processes. Compositional<br />
changes, e.g. segregation of alloy constituents <strong>in</strong> states before and after hydrogen sulfide<br />
exposure was <strong>in</strong>vestigated by non-destructive chemical HAXPES depth profil<strong>in</strong>g.<br />
The HAXPES data are completed by results of AES provid<strong>in</strong>g data characteristic of<br />
the uppermost surface and EDX data characteristic of the bulk of the alloys.<br />
304 Saturday 9:00 - 11:30 Poster 247
Characteriz<strong>in</strong>g electrostatic <strong>in</strong>teractions for drug design<br />
purposes<br />
Marta Kulik ∗ , Anna Maria Goral † , Paul<strong>in</strong>a Maria Dom<strong>in</strong>iak † , Joanna Trylska ∗<br />
∗ Centre of New Technologies – University of Warsaw – Żwirki i Wigury 93 – Warsaw –<br />
POL<br />
† Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL<br />
m.kulik@cent.uw.edu.pl<br />
Accurate tools to establish recognition patterns between small ligands and their receptor<br />
biomolecules are needed <strong>in</strong> order to improve drug design process. Electrostatic<br />
<strong>in</strong>teractions are often crucial <strong>in</strong> recognition of ligands b<strong>in</strong>d<strong>in</strong>g to nucleic acids (for<br />
example, <strong>in</strong> the case of am<strong>in</strong>oglycoside antibiotics target<strong>in</strong>g various RNA motifs). Reconstruct<strong>in</strong>g<br />
the electron density with the s<strong>in</strong>gle po<strong>in</strong>t charge models, as <strong>in</strong> classical<br />
molecular mechanics potential energy functions, lacks the accuracy of the multi-pole<br />
expansion approaches. The methodology that accounts for other than s<strong>in</strong>gle-po<strong>in</strong>t<br />
charge terms <strong>in</strong> the description of electrostatics was applied.<br />
The idea of University at Buffalo Databank (UBDB) [1] is based on the transferability<br />
of electron density parameters between atoms that are <strong>in</strong> chemically equivalent<br />
vic<strong>in</strong>ities. The UBDB parameters allow reconstruct<strong>in</strong>g the electron density from the<br />
experimental structural data even for large systems. The UBDB and the Exact Potential<br />
Multipole Method (EPMM) developed by Volkov [2] were applied to estimate<br />
the electrostatic energy of <strong>in</strong>teractions and its per-r<strong>in</strong>g contributions between RNA<br />
and am<strong>in</strong>oglycosides as the electrostatic effects dom<strong>in</strong>ate the b<strong>in</strong>d<strong>in</strong>g process. [3]<br />
Understand<strong>in</strong>g the amplitude of electrostatic <strong>in</strong>teractions between am<strong>in</strong>oglycosides<br />
and their ribosomal RNA target is necessary to <strong>in</strong>troduce am<strong>in</strong>oglycoside modifications<br />
that would enhance their b<strong>in</strong>d<strong>in</strong>g.<br />
[1] K.N. Jarzembska, P.M. Dom<strong>in</strong>iak, Acta Cryst. 2012, A68, 139-147.<br />
[2] A. Volkov, T. Koritsanszky, P. Coppens, Chem. Phys. Lett. 2004, 391, 170-175.<br />
[3] H. Wang, Y. Tor, Angew. Chem. 1998, 37, 109-111.<br />
The authors acknowledge support from the Foundation for Polish Science Team project (TEAM/2009-<br />
3/8) co-f<strong>in</strong>anced by European Regional Development Fund operated with<strong>in</strong> Innovative Economy<br />
Operational Programme.<br />
Poster 248 Saturday 9:00 - 11:30 305
Coord<strong>in</strong>ation Behavior and Spectroscopic Studies of<br />
Biologically Active Metal Complexes of Triterpene Acid.<br />
Khadija Shahid<br />
Riphah Institute of Pharmaceutical Sciences –<br />
Riphah International University, Islamabad – 7th Avenue, G-7/4 – Islamabad – PAK<br />
khadijajee@yahoo.com<br />
New metal complexes of triterpene acid were synthesized <strong>in</strong> stoichiometric ratio <strong>in</strong><br />
anhydrous toluene under the reflux yield the organometallic complexes [1] with general<br />
formula R4-nMLn(R= Me, n-Bu, Ph, and n= 2, 3 where M= Zn, Fe, Sn, Cu, Sb). All<br />
the complexes have been characterized by various spectroscopic methods (IR,1H,13C<br />
NMR) and atomic absorption spectroscopy. These compounds have also been screened<br />
for biological activities [2] to establish their significance.<br />
[1] (a) K. Shahid, S. Ali, S. Shahzadi, J. Coord. Chem, 2009, 62 (17), 2919-2926; (b) K. Shahid,<br />
S. Shahzadi, J. Serb. Chem. Soc. 2009, 74 (2), 141-154.<br />
[2] A. Rahman, M.I. Choudhary, W.J. Thomsen, Bioassay Techniques for Drug Development,<br />
Hardward Academic Press, Amsterdam 2001.<br />
Key words: Triterpene acid, Biological activity and Spectroscopy.<br />
306 Saturday 9:00 - 11:30 Poster 249
Tun<strong>in</strong>g Selectivity of Switchable Multicomponent<br />
Heterocyclizations <strong>in</strong>volv<strong>in</strong>g am<strong>in</strong>oazoles, salicylaldehydes<br />
and pyruvic acids<br />
Maryna Murlyk<strong>in</strong>a, Yana Sakhno, Valent<strong>in</strong> Chebanov<br />
Department of Heterocyclic Compounds Chemistry –<br />
State Scientific Institution “Institute for S<strong>in</strong>gle Crystals” NAS of Ukra<strong>in</strong>e –<br />
Len<strong>in</strong> ave. / 60 – Kharkiv – UKR<br />
mar<strong>in</strong>avladimirmur@gmail.com<br />
The <strong>in</strong>tense <strong>in</strong>terest <strong>in</strong> multicomponent heterocyclizations of am<strong>in</strong>oazoles, aldehydes<br />
and pyruvic acids is connected with the possibility of realization of several different reaction<br />
pathways depend<strong>in</strong>g on the reagents’ structure, type of solvent and catalyst. [1]<br />
It was also shown that the <strong>in</strong>troduction of OH-group <strong>in</strong> ortho-position of the aldehyde<br />
allows yield<strong>in</strong>g among several types of f<strong>in</strong>al compounds also oxygen-bridged<br />
structures. [2-4]<br />
The present work is dedicated to the tun<strong>in</strong>g selectivity of multicomponent reactions<br />
of am<strong>in</strong>oazoles, salicylaldehydes and pyruvic acid derivatives.<br />
It was shown that the control the direction of these three-component reactions can<br />
be carried out by vary<strong>in</strong>g the temperature condition with the help of non-classical<br />
activation methods (microwave and ultrasonic irradiation). It should be noted, that<br />
<strong>in</strong> comparison with ord<strong>in</strong>ary mechanical stirr<strong>in</strong>g, ultrasonication doesn’t <strong>in</strong>fluence on<br />
the reaction mechanism and direction and its effect comes to decreas<strong>in</strong>g of the reaction<br />
time for account of the effective mass transfer and homogenization.<br />
Scheme 1<br />
[1] V. A. Chebanov, K. A. Gura, S. M. Desenko, Top. Heterocycl. Chem. 2010, 23, 41-84.<br />
[2] Ya. I. Sakhno, S. V. Shishk<strong>in</strong>a, O. V. Shishk<strong>in</strong> et al., Mol. Divers. 2010, 14, 523-531.<br />
[3] N. Yu. Gorobets, Y. V. Sedash, K. S. Ostras et al., Tetrahedron Lett. 2010, 51, 2095-2098.<br />
[4] J. Svetlik, V. Kettmann, Tetrahedron Lett. 2011, 52, 1062-1066.<br />
Poster 250 Saturday 9:00 - 11:30 307
α, β, and ω<br />
Marko Popovic<br />
Faculty of chemistry, University of Belgrade – University of Belgrade – St.Trg 12 –<br />
Belgrade – SER<br />
popovic.pasa@gmail.com<br />
The proposed thermodynamic model of an biological system satisfies the follow<strong>in</strong>g<br />
caracteristics of a liv<strong>in</strong>g organism: the exchange of substance and energy with its<br />
surround<strong>in</strong>gs (open system); the property of growth, so that <strong>in</strong>put of matter <strong>in</strong>to<br />
the system is greater than the output; the membrane is semipermeable; the analyzed<br />
system requires energy and matter from outside for its growth; chemical reactions are<br />
go<strong>in</strong>g on <strong>in</strong> the system and complex structures are formed; it cont<strong>in</strong>uously changes its<br />
state; dur<strong>in</strong>g the change of state errors happen and accumulate over time; there is a<br />
mechanism which repairs the errors but it isn’t perfect; the liv<strong>in</strong>g system has two (or<br />
more) subunits; the subunits are differentiated and each has its role (which represents<br />
the differentiation of cells <strong>in</strong> complex organisms); the function of α subsystem is<br />
dependent on the function of β subsystem (because the catalyst DEF can be produced<br />
only <strong>in</strong> a specialized β cell). The subsystems α and β function as one entity αβ,<br />
surrounded by ω. Based on Schrod<strong>in</strong>ger’s [1] assumption supported by Ho [2] and<br />
Hansen [3] , as well as on the assumption of von Bertalanffy [4] that liv<strong>in</strong>g systems act<br />
as open thermodynamic systems, and on Prigog<strong>in</strong>e’s work [5,6] , the ag<strong>in</strong>g of liv<strong>in</strong>g<br />
systems is described. Ag<strong>in</strong>g of biological systems is directly related to the processes<br />
of life, and is described by thermodynamic equation which shows two tendencies: one<br />
to <strong>in</strong>crease the entropy and the other is an act of the organized biological mach<strong>in</strong>e<br />
to decrease the entropy. Ag<strong>in</strong>g is a consequence of imbalance between these two<br />
tendencies. It’s also concluded that because of the property of growth the <strong>in</strong>put<br />
and output of substance aren’t equal, because a part of the substance rema<strong>in</strong>s <strong>in</strong><br />
the system, as a consequence of that the system is <strong>in</strong> a quasi-steady state. This<br />
means that pressure, temperature, molarity and mol fractions are constant; while the<br />
quantity of substance and entropy of the system are variable.<br />
308 Saturday 9:00 - 11:30 Poster 251
Stereoselective modifications of salen-like ligands - chiral<br />
chelates and macrocycles<br />
Paweł Tokarz ∗ , Jarosław Lewkowski ∗ , Anna Krzyczmonik ∗ , Katarzyna Ślepokura † ,<br />
Tadeusz Lis †<br />
∗ Department of Organic Chemistry – University of Łódź – Ul. Tamka 12 – 91-403 Łódź –<br />
POL<br />
† Department of Chemistry – University of Wroclaw – Ul. F. Joliot-Curie 14 –<br />
Wrocław – POL<br />
paweltokarz.chem@gmail.com<br />
Compounds derived from 1,2 -diam<strong>in</strong>ocyclohexane (DACH ) play a crucial role <strong>in</strong> the<br />
modern chemistry of chiral synthesis. One of the most spectacular substances, derived<br />
from this simple am<strong>in</strong>e, are macrocyclic molecules that can be obta<strong>in</strong>ed by so-called<br />
cyclocondensation. [1] Such macrocycles have found numerous applications, only to<br />
mention a few - the asymmetric catalysis or the chiral recognition of biologically<br />
active agents. [2,3]<br />
Until now little is known about modified structures of DACH -based macromolecules,<br />
<strong>in</strong> particular, those conta<strong>in</strong><strong>in</strong>g lipophilic substituents. We have decided to provide<br />
a simple and stereoselective method of the <strong>in</strong>troduction of long carbon cha<strong>in</strong>s <strong>in</strong>to<br />
the macrocyclic moiety. We have used dialkyl phosphites as cha<strong>in</strong> carriers. In this<br />
way it was possible for us to <strong>in</strong>troduce two cha<strong>in</strong>s per one azometh<strong>in</strong>e bond. We<br />
developed a novel synthetic protocol apply<strong>in</strong>g use of sodium hydride which gave us<br />
diastereoisomeric ratios as high as 100:1:1 for acyclic model systems. In case of the<br />
large, cyclic systems the problem becomes more complex due to a number of possible<br />
isomeric products.<br />
Synthesis of lipophilically modified DACH -based macrocycles<br />
[1] N. E. Borisova, M. D. Reshetova, Y. A. Ustynyuk, Chem. Rev. 2007, 107, 46-79.<br />
[2] G. Zhou, Y. Cheng, L. Wang, X. J<strong>in</strong>g, F. Wang Macromolecules 2005, 38, 2148.<br />
[3] R. D. Hancock Pure Appl. Chem. 1986, 58, 1445-1452.<br />
Poster 252 Saturday 9:00 - 11:30 309
Dihydrogen-bonded complexes as active <strong>in</strong>termediates at<br />
acid mediated transformations of transition metal<br />
tetrahydroborates<br />
Igor E. Golub ∗ , Oleg A. Filippov † , Viktor P. Dyadchenko ∗ , Elena S. Shub<strong>in</strong>a †<br />
∗ Chemistry Department – M.V. Lomonosov Moscow State University –<br />
Len<strong>in</strong>skiye Gory 1-3 – Moscow – RUS<br />
† A.N. Nesmeyanov Institute of Organoelement Compounds (INEOS RAS) –<br />
Vavilov Street 28 – Moscow – RUS<br />
seraph347@gmail.com<br />
The dihydrogen-bonded (DHB) complexes are known to form at the first step of<br />
proton-transfer reaction. These complexes previously <strong>in</strong>vestigated for different types<br />
of metal hydrides and hydrides of ma<strong>in</strong> group elements, but for metal tetrahydroborates<br />
study of <strong>in</strong>fluence <strong>in</strong>termolecular <strong>in</strong>teractions on chemical properties of such<br />
compounds.<br />
The mechanism of acid mediated transformation of transition metal tetrahydroborates<br />
was thoroughly studied by means of comb<strong>in</strong>ation of experimental (IR and NMR,<br />
190-300 K) and computational (DFT/M06) methods. Formation of DHB complexes<br />
as the first reaction step and their thermodynamic characteristic was established<br />
experimentally. By means of theoretical <strong>in</strong>vestigation possible coord<strong>in</strong>ation modes of<br />
DHB complexes were revealed. Despite of existence a large number of DHB different<br />
types (mono-, bi- and trifurcate complexes) and competition between these forms,<br />
only one type of DHB bifurkate complex with participation of term<strong>in</strong>al and bridge<br />
hydrides of tetrahydroborate-group is active <strong>in</strong>termediate of the reactions.<br />
Acknowledgment: This work was supported by Russian Foundation for Basic Research<br />
(project No 13-03-00604).<br />
310 Saturday 9:00 - 11:30 Poster 253
<strong>JungChemikerForum</strong> Aachen<br />
Jeanne Fronert, Peter Becker, Julian Kleemann<br />
Institutes of Chemistry – RWTH Aachen University – Landoltweg 1 – Aachen – GER<br />
jeanne.fronert@gmail.com<br />
The JCF Aachen is a group of 18 active members, who are Bachelor-, Master- or<br />
doctoral students. We meet regularly every four weeks to discuss new projects or<br />
just to meet each other for exchange <strong>in</strong> a casual atmosphere. We organize lectures<br />
that are ma<strong>in</strong>ly addressed to students. Furthermore we realize excursions to chemical<br />
companies. Another special event is our beachvolleyball tournament, that takes place<br />
every summer.<br />
In 2012 the follow<strong>in</strong>g events took place <strong>in</strong> Aachen:<br />
Lecture by Prof. Dr. Klaus Roth – “Vom ersten Bier zum Kater.”:<br />
To the “Tag der Chemie” of the RWTH Aachen University we <strong>in</strong>vited Prof. Dr.<br />
Klaus Roth to give an <strong>in</strong>terest<strong>in</strong>g and enterta<strong>in</strong><strong>in</strong>g lecture related to the <strong>in</strong>teraction<br />
of alcohol with the human body.<br />
Beachvolleyball Tournament:<br />
In July we arranged the annual beachvolleyball tournament with 20 teams and many<br />
spectators. With perfectly sunny weather, music and cold dr<strong>in</strong>ks we had a great<br />
day. After sports we enjoyed a barbecue <strong>in</strong> front of the chemistry department and<br />
decorated the w<strong>in</strong>ners of the tournament.<br />
Excursion to AIXTRON SE:<br />
In August we had the chance to visit AIXTRON SE, which is a lead<strong>in</strong>g provider<br />
of deposition equipment to the semiconductor <strong>in</strong>dustry and has been established <strong>in</strong><br />
Aachen. We listened to <strong>in</strong>terest<strong>in</strong>g presentations and we were given the chance to see<br />
how the deposition equipment is built up.<br />
Our plans for <strong>2013</strong>:<br />
In February a lecture will be held by Prof. Dr. Thomas Loetzbeyer – “Molekulare<br />
Küche - E<strong>in</strong> Experimentalvortrag über Gaudi, Genuss und Lebensfreude.”<br />
In the end of February we are go<strong>in</strong>g to conduct another excursion to LANXESS AG<br />
<strong>in</strong> Cologne.<br />
In March we will pay a visit to the pharmaceutical company Grünenthal GmbH.<br />
Furthermore we organize an experimental lecture <strong>in</strong> the summer term and want to<br />
organize a spr<strong>in</strong>g party afterwards.<br />
Another highlight will be the annual beachvolleyball tournament, that will take place<br />
<strong>in</strong> summer aga<strong>in</strong>.<br />
Poster 254 Saturday 9:00 - 11:30 311
<strong>JungChemikerForum</strong> Gießen<br />
Michael L<strong>in</strong>den ∗ , Rabea Dippel †<br />
∗ Institute of Organic Chemistry – Justus-Liebig-University – He<strong>in</strong>rich-Buff-R<strong>in</strong>g 58 –<br />
Giessen – GER<br />
† Institute of Physical Chemistry – Justus-Liebig-University – He<strong>in</strong>rich-Buff-R<strong>in</strong>g 58 –<br />
Giessen – GER<br />
jcf@chemie.uni-giessen.de<br />
S<strong>in</strong>ce the foundation of the JCF Gießen <strong>in</strong> 2005, the group of members has grown<br />
steadily with about ten of them be<strong>in</strong>g actively engaged. We regularly meet at the<br />
“JCF Stammtisch”, where we plan our events and discuss current topics, problems or<br />
just spend some quality time together.<br />
Lectures:<br />
Each Semester, we have the possibility to <strong>in</strong>vite special guests dur<strong>in</strong>g the ongo<strong>in</strong>g<br />
term of GDCh lectures. We highly appreciate guests who are talk<strong>in</strong>g about uncommon<br />
chemical topics, for example, “Supramolekulare Detektion von Sprengstoffen –<br />
Grundlagen und Anwendungen“ (Prof. Dr. Siegfried R. Waldvogel, Johannes Gutenberg<br />
Universität Ma<strong>in</strong>z); “Das Problem der nuklearen Entsorgung” (Prof. Horst Geckeis,<br />
Institut für Nukleare Entsorgung KIT).<br />
A special lecture was given by Prof. Richard Ernst <strong>in</strong> November 2010. The noble<br />
laureate gave the audience an extraord<strong>in</strong>ary example of <strong>in</strong>terdiscipl<strong>in</strong>ary work <strong>in</strong> his<br />
talk entitled: “Die <strong>in</strong>terkulturelle Passion e<strong>in</strong>es Naturwissenschaftlers: Tibetische<br />
Malkunst, Pigmentanalyse und Wissensvermittlung an tibetische Mönche”.<br />
Theme nights:<br />
Furthermore, we organize theme nights where we take a chemical view at different<br />
topics. For example:<br />
“Themenabend CSI: Chemiker suchen Indizien” Lecture: Dr. H. Wollersen,<br />
Dr. P. Weis<br />
“Berufse<strong>in</strong>stieg für Chemiker” and different lecturers from chemical companies, e. g.,<br />
Evonik, Heraeus, VAA.<br />
Excursions:<br />
So far, we have organized excursions to chemical companies close to Gießen, e. g.,<br />
Merck (Darmstadt), Seidel (Marburg/Fronhausen), ESA (Darmstadt), etc. In the<br />
summer of 2011, we arranged a three-day trip to Leipzig, where we met the JCF<br />
Leipzig and visited BELL and the department of chemistry at the university.<br />
In December 2010, we organized an excursion to BASF Coat<strong>in</strong>gs (Münster) together<br />
with the JCF Münster, followed by a jolly trip to the Christmas market.<br />
Other activities:<br />
In addition, we arrange a number sem<strong>in</strong>ars on different subjects (e.g., presentation<br />
techniques, career entry), and represent the JCF/GDCh at the “Hochschul<strong>in</strong>formationstag”<br />
and the “Studiene<strong>in</strong>führungswoche”.<br />
Together with the association “Vere<strong>in</strong> der Freunde der chem. Institute e.V.” we organize<br />
a regular barbecue to celebrate the end of the summer term.<br />
312 Saturday 9:00 - 11:30 Poster 255
Das JCF Halle<br />
Bob-Dan Lechner, Marlou Keller, Tobias Jost, Ludwig Riedel<br />
<strong>JungChemikerForum</strong> Halle – Mart<strong>in</strong>-Luther-Universität Halle-Wittenberg –<br />
Von-Danckelmann-Platz 4 – Halle (Saale) – GER<br />
jcfHalle@googlemail.com<br />
“Chemie gibt Brot, Wohlstand und Schönheit!”, so der Slogan der chemischen Industrie<br />
der DDR. Insbesondere des Chemiedreieck unserer Region warb damit. Wir haben<br />
uns dieses Motto zum Titel des JCFs gewählt, da auch bei uns derartige Aspekte e<strong>in</strong>e<br />
essentielle Rolle spielen.<br />
Brot: steht für unsere <strong>in</strong>tensiv gepflegte Verb<strong>in</strong>dung zu den hiesigen Lebensmittelchemikern,<br />
die sich <strong>in</strong> der „AG Junge Lebensmittelchemiker“ selbst organisieren, mit<br />
denen wir dann öfter geme<strong>in</strong>same Aktionen durchführen.<br />
Wohlstand: Obgleich man e<strong>in</strong>en solchen den Bewohnern der neuen Bundesländern immer<br />
abschätzig macht, weist das JCF Halle trotzdem selbiges erst kurze Zeit besteht,<br />
e<strong>in</strong>e wahre Fülle an Mitgliedern auf. E<strong>in</strong>e gute Beziehung zum Ortsverbandsvorsitzenden<br />
der GDCh erlaubt uns darüber h<strong>in</strong>aus auch größere Veranstaltungen und<br />
GDCh/JCF Double-features zu erleben.<br />
Schönheit: Nun, was soll man sagen. Schönheit ist e<strong>in</strong> vielberedter Begriff. Man<br />
spricht e<strong>in</strong>erseits von der Schönheit des Rotkohlsaftes, andererseits von der Schönheit<br />
mancher geme<strong>in</strong>samer JCF Abende und natürlich der Schönheit der Frauen unserer<br />
Uni. Nicht umsonst heißt es “Hier bei uns <strong>in</strong> Anhalt-Sachsen, wo die schönen Mädchen<br />
wachsen.“.<br />
http://jcf.chemie.uni-halle.de<br />
Poster 256 Saturday 9:00 - 11:30 313
Index<br />
315
Index<br />
A<br />
Abarca, Belen, 253<br />
Abbasi, Muhammad S. A., 200<br />
Abramczyk, Katarzyna, 119<br />
Abt, Bärbel, 101<br />
Adam, Rosa, 253<br />
Adamczyk, Zbigniew, 90<br />
Adaszyńska, Michal<strong>in</strong>a, 184, 196<br />
Aghatabay, Naz Mohammed, 118<br />
Akhmadull<strong>in</strong>a, Nailya, 210, 260<br />
Albrecht, Ralf, 213<br />
Almazahreh, Laith, 37<br />
Alom, Shamim, 253<br />
Alshakova, Ir<strong>in</strong>a, 187<br />
Altınbaş Özpınar, Gül, 186<br />
Altamura, Emiliano, 168<br />
Altenburg, Horst XXX, 315<br />
Alt<strong>in</strong>bas Ozp<strong>in</strong>ar, Gul<br />
Alt<strong>in</strong>dal, Ahmet, 69, 153<br />
Altun, Altan Alpay<br />
Amakawa, Kazuhiko, 133<br />
Amir, M. D., 118<br />
Andrić, Jelena, 115, 122<br />
Antonschmidt, Leif<br />
Apfel, Ulf Peter, 37<br />
Araqelyan, Qnar, 200<br />
Arbuzova, Anna, 121<br />
Arenz, Christoph, 160<br />
Arkosi, Mariann K<strong>in</strong>ga, 70<br />
Asmis, Knut, 54<br />
Audisio, Davide, 156<br />
August<strong>in</strong>, André<br />
August<strong>in</strong>, Ewa, 278<br />
Avciata, Ulvi, 214, 235<br />
B<br />
Babur<strong>in</strong>, Igor A., 43<br />
Bachl, Jürgen, 116<br />
Baier, Susann, 199<br />
Balabhadra, Sangeetha, 231<br />
316<br />
Bald, Adam, 119<br />
Ballesteros, Rafael, 253<br />
Banerjee, Rahul, 116<br />
Bansen, Roman, 96<br />
Barberá, Joaquín, 53<br />
Barkleit, Astrid, 111<br />
Barner, Leonie, 71<br />
Barner-Kowollik, Christopher, 71<br />
Barta, Christoph<br />
Bartetzko, Max<br />
Bartl<strong>in</strong>g, Christian<br />
Barzen, Sebastian, 177<br />
Baudequ<strong>in</strong>, Christ<strong>in</strong>e, 117<br />
Bauer, Ingmar, 240<br />
Baum, Anne-Kathr<strong>in</strong>, 36<br />
Baumann, Arne, 263<br />
Bayraktar, S<strong>in</strong>em, 258<br />
Beceren-Braun, Figen, 202<br />
Becker, J. Sab<strong>in</strong>e, 28<br />
Becker, Peter, 205, 311<br />
Beeg, Sebastian<br />
Begunk, Robert, 292<br />
Behrens, Malte, 129, 150<br />
Bei, Iryna<br />
Beil, Sebastian<br />
Beleboukhari, Nasser, 165<br />
Beller, Matthias, 74, 280<br />
Belov, Vladimir N., 220<br />
Berger, Robert, 188<br />
Berger, Walter, 46<br />
Bernard, Marek, 191<br />
Bernsdorf, Arne<br />
Biczak, Robert, 206<br />
Bieker, Georg<br />
Bielska, Dorota, 170<br />
Bilg<strong>in</strong>-Eran, Belkıs, 64, 68<br />
Bilyachenko, Aleksey, 79<br />
B<strong>in</strong>der, Wolfgang H., 303<br />
B<strong>in</strong>der, Yvonne<br />
B<strong>in</strong>sker, Florian<br />
Birczyński, Artur, 49<br />
Bisschops, Tom, 127<br />
Bita, Andrei, 291
Blay, Gonzalo, 92, 197, 268<br />
Błauż, Andrzej, 252<br />
Blume, Alfred, 303<br />
Blümel, Marcus, 199<br />
Boeck, Florian, 127<br />
Boeck, Torsten, 96<br />
Böhm, Marv<strong>in</strong><br />
Böhme, Uwe, 195<br />
Böhnert, Tim, 65<br />
Bojarski, Andrzej, 238<br />
Bojić, Aleksandar, 103<br />
Bojić, Danijela, 103<br />
Böker, Birte, 234<br />
Bolm, Carsten, 139, 300<br />
Borissova, Aleksandra, 210<br />
Börner, Hans G., 85<br />
Borriss, Ra<strong>in</strong>er, 178<br />
Bösmann, A., 112<br />
Bouche, Léa, 202<br />
Braun, Beatrice, 297<br />
Braun, Thomas, 209<br />
Bräutigam, Maximilian<br />
Brcanović, Jelena M., 284, 296<br />
Brela, Mateusz, 215<br />
Brendler, Erica, 195<br />
Brendler, V<strong>in</strong>zenz, 73, 111<br />
Breunig, Jens Michael<br />
Brieger, Claudia, 138, 155<br />
Brodersen, Nicolai, 121<br />
Bronste<strong>in</strong>, Lyudmila M., 75<br />
Brör<strong>in</strong>g, Mart<strong>in</strong>, 234<br />
Brudzisz, Anna, 109<br />
Brunner, Eike, 82, 111<br />
Brzózka, Agnieszka, 109<br />
Büchner, Christ<strong>in</strong><br />
Bucila, Virg<strong>in</strong>ia Ramona, 287<br />
Budniak, Adam, 86<br />
Budniak, Urszula, 169<br />
Bulearca, Anca-Mihaela, 291<br />
Burda, Kvetoslava, 228<br />
Butschke, Burkhard, 38<br />
C<br />
Cakar, Fatih, 64, 68<br />
Cal, Dariusz, 243<br />
Calvete, Juan J., 161<br />
Cankurtaran, Ozlem, 64, 68<br />
Carafa, Marianna, 247<br />
Carl, Peter<br />
Carrillo-Cabrera, Wilder, 43<br />
Cativiela, Carlos, 116<br />
Cędrowski, Jakub, 174<br />
Çelebi, Mithat, 77, 104<br />
Celichowski, Grzegorz, 78, 83, 136<br />
Ceylan, Özgür, 77, 104<br />
Chang, Kaich<strong>in</strong>, 56<br />
Chebanov, Valent<strong>in</strong>, 307<br />
Cherepanov, Il’ia A., 219<br />
Cheriti, Abdelkrim, 165<br />
Churakov, Andrei, 260<br />
Ciejka, Justyna, 170<br />
Cieślak, Małgorzata, 136<br />
Cîrcu, Monica Violeta, 298<br />
Cotta, M.A., 101<br />
Cuñat, Ana C., 126<br />
Cybulak, Marta, 264<br />
Cyza, Małgorzata, 179<br />
Czochara, Robert, 163<br />
D<br />
Dabrowska, Anna, 227<br />
Dabrowska, Anna Maria, 132<br />
Dalkowski, Radoslaw, 290<br />
Damian, Grigore, 70<br />
Daniliuc, Constant<strong>in</strong>, 63, 194<br />
Dathe, Margitta, 51<br />
Davis, Ben G., 47<br />
De Keukeleere, Katrien, 44<br />
De Roo, Jonathan, 44<br />
de Souza, A.A., 101<br />
Delso, Ignacio, 48, 131<br />
Demeshko, Serhiy, 297<br />
Dernedde, Jens, 202<br />
Desenko, Sergey, 236<br />
Díaz Díaz, David, 116<br />
Diederichsen, Ulf, 273, 293<br />
Diehl, Andreas<br />
Diehl, Bernd, 302<br />
Diehl, Claudia<br />
Dieskau, André P., 154<br />
Dietl, Nicolas, 54<br />
D<strong>in</strong>cer, Hatice, 258<br />
Dipalo, Maria Concetta, 168<br />
Dippel, Rabea, 312<br />
Diudea, Mircea V., 287<br />
Djordjevic, Aleksandra , 294<br />
317
Dlugaszewska, J., 50<br />
Dmitriev, Aleksey, 79<br />
Dmitrieva, Jana<br />
Dobrowolski, Dariusz, 89<br />
Doerfler, Denise, 162<br />
Dom<strong>in</strong>iak, Paul<strong>in</strong>a Maria, 169, 305<br />
Donten, Mikolaj, 278<br />
Drabińska, Beata, 238<br />
Drath, Christ<strong>in</strong>e<br />
Dronova, Mar<strong>in</strong>a, 79<br />
Drzymala, Sarah, 190<br />
Düdder, Hendrik, 150<br />
Duric, Sasa, 137, 146<br />
Dutkiewicz, Zbigniew, 191<br />
Düzgünes, Nejat, 50, 248, 279<br />
Dyadchenko, Viktor P., 310<br />
Dzieciuch, Monika, 295<br />
E<br />
Ebersbach, Ben<br />
Efimenko, Inessa, 260<br />
Ehlers, Peter, 246<br />
Eisenblätter, Jördis, 71<br />
Eitner, Krystian, 107<br />
Ejsmont, Krzysztof, 286<br />
El Fray, Mirosława, 269<br />
El-khateeb, Mohammed, 37<br />
Emen, Fatih Mehmet, 186<br />
Emmerl<strong>in</strong>g, Franziska, 96<br />
Enderle, Eric<br />
Enders, Dieter, 127<br />
Engeser, Marianne, 128<br />
Erden, Ibrahim, 100, 256<br />
Erdoğmuş, Ali, 100, 166, 214, 235,<br />
256<br />
Ernst<strong>in</strong>g, Nikolaus P., 277<br />
Erol, Ismail, 68<br />
Escamilla, Ana, 126<br />
Esser, Norbert, 263<br />
Ester, Movsisyan<br />
Eychmüller, Alexander, 43, 62, 72, 82,<br />
110, 181, 193, 267<br />
F<br />
Fehrenbacher, Ulrich, 71, 241<br />
Feist, Michael, 250<br />
318<br />
Fensterbank, Louis, 148<br />
Fer<strong>in</strong>gán, Beatriz, 53<br />
Feys, Jonas, 44<br />
Fiechter, Fridol<strong>in</strong><br />
Filipek, Elżbieta, 249<br />
Filippov, Oleg A., 310<br />
F<strong>in</strong>k, Daniel, 217<br />
Fischer, Cathleen, 82<br />
Fischer, Franziska<br />
Fischer, Tobias, 130<br />
Fischer-Fodor, Eva, 70<br />
Fita, Piotr, 228, 266<br />
Fopp, Carol<strong>in</strong><br />
Ford, Leigh, 41<br />
Fornal, Emilia, 232<br />
Foucout, Lénaig, 262<br />
Frei, Maren<br />
Freytag, Matthias, 63, 194<br />
Fr<strong>in</strong>gs, Marcus, 139<br />
Fritz, Maria, 56<br />
Fronert, Jeanne, 127, 311<br />
G<br />
Gabriel, Stefanie, 62<br />
Gambacorta, Augusto, 40<br />
Gandor, Felix<br />
Gaponik, Nikolai, 181, 267<br />
Garcia-Gonzalez, Eva, 178<br />
Gasiorek, Friederike<br />
Gasperi, Tecla, 40<br />
Gawel, Marta, 227<br />
Gehne, Sören, 51<br />
Genersch, Elke, 178<br />
Gensch, Tobias, 240<br />
Gensel, Julia<br />
Gericke, Eike, 96<br />
Gerigk, Melanie<br />
Gevorgyan, Ashot, 200<br />
Ghirardello, Mattia, 175<br />
Ghochikyan, Tariel, 246<br />
Girón, Rosa María, 268<br />
Gliemann, Bett<strong>in</strong>a, 211<br />
Glitscher, Emanuel<br />
Glöckner, Andreas, 194<br />
Glor, C<strong>in</strong>dy , 123<br />
Głowacki, Ireneusz, 282<br />
Goddard, Jean Philippe, 148<br />
Gölden, Simon
Golub, Igor E., 310<br />
Gomollon-Bel, Fernando, 48, 175<br />
Gooßen, Lukas J., 145<br />
Goral, Anna Maria, 305<br />
Górecka, Ewa, 91<br />
Görls, Helmar, 37<br />
Gorobets, Nikolay, 236<br />
Goroncy, Christian, 93<br />
Gosl<strong>in</strong>ski, Tomasz, 50, 143, 191, 228,<br />
248, 272, 279<br />
Göth, Melanie<br />
Gracia, Ismael, 53<br />
Graf, Christ<strong>in</strong>a, 93<br />
Graf, Matthias, 72<br />
Grela, Karol, 144<br />
Grobelny, Jaroslaw, 78, 83<br />
Grolik, Maria, 89<br />
Große, Steffi<br />
Großmann, Kay, 73<br />
Grosu, Ion, 113, 117<br />
Groth, Ulrich, 208<br />
Grünert, Anna<br />
Grunst, Michael, 211<br />
Grześkowiak, Magdalena, 157<br />
Grzyb, Tomasz, 76<br />
Gschw<strong>in</strong>d, Ruth M., 147<br />
Gul, Ahmet, 214, 235<br />
Gumrukcu, Gulsah, 214, 235<br />
Gut, Arkadiusz, 179<br />
H<br />
Hakobyan, Ani, 200<br />
Hamkalo, Michal, 266<br />
Hann, Stephan, 46<br />
Hanßke, Felix<br />
Hashmi, A. Stephen K., 24<br />
Hatami, Soheil, 267<br />
Hathazi, Gabriela Denisa, 70, 176<br />
Hauser, Anett<br />
Heck, Jürgen, 36, 134, 229, 237<br />
Heffeter, Petra, 46<br />
He<strong>in</strong>ze, Katja, 225<br />
Heislbetz, Sandra, 180<br />
Hell, Stefan W., 220<br />
Hendel, Thomas<br />
Hennig, Andreas, 159<br />
Hens, Zeger, 44<br />
Hermann, Gerrit, 46<br />
Hermes, Michael<br />
Herrmann, Andreas, 121<br />
Herrmann, Anne-Krist<strong>in</strong>, 181<br />
Herrmann, Roy, 209<br />
Herwig, Christian, 250<br />
Hey-Hawk<strong>in</strong>s, Evamarie, 204<br />
Hickey, Stephen G., 43, 62, 110, 193<br />
Hnida, Katarzyna, 65<br />
Hochkirch, Ulrike, 173<br />
Hoffmann, Mart<strong>in</strong>, 234<br />
Hofmann, Anna<br />
Hofmann, Bett<strong>in</strong>a, 177<br />
Hofmann, Johanna, 173<br />
Holyst, Robert, 45<br />
Holzweber, Markus, 162<br />
Horeglad, Pawel, 132<br />
Horn, Bett<strong>in</strong>a, 250<br />
Huang, Xueliang , 141<br />
Huh, Joonsuk, 188<br />
Hurtado-Guerrero, Ramon, 48<br />
Hussner, Jan<strong>in</strong>e, 292<br />
Huster, Daniel, 121<br />
Hüttenha<strong>in</strong>, Stefan H., 161<br />
Hutter, Herbert, 162<br />
Huzar, Elżbieta , 189<br />
I<br />
Iannone, Francesco, 247<br />
Iaroshenko, Viktor O., 198, 200, 223,<br />
292, 301<br />
Iglesias, Álvaro, 205<br />
Ilic, Marija, 98, 294<br />
Imhof, Wolfgang, 37<br />
Intelmann, Matthias<br />
Ivanov, Anton, 198<br />
J<br />
Jähnigen, Sandra, 195<br />
Janissen, R., 101<br />
Janoschka, Tobias<br />
Jantschke, Anne, 82<br />
Janus, Ewa, 261<br />
Jarosz, Magdalena, 58<br />
Jarzeb<strong>in</strong>ska, Anita, 278<br />
Jarzembska, Katarzyna N., 169<br />
Jarzynski, Szymon, 233<br />
319
Jasiński, Marc<strong>in</strong>, 251<br />
Jaskuła, Marian, 58, 65, 80, 84<br />
Jemielity, Jacek, 239<br />
Jevric, Lidija, 274, 281<br />
Jones, Peter G., 63, 194<br />
Jost, Tobias, 313<br />
Joswig, Jan-Ole, 267<br />
Jovanović, Ljiljana, 222<br />
Jovanovic, Olga, 294<br />
Jovanovic, Snezana, 98, 294<br />
Jóźwiak, Andrzej, 243<br />
Jung, Jarosław, 282<br />
Junge, Henrik, 74<br />
Junge, Kathr<strong>in</strong>, 280<br />
K<br />
Käbisch, Bert, 241<br />
Kaczor-Kamińska, Marta, 99<br />
Kähler, Kev<strong>in</strong>, 150<br />
Kahraman, Gizem, 88<br />
Kaiser, Sel<strong>in</strong>a<br />
Kalajdzija, Natasa, 274, 281<br />
Kalevaru, Narayana, 124, 275<br />
Kal<strong>in</strong>ichenko, Kira<br />
Kal<strong>in</strong><strong>in</strong>, Valery N., 219<br />
Kalwarczyk, Tomasz, 45<br />
Kam<strong>in</strong>ski, Kamil, 170<br />
Kandemir, Timur<br />
Kapoor, Iti, 116<br />
Kapusta-Kołodziej, Joanna, 80<br />
Karaagac, Erdal<br />
Karaman, Ferdane, 64, 68<br />
Karaoglan, Gulnur Keser, 214<br />
Karavelioğlu, Selvi<br />
Karewicz, Anna, 170<br />
Kastner, Kathar<strong>in</strong>a, 226<br />
Katona, Jaroslav, 265<br />
Kaya, Mehmet Arif, 69, 77, 104, 166<br />
Keßler, Eva<br />
Keller, Marlou, 313<br />
Kępczyński, Mariusz, 171, 179, 295<br />
Keser Karaoglan, Gulnur, 235<br />
Keshavarz, Elahe<br />
Kesk<strong>in</strong>, Bahadir, 153<br />
Kettemann, Frieder<br />
Kierys, Agnieszka, 227<br />
Kılıçarslan, Fatma Aytan, 256<br />
Kırbac, Erkan, 100<br />
320<br />
Kiril<strong>in</strong>, Aleksey, 79<br />
Kittler, Katr<strong>in</strong>, 283<br />
Kittler, Susann, 110<br />
Kivala, Milan, 211<br />
Kjaer Nielsen, Pia, 133<br />
Klaper, Matthias, 125<br />
Kleemann, Julian, 311<br />
Kle<strong>in</strong>e, Tillmann, 300<br />
Klimczak, Anna Agnieszka, 206<br />
Klimczyk, Sebastian , 141<br />
Klos, Manuel Rudolf<br />
Klucznik, Tomasz, 221<br />
Kluza, Rafal, 218<br />
Knar, Arakelyan<br />
Knölker, Hans-Joachim, 240<br />
Knyazyan, Aram<br />
Kob<strong>in</strong>, Björn<br />
Koch, Gregor, 55, 142<br />
Koch, Matthias, 190, 271, 283<br />
Köckert, Hansjochen<br />
Koczorowski, Tomasz, 228<br />
Koel, Mihkel, 162<br />
Koellensperger, Gunda, 46<br />
Kollmorgen, Patrick, 124<br />
Konopka, Krystyna, 50, 248, 279<br />
Koplak, Oksana, 79<br />
Körber, Wieland<br />
Kotus, Joanna<br />
Kovacevic, Strah<strong>in</strong>ja, 274, 281<br />
Kowalczyk, Agata, 278<br />
Kowalkiewicz, Zuzanna, 97, 106, 183<br />
Kowalska, Joanna, 239<br />
Kowalski, Marc<strong>in</strong>, 259<br />
Kowollik, Sandro<br />
Kranz, C., 101<br />
Krause, Norbert, 130<br />
Kraushaar, Konstant<strong>in</strong><br />
Krawczyk, Barbara, 290<br />
Kretzschmar, Jérôme, 111<br />
Kreye, Markus, 194<br />
Krich, Christopher, 263<br />
Krogul, Agnieszka<br />
Kroke, Edw<strong>in</strong>, 195, 241<br />
Krówczyński, Adam, 91<br />
Krstić, Nenad, 103<br />
Kruk, Danuta, 49<br />
Krumbe<strong>in</strong>, Angelika, 283<br />
Kryjewski, Michal, 143<br />
Krys<strong>in</strong>ski, Pawel, 278<br />
Krzyżanowska, Anna, 289<br />
Krzyczmonik, Anna, 309
Kuźmicz, Danuta, 89<br />
Kubiak, Katarzyna, 90<br />
Kubica, Aleksandra, 49<br />
Kubicka, Aleksandra, 232<br />
Küchenthal, Christian<br />
Kuchk<strong>in</strong>a, N<strong>in</strong>a V., 75<br />
Kuc<strong>in</strong>ska, M., 50<br />
Kuckl<strong>in</strong>g, Dirk, 67<br />
Kühbeck, Dennis, 116<br />
Kühl, Stefanie, 150<br />
Kühn, Julius, 304<br />
Kuhrt, Patrick, 123<br />
Kujawski, Jacek, 191, 238<br />
Külcü, Nevzat, 186<br />
Kulik, Marta, 305<br />
Kumke, Michael U., 51<br />
Kurczab, Rafal, 238<br />
Kurowska, Elżbieta, 84<br />
Kuryltso, Vladyslav, 95<br />
Kwiecień, Hal<strong>in</strong>a, 189, 196, 224<br />
Kwolek, Urszula, 171<br />
L<br />
Lalović, Mirjana, 222, 245<br />
Landschulze, Dirk<br />
Lang, He<strong>in</strong>rich, 257<br />
Langer, Peter, 198, 223, 246<br />
Łapok, Łukasz, 179<br />
Lar, Claudia, 113<br />
Lechner, Bob-Dan, 303, 313<br />
Lee, Michael, 279<br />
Lempke, L<strong>in</strong>da, 130<br />
Lentz, Dieter, 146<br />
Leovac, Vukad<strong>in</strong>, 222, 245<br />
Lesniak, Anna, 244<br />
Lesniak, Stanislaw, 233<br />
Leubner, Susanne, 267<br />
Levacher, V<strong>in</strong>cent, 262<br />
Levitsky, Mikhail, 79<br />
Lewandrowska, Anna, 285<br />
Lewkowski, Jarosław, 206, 309<br />
Li, Yuehui, 280<br />
Liebscher, Jürgen, 121<br />
Liebscher, Lydia, 43, 62<br />
Lijewski, Sebastian, 279<br />
Lill, Andreas, 177<br />
Limberg, Christian, 201, 230, 250, 297<br />
L<strong>in</strong>del, Thomas, 39<br />
L<strong>in</strong>den, Michael, 312<br />
L<strong>in</strong>dermayr, Kathar<strong>in</strong>a<br />
L<strong>in</strong>ert, Wolfgang, 162<br />
L<strong>in</strong>ke, Vanessa<br />
L<strong>in</strong>ker, Torsten, 125<br />
L<strong>in</strong>scheid, Michael W., 173<br />
Lipiecka, Sylwia, 97, 106, 183<br />
Lips, Katr<strong>in</strong> Susanne, 202<br />
Lis, Stefan, 61, 231<br />
Lis, Tadeusz, 309<br />
Litw<strong>in</strong>ienko, Grzegorz, 163, 174<br />
Litw<strong>in</strong>ska, Anna, 132<br />
Liu, Shanshan, 276<br />
Loew, Mart<strong>in</strong>, 121<br />
Löhmann, Oliver<br />
Lojovic, Maja, 281<br />
Lommens, Petra, 44<br />
Loncar, Eva, 274<br />
Lorenz, Tommy, 267<br />
Loreto, Maria Antonietta, 40<br />
Lorite, G.S., 101<br />
Losensky, Louisa, 121<br />
Loth, Sebastian, 26<br />
Lu, Liang-Qiu, 280<br />
Ludwig, Ralf, 277, 288<br />
Lukomska, Marlena, 286<br />
Lükermann, Daniel, 263<br />
Lungwitz, Ralf, 162<br />
Lupan, Iulia, 70<br />
Luparia, Marco, 156<br />
Lyczkowska, Patrycja, 136<br />
M<br />
Maaß, Sebastian<br />
Maekawa, Miyuki, 63<br />
Magerle, Robert, 303<br />
Mahrwald, Ra<strong>in</strong>er, 207<br />
Mahut, Sonia, 176<br />
Majcher, Aldona, 285<br />
Makowska, Katarzyna, 97, 106, 183<br />
Makuch, Edyta, 151<br />
Malec, Katarzyna, 58<br />
Mandel, Miles<br />
Mandić, Emanuela<br />
Mansuy, Virg<strong>in</strong>ie, 148<br />
Marca, Eduardo, 48<br />
Marc<strong>in</strong>kowska, Magdalena, 254<br />
Märker, Björn<br />
321
Marosanovic, Biljana , 281<br />
Marrero-Tellado, José Juan, 116<br />
Marten, Silvia, 190<br />
Mart<strong>in</strong>, Andreas, 124, 275<br />
Mart<strong>in</strong>a, Miceli<br />
Matusiak, Agnieszka, 206<br />
Matviitsuk, Anastassia, 207<br />
Maul, Ronald, 271, 283<br />
Maulide, Nuno, 141, 156<br />
Mavelli, Fabio, 168<br />
Mazerska, Zofia, 278<br />
Mazur, Maciej, 86<br />
Mazziotta, Andrea, 40<br />
McDonough, Michael, 47<br />
Mebs, Stefan, 250<br />
Meißler, Maria, 85<br />
Meißner, Gisa, 123<br />
Meier, Patrick, 188<br />
Me<strong>in</strong>eck, Myriam<br />
Mele, Valent<strong>in</strong>a, 247<br />
Mellmann, Dörthe, 74<br />
Mer<strong>in</strong>o, Pedro, 48, 131, 175, 216<br />
Mert Balaban, Humeyra, 258<br />
Mette, Kathar<strong>in</strong>a, 150<br />
Metz, Peter, 199<br />
Meyer zu Schwabedissen, Henriette, 292<br />
Meyer, Franc, 297<br />
Miceli, Mart<strong>in</strong>a, 40<br />
Michel, Kathr<strong>in</strong><br />
Middel, Stephen, 293<br />
Mielcarek, Jadwiga, 50, 143, 228, 248,<br />
272, 279<br />
Milchert, Eugeniusz, 289<br />
Milewska, Aleksandra, 170<br />
Miliut<strong>in</strong>a, Mariia, 198<br />
Milovanović, Milan, 115<br />
Mis<strong>in</strong>i, Majda, 115<br />
Misztal, Krzysztof<br />
Mitić, Milan N., 284<br />
Mitić, Snežana S., 284<br />
Mitic, Violeta, 98, 294<br />
Mitrović, Jelena, 103<br />
Mizaikoff, B., 101<br />
Mkrtchyan, Satenik, 200, 301<br />
Mlostoń, Grzegorz, 203, 218, 255, 259<br />
Mohamed Saied Mostafa, Essa<br />
Monleón, Alicia, 92<br />
Montes<strong>in</strong>os Magraner, Marc, 268<br />
Morawski, Antoni W., 157<br />
Mot, August<strong>in</strong> Catal<strong>in</strong>, 70<br />
Muhler, Mart<strong>in</strong>, 150<br />
322<br />
Müller, Fabian<br />
Müller, Jens, 120<br />
Müller, Sebastian, 178<br />
Muñiz, Kilian, 205<br />
Münzel, Mart<strong>in</strong>, 47<br />
Murias, M., 50<br />
Murillo Munar, D.M., 101<br />
Murlyk<strong>in</strong>a, Maryna, 307<br />
Myka, Anna, 238<br />
N<br />
Nalivayko, Peter, 185, 187<br />
Narozny, Maciej, 107<br />
Naurecka, Magdalena Ligia, 285<br />
Nechifor, Gheorghe, 105<br />
Neda, Ion, 113<br />
Neff, Michael, 182<br />
Neidl<strong>in</strong>ger, Andreas, 225<br />
Neumann, Mike, 102<br />
Neumann, Wilma, 204<br />
Nielsch, Kornelius, 65<br />
Niemczyk, Agata, 269<br />
Nikolić, Ružica, 103<br />
Nikolic-Mandic, Snezana, 98<br />
N<strong>in</strong>ković, Dragan, 115, 122<br />
N<strong>in</strong>nemann, N<strong>in</strong>a M., 146<br />
Niyomchon, Supaporn, 156<br />
Niza Silva, B.C., 101<br />
Nizamov, Shamil, 220<br />
Njaradi, Sandra , 265<br />
Njie, Abdoulie<br />
Nojoumi, Saba<br />
Nowak, Michal, 143<br />
Nowakowska, Maria, 59, 87, 89, 170,<br />
171, 179, 295<br />
Nowicka, Anna Maria, 278<br />
Nüesch, Frank Ala<strong>in</strong>, 298<br />
O<br />
Obesser, Kathar<strong>in</strong>a, 112<br />
Obijalska, Emilia, 203, 218, 255, 259<br />
Ocak, Hale, 64, 68<br />
Olubummo, Adekunle, 303<br />
Omenat, Ana, 53<br />
Oppermann, Alex<br />
Opriş, Dor<strong>in</strong>a Maria, 298
Orbeci, Crist<strong>in</strong>a, 105<br />
Orzechowska, Aleksandra, 228<br />
Oschetzki, Dom<strong>in</strong>ik, 182<br />
Osipov, Alexander P., 164<br />
Ossowicz, Paula, 261<br />
Ostrovskyi, Dmitro, 200<br />
Oudeyer, Sylva<strong>in</strong>, 262<br />
Owińska, Maria, 215<br />
Özdemir, Merve, 256<br />
Ozdemir, Zafer Omer, 158<br />
Ozkal, Selma, 64<br />
Özpınar, Celal, 186<br />
Ozturkcan, S. Arda, 108, 153<br />
P<br />
Pacześna, Agnieszka, 249<br />
Palumbo, Chiara, 40<br />
Palusiak, Marc<strong>in</strong>, 286<br />
Panse, Cornelia H., 293<br />
Papamicaël, Cyril, 262<br />
Paunovic, Dusan Ð., 296<br />
Pavlović, Aleksandra N., 284, 296<br />
Pavlović, Jovana Lj., 284<br />
Pedersen, Kasper<br />
Pedro, José Ramón, 92, 197, 268<br />
Pescador, Paula, 121<br />
Petersen, Diana, 273<br />
Petit, Sylva<strong>in</strong>, 262<br />
Petkova, Nadezhda<br />
Petran, Anca, 121<br />
Petras, Daniel, 161<br />
Petrosyan, Andranik, 246<br />
Petrovic, Goran, 294<br />
Pfeffer, Inga, 47<br />
Pfeiffer, Florian, 180<br />
Pfister, Andrea<br />
Pfister, Kai, 145<br />
Pilawka, Ryszard, 261<br />
P<strong>in</strong>kert, Denise, 297<br />
P<strong>in</strong>kert, Thomas, 160<br />
Pirovano, Claudio, 275<br />
Pirwerdjan, Ramona, 300<br />
Piskorz, Jaroslaw, 248<br />
Piskorz, Tomasz, 140<br />
Plachetta, Silke, 123<br />
Plażuk, Damian, 252<br />
Plietker, Bernd, 154<br />
Płotka, Mieczysław W., 243<br />
Podunavac Kuzmanovic, Sanja, 274,<br />
281<br />
Polte, Jörg, 42<br />
Polupanow, Tatjana, 273<br />
Popielarska, Hanna, 238<br />
Popovic, Marko, 308<br />
Poppe, Jan, 62, 110<br />
Porshneva, Ksenia, 167<br />
Pospiech, Steffen<br />
Potempa, Jan, 170<br />
Povie, Guillaume, 41<br />
Pozzi, Davide, 41<br />
Proserpio, Davide M., 287<br />
Proske, Matthias, 271<br />
Prymak, Iuliia, 124<br />
Przepiórski, Jacek, 157<br />
Przybylska, Dom<strong>in</strong>ika, 94<br />
Puchala, Agnieszka, 244<br />
Puciul-Mal<strong>in</strong>owska, Agnieszka, 95<br />
Purtak, Katarzyna, 91<br />
Pyrc, Krzysztof, 170<br />
Q<br />
Quaranta, Eugenio, 247<br />
R<br />
Rachwalski, Michal, 233<br />
Rademann, Klaus, 42, 96<br />
Radović, Miljana, 103<br />
Raimer, Björn, 39<br />
Ramondenc, Yvan, 117<br />
Rasala, Danuta, 254<br />
Räthel, Jochen, 263<br />
Rauhut, Guntram, 180, 182, 188<br />
Reimann, Sebastian, 277, 288<br />
Re<strong>in</strong>hardt, Ulrike<br />
Reissig, Hans-Ulrich, 202<br />
Reitz, Annika, 67<br />
Renaud, Philippe, 41<br />
Resch-Genger, Ute, 159, 267<br />
Ressler, Thorsten, 55, 135, 142<br />
Reznikov, Ivan<br />
Richter, Constanze, 73<br />
Riedel, Ludwig, 313<br />
Riemer, Mart<strong>in</strong>, 149<br />
Risch, Stefan, 190<br />
323
Roca-López, David, 216<br />
Rodić, Marko, 222, 245<br />
Rödl, Carmen B., 177<br />
Roelens, Stefano, 116<br />
Rohn, Sascha, 283<br />
Röhr, Merle Insa Silja<br />
Romanova, Natalia A., 56<br />
Romański, Jarosław, 251<br />
Rommel, Susanne, 154<br />
Rosenow, Phil, 270<br />
Rosowski, Marc<strong>in</strong>, 78, 83<br />
Rosseeva, Elena, 43<br />
Rossow, Torsten, 52<br />
Roth, Christian, 288<br />
Roth, Christ<strong>in</strong>a, 138, 155<br />
Roth, Klaus, 32<br />
Rozwadowski, Zbigniew, 261<br />
Rudolf, Bogna, 232<br />
Rudolph, Manfred, 37<br />
Ruhe, Lena, 173<br />
Runowski, Marc<strong>in</strong>, 231<br />
Rurack, Knut, 130<br />
Rybarczyk-Pirek, Agnieszka, 286<br />
Rychlik, Błażej, 252<br />
Rychter, Piotr, 206<br />
Rys, Barbara, 215<br />
Rząd, Ewa, 171<br />
S<br />
Sachs, Anne, 134<br />
Sadaba, David, 131, 175<br />
Saghyan, Ashot, 246<br />
Saha, Subhadeep, 116<br />
Şah<strong>in</strong>, Gizem<br />
Sakhno, Yana, 307<br />
Sallmann, Madleen, 201<br />
Samarskaya, Al<strong>in</strong>a S., 219<br />
Samojłlowicz, Cezary<br />
Samsonova, Janna V., 164<br />
Sanz, Juan F., 126<br />
Sanz-Marco, Amparo, 197<br />
Savych, Iryna, 223<br />
Sawoszczuk, Tomasz, 58<br />
Scharf, Daniel<br />
Scharf, Philipp, 120<br />
Schaumberg, Christian<br />
Schax, Fabian, 297<br />
Scheer, Elke, 208<br />
324<br />
Scheidt, Holger, 121<br />
Schendzielorz, Florian<br />
Scheunemann, Jana<br />
Schilde, Uwe, 102<br />
Schlangen, Maria, 54<br />
Schlecht, Sab<strong>in</strong>e, 202<br />
Schlögl, Robert, 129, 133, 150<br />
Schloß, Svenja, 271<br />
Schmidt, Bernd, 149<br />
Schmidt, Bernd M., 146<br />
Schmidt, Lena, 142<br />
Schmidt, Mart<strong>in</strong>, 128<br />
Schmode, Stella, 277, 288<br />
Schmudde, Madlen, 93<br />
Schober, Katr<strong>in</strong>, 147<br />
Schofield, Christopher J., 47<br />
Schökel, Alexander, 138, 155<br />
Schollmeyer, Mart<strong>in</strong><br />
Scholz, Juliane, 135<br />
Schön, Eva-Maria, 116<br />
Schönborn, Enno, 275<br />
Schre<strong>in</strong>er, Monika, 283<br />
Schre<strong>in</strong>er, Peter R., 30<br />
Schröder, Felix, 148<br />
Schulz, Christian<br />
Schulz, Matthias, 303<br />
Schumann, Julia, 129<br />
Schütz, Denise<br />
Schwarz, Helmut, 38, 54<br />
Scorei, Romulus Ion, 291<br />
Sednev, Maksim V., 220<br />
Seidt, Britta<br />
Seiffert, Sebastian, 52<br />
Sekkoum, Khaled, 165<br />
Sen, Betul Nur, 258<br />
Sener, Muhammet Kasim, 69<br />
Senf, Antti<br />
Serrano, Jose Luis, 53<br />
Sevim, Ilhan, 114<br />
Shahid, Khadija, 306<br />
Shifr<strong>in</strong>a, Z<strong>in</strong>aida B., 75<br />
Shishilov, Oleg, 210, 260<br />
Shub<strong>in</strong>a, Elena S., 79, 310<br />
Shyichuk, Andrii, 61<br />
Sieredz<strong>in</strong>ska, Bianka, 285<br />
Sikorski, Andrzej, 140<br />
Silaghi-Dumitrescu, Radu, 70, 176<br />
Simon, Paul, 43<br />
Simonovic, Strah<strong>in</strong>ja, 98<br />
Six, Alice, 255<br />
Skup<strong>in</strong>-Mrugalska, P., 50
Ślepokura, Katarzyna, 309<br />
Sloniec, Jagoda, 159<br />
Smirnova, Daria V., 164<br />
Śmist, Małgorzata, 184, 196<br />
Smolan, Willi<br />
Smusz, Sab<strong>in</strong>a, 238<br />
Sobczak, Justyna, 189<br />
Sobotta, Lukasz, 50, 228, 272, 279<br />
Sobottka, Sebastian<br />
Sokolowski, Anja, 152<br />
Soliwoda, Katarzyna, 78, 83<br />
Sośnicki, Jacek G., 192<br />
Sosnovskikh, Vyacheslav, 223<br />
Souto, José A., 205<br />
Söyler, Zafer, 118<br />
Sozanski, Krzysztof, 45<br />
Spange, Stefan , 162<br />
Speck, Matthäus, 257<br />
Speiser, Eugen, 263<br />
Spitzner, Eike-Christian, 303<br />
Sponholz, Peter, 74<br />
Srivastava, Vishnu P., 242<br />
Stachniuk, Justyna, 290<br />
Stachowski, Gordon M., 193<br />
Stange, Uta Cor<strong>in</strong>na<br />
Staniszewski, Zygmunt, 269<br />
Stankov-Jovanovic, Vesna, 98, 294<br />
Stanković, Maja, 103<br />
Stano, Pasquale, 168<br />
Stark, Holger, 177<br />
Stefaniak, Monika, 251<br />
Stefaniuk, Anna, 282<br />
Ste<strong>in</strong>hilber, Dieter, 177<br />
Ste<strong>in</strong>kamp, Anne-Dorothee, 139<br />
Sternberg, Katr<strong>in</strong>, 292<br />
Stockmann, Madlen, 73<br />
Stojanovic, Branka T., 296<br />
Stojanovic, Gordana, 294<br />
Stojek, Zbigniew, 278<br />
Stojkovic, Milan M., 296<br />
Strauch, Peter, 102<br />
Streb, Carsten, 226<br />
Struk, Łukasz, 192<br />
Stuckmann, Alexandra<br />
Stutz, Christian<br />
Su, Meng, 172<br />
Sulka, Grzegorz D., 58, 65, 80, 84, 109<br />
Supe, L<strong>in</strong>da, 292, 200<br />
Süßmuth, Roderich, 178<br />
Süssmuth, Roderich D., 161<br />
Svensson, Emma, 137<br />
Swarcewicz, Maria, 184<br />
Sydow, Karl, 51<br />
Sygula-Cholew<strong>in</strong>ska, Justyna, 58<br />
Symonowicz, Michał, 163<br />
Sypaseuth, Fanni, 299<br />
Sysoiev, Dmytro, 208<br />
Szafraniec, Joanna, 87<br />
Szczepaniak, Grzegorz, 144<br />
Szczolko, W., 50<br />
Szczolko, Wojciech, 191, 228<br />
Szczubiałka, Krzysztof, 89, 170<br />
Szczukocki, Dom<strong>in</strong>ik , 290<br />
Szemraj, Janusz, 206<br />
Szewczyk, Grzegorz, 179<br />
Szpak, Agnieszka, 59<br />
Szuwarzyński, Michał, 66<br />
Szydłowska, Natalia, 295<br />
T<br />
Taden, Andreas, 85<br />
Talantsev, Artem, 79<br />
Taleb, Safia, 165<br />
Tamm, Matthias, 194<br />
Tamm, Nadezhda B., 56<br />
Tarasov, Andrey, 129<br />
Tatev, Grigoryan<br />
Tavernaro, Isabella, 202<br />
Tegenkamp, Christoph, 263<br />
Tejero, Tomás, 48, 131, 175, 216<br />
Teng, Heidi<br />
Terec, Anamaria, 113, 117<br />
Thiedemann, Birk<br />
Thomale, Jürgen, 173<br />
Thomas, Nygil, 129<br />
Tikhonova, Julia<br />
Țînțaş, Mihaela-Liliana, 262<br />
Tkacz-Szczesna, Beata, 78, 83<br />
Tokarz, Paweł, 309<br />
Töllner, William, 65<br />
Tomsik, Alena, 265<br />
Tonner, Ralf, 270<br />
Tosic, Snezana B., 296<br />
Tosun, Ece, 81<br />
Tr<strong>in</strong>kaus, Katja, 202<br />
Troyanov, Sergey I., 56<br />
Trunschke, Annette, 133<br />
Trützschler, Anne-Krist<strong>in</strong><br />
Trylska, Joanna, 305<br />
325
Tschersich, Carol<strong>in</strong>, 230<br />
Tugcu, Fatma Tülay, 60, 81, 88<br />
Turgut, Zuhal, 108<br />
Turhan, Kadir, 108<br />
Tykarska, Ewa, 50, 279<br />
Tzschucke, C. Christoph, 123, 137, 146,<br />
152, 213, 276, 299<br />
U<br />
Uebele, Kathar<strong>in</strong>a<br />
Ugarova, Natalia N., 164<br />
Uğur, Ahmet Lütfi, 100, 166<br />
Untea, Ion, 105<br />
Urbaniak, Alicja<br />
Urbaniak, Włodzimierz, 97, 106, 107,<br />
183<br />
Utecht, Greta, 203<br />
V<br />
Van Driessche, Isabel, 44<br />
Vasilkevich, Alexey<br />
Veiros, Luis F., 141<br />
Veljković, Jovana N., 284, 296<br />
Viehoff, Maria<br />
Viktor, Iaroshenko<br />
Vilches-Herrera, Marcelo, 200<br />
Villa, Giorgio, 41<br />
Vill<strong>in</strong>ger, Alexander, 223, 301<br />
Vishchuk , Olesya S., 167<br />
Vlad, Miranda Petronella, 287<br />
Vodolazhenko, Mariia, 236<br />
Voigt, Benjam<strong>in</strong>, 207<br />
Voj<strong>in</strong>ović-Ješić, Ljiljana, 222, 245<br />
von Kiedrowski, Gunter, 114<br />
von Rekowski, Felicitas, 147<br />
Vondung, Lisa<br />
W<br />
Wagler, Jörg, 212<br />
Wahl, Sebastian<br />
Walczak, Aleksandra, 254<br />
Walczak, Sylwia, 239<br />
Wallis, Philipp, 275<br />
Walter, Marc D., 63, 194<br />
326<br />
Warncke, Gisela, 212<br />
Wasserscheid, P., 112<br />
Watal, Geeta, 242<br />
Węcławiak, Mariusz<br />
Weidemann, Stefan, 96<br />
Weigand, Wolfgang, 37<br />
Wendt, Robert<br />
Wiebalck, Swantje, 123<br />
Wieczorek, Anna, 252<br />
Wieczorek, Sebastian<br />
Wierzchowski, Marc<strong>in</strong>, 50, 228, 272,<br />
279<br />
Wiglusz, Rafał, 94<br />
Wildenhof, Thomas<br />
Wilhelm, René, 67<br />
W<strong>in</strong>d, Marie-Louise<br />
W<strong>in</strong>kler, Helmut<br />
W<strong>in</strong>kler, Rajko<br />
W<strong>in</strong>ter, Ra<strong>in</strong>er, 217<br />
Wohlrab, Sebastian, 124, 275<br />
Woiczechowski-Pop, Adrian, 117<br />
Wojtczak, Błażej, 239<br />
Wolfram, Benedikt, 234<br />
Wolski, Karol, 66<br />
Wolter, Anne, 229<br />
Wolter, Klaus-Jürgen, 72<br />
Wolters, Daniel<br />
Wolz, André, 155<br />
Wowra, Bogumił , 89<br />
Wozniak, Mart<strong>in</strong><br />
Wróblewska, Agnieszka, 151<br />
Wrona, Ewa, 215<br />
Wrześniewska, Agata, 224<br />
Wuithschick, Maria, 42<br />
Wuttke, Evelyn, 217<br />
Wybranska, Iwona, 58<br />
Wylęgała, Edward, 89<br />
Y<br />
Yadav, Arv<strong>in</strong>d K., 242<br />
Yadav, Deepak K., 242<br />
Yadav, L. D. S., 242<br />
Yasa, Göknur, 100, 256<br />
Yıldırım, Hüsey<strong>in</strong>, 77, 104<br />
Yurtseven, Hilal, 69<br />
Yuzik-Klimova, Ekater<strong>in</strong>a Yu., 75
Z<br />
Zagórski, Piotr, 243<br />
Zailer, El<strong>in</strong>a, 302<br />
Zakrzewski, Janusz , 252<br />
Zakrzewski, Robert, 290<br />
Zapotoczny, Szczepan, 59, 66, 87, 95<br />
Zarić, Snežana, 115, 122<br />
Zaspel, Irmtraut, 271<br />
Zeuschner, Janek<br />
Zhikol, Oleg, 236<br />
Ziel<strong>in</strong>ski, Adam, 144<br />
Ziemann, Elisabeth, 237<br />
Zitterbart, Robert<br />
Zlatkovic, Bojan, 294<br />
Zorlu, Yunus<br />
Zucker, S<strong>in</strong>a P., 146, 137<br />
Zühlke, Mart<strong>in</strong><br />
Zvyag<strong>in</strong>tseva, Tatiana N., 167<br />
327
328
Sudoku<br />
329
330<br />
C O H B<br />
F He<br />
O Li H Be He C N<br />
Li N<br />
Be He C H F<br />
B Li<br />
He N F Be F Li C<br />
He N<br />
B Be Li N
Mg<br />
S Mg P Na Ne<br />
Al Mg Si S<br />
Ne Si Mg<br />
Mg S Cl Ne P<br />
Ar Na Cl<br />
Cl Al Mg S<br />
Ne Al Ar S Na<br />
Na<br />
331
332<br />
Ga Kr<br />
Kr Se Ca<br />
Ca As Rb<br />
Rb As Se Ge<br />
As K<br />
Ca K Ga Kr<br />
Kr Se Br<br />
K Ga Ge<br />
K Rb
I Sb Cs Sn<br />
Sb Sn Xe<br />
In I Te<br />
Sn Cs<br />
Ba Sb<br />
Te Ba<br />
Ba Sr I<br />
In Ba Xe<br />
I Sr Xe Sn<br />
333
Supporters
9:00<br />
1 0:00<br />
1 1 :00<br />
1 2:00<br />
1 3:00<br />
1 4:00<br />
1 5:00<br />
1 6:00<br />
1 7:00<br />
1 8:00<br />
1 9:00<br />
20:00<br />
Wednesday<br />
March 6 th<br />
Registration<br />
1 2:00-20:00<br />
Social Activities<br />
1 6:00-1 9:00<br />
Welcome Reception<br />
20:00<br />
Thursday<br />
March 7 th<br />
Open<strong>in</strong>g Ceremony<br />
8:50-9:30<br />
Plenary Lecture<br />
Prof. Dr. S. Hashmi<br />
9:30-1 0:30<br />
Break<br />
1 0 m<strong>in</strong> Poster Talks<br />
3x 20 m<strong>in</strong> Oral<br />
Presentations<br />
1 0:50-1 2:00<br />
Friday<br />
March 8 th<br />
Lunch Break Lunch Break<br />
3x 20 m<strong>in</strong> Oral<br />
Presentations<br />
1 3:30-1 4:30<br />
3x 20 m<strong>in</strong> Oral<br />
Presentations<br />
1 3:30-1 4:30<br />
Break Break<br />
Plenary Lecture<br />
Dr. S. Loth<br />
1 4:50-1 5:50<br />
Break<br />
1 0 m<strong>in</strong> Poster Talks<br />
4x 20 m<strong>in</strong> Oral<br />
Presentations<br />
1 6:1 0-1 7:40<br />
Poster Session<br />
and Champagne<br />
Reception<br />
1 7:40-20:1 0<br />
Plenary Lecture<br />
Dr. habil. J. S. Becker<br />
9:1 0-1 0:1 0<br />
Break<br />
1 0 m<strong>in</strong> Poster Talks<br />
4x 20 m<strong>in</strong> Oral<br />
Presentations<br />
1 0:30-1 2:00<br />
Plenary Lecture<br />
Prof. Dr. P. R. Schre<strong>in</strong>er<br />
1 4:50-1 5:50<br />
Break<br />
1 0 m<strong>in</strong> Poster Talks<br />
4x 20 m<strong>in</strong> Oral<br />
Presentations<br />
1 6:1 0-1 7:40<br />
Break<br />
Conference D<strong>in</strong>ner<br />
1 9:00-21 :30<br />
Conference Party<br />
22:00<br />
Saturday<br />
March 9 th<br />
Poster Session<br />
and<br />
"Frühschoppen"<br />
9:00-1 1 :30<br />
Clos<strong>in</strong>g Lecture<br />
Prof. Dr. K. Roth<br />
1 1 :30-1 2:30<br />
Clos<strong>in</strong>g Ceremony<br />
1 2:30-1 3:30<br />
Break<br />
Social Activities<br />
1 4:00-1 9:00