International Summer School PROGRAM - Laboratoire d'Infochimie ...

4 th International
Summer School
September, 12-15 2011
University Regensburg/Germany

4 th International
Summer School
We are grateful for the financial support from the following
institutions:
Universitätsstiftung Hans Vielberth
Bayerisches Hochschulzentrum für
Mittel-, Ost- und Südosteuropa
Universität Regensburg
Forschungsrat UR
VolkswagenStiftung
FCI Fond der chemischen Industrie

4 th
International Summer School
“Supramolecular Systems in Chemistry and Biology”
PROGRAM
September, 12-15 2011, Regensburg (Germany)
Monday, September 12 th
10 am – 2 pm Registration of Participants (Chemistry Building)
2 – 2.30 pm Welcome Address
2.30 – 4 pm Session I (Functional Supramolecular Systems)
Chair: Vitaly Kalchenko
Opening lecture 2.30 – 3.30 pm David Reinhoudt, Twente, The Netherlands (L1)
4.15 – 4.45 pm Coffee Break
“From Supramolecular Chemistry to
Nanofabrication”
3.30 – 4 pm Aslan Tsivadze, Moscow, Russian Fed. (L2)
“Innovative Developments on the Basis of
Supramolecular Systems”
4 – 4.15 pm Benjamin Gruber, Regensburg, Germany (ST1)
“Synthetic Vesicle Membranes: Molecular
Recognition and Reactivity at the Interface”

4.45 – 6.15 pm Session II (Inclusion Compounds I)
Chair: Alexandre Varnek
4.45 – 5.15 pm Igor Antipin, Kazan, Russian Fed. (L3)
„Calixarenes: From Molecular Receptor to
Supramolecular Systems“
5.15 – 5.45 pm Jürgen Schatz, Erlangen, Germany (L4)
„Metathesis in Water – A Case Study for
Supramolecular Modification of Reactivity“
5.45 – 6.15 pm Vladimir Král, Prague, Czech Republic (L5)
“Controlled and Targeted Drug Delivery Using a
Supramolecular System”
6.15 – 6.30 pm Ivan Vatsouro, Moscow, Russian Fed. (ST2)
“Novel Calixarene- and Biscalixarene Based
Heteroditopic Receptors”
7 – 8.30 pm Mix and Mingle – Barbeque and Beer

Tuesday, September 13 th
9 – 10.30 am Session III (Bio-Inspired Systems)
Chair: Aslan Tsivadze
10.30 – 11 am Coffee Break
9 – 9.30 am Carsten Schmuck, Essen, Germany (L6)
„What does the Recognition of Biomolecules
and Switchable Nanoassemblies have in
Common? Interacting Molecules!
9.30 – 10 am Sylvie Ferlay, Strasbourg, France (L7)
“Variation around Charge-Assisted H-Bonded
Molecular Networks”
10 – 10.15 am Veronique Hubscher, Strasbourg, France (ST3)
“Binding Properties of Calix[4]Arene-Amides
and Thioamides and their Application in Ion
Selective Electrodes”
10.15 – 10.30 am Sergey Paramonov, Moscow, Russian Fed. (ST4)
11 – 12.30 am Session IV (Bio-Inspired Systems)
Chair: Sabine Amslinger
“Photo-Control of Binding Ability of Crown-
Annelated Chromenes”
11 – 11.30 am Piotr Bregestovsky, Marseille, France (L8)
“Light and Molecular Design in Biological
Applications”
11.30 – 12 am Evgeny Kataev, Chemnitz, Germany (L9)
“ Identification of Sensors and Recognition
Mechanisms from Ligand-Metal-Analyte
Libraries”

12.30 – 2.30 pm Lunch Break
12 – 12.15 am Pascal Jonkheijm, Twente, The Netherlands
(ST5)
“Supramolecular protein immobilization”
12.15 – 12.30 am Alexandr Shkrabak, Kyiv, Ukraine (ST6)
“The Effect of Calixarene C-107 On Kinteic
Characteristics Of Nа+,К+-АТРase Of
Myometrium Plasma Membrane”
2.30 – 4 pm Session V (Inclusion Compounds II)
Chair: Vladimir Fedin
4 – 4.30 pm Coffee Break
2.30 – 3 pm Oren Scherman, Cambridge, United
Kingdom (L10)
“Cucurbiturils at the Interface between
Supramolecular Chemistry and Materials
Science”
3 – 3.30 pm Vitaly Kalchenko, Kyiv, Ukraine (L11)
“Supramolecular Chemistry of Calixarenes.
Fundamental and Practical Aspects”
3.30 – 3.45 pm Tim Reimers, Kiel, Germany (ST7)
“Chiral Concave N-Heterocyclic Carbenes”
3.45 – 4 pm Rustem Zairov, Kazan, Russian Fed. (ST8)
“Europium(III) Doped Polyelectrolyte
Nanocapsules. Collodial and Photophysical
Properties”

4.30 – 5.30 pm Poster Short Talks (10 x 5 min Short Oral Presentations)
Chair: Sylvie Ferlay / Julia Gorbunova
Vladimir Burilov, Kazan, Russian Fed. (PT1)
“The Sensing of Interfacial Interactions of Tb-Doped Silica
Nanoparticles with Various Substrates through the "On Off-On"
Switching of Tb-Centered Luminescence. Mechanisms and
Applications.”
Josè Augusto Berrocal, Rome, Italy (PT2)
“Thermodynamic Template Effect in Dynamic Combinatorial
Chemistry"
Alexander Gerasimov, Kazan, Russian Fed. (PT3)
“Molecular Recognition of Organic Quests by Thin Layers of
Phosphorous-Containing Dendrimers”
Oleksandr Zaichenko, Lviv, Ukraine (PT4)
"Bioactive Nanoscale Supramolecular Assemblies of Ionic and Non
Ionic Oligoperoxide Based Surfactants with Drugs, DNA and RNA in
Water”
Alexander Martynov, Moscow, Russian Fed. (PT5)
“Towards a Molecular Assembly Based on 1,10-Phenanthroline-
Functionalized Phthalocyanines”
Kerstin Anhuth, Duisburg-Essen, Germany (PT6)
"Metallosupramolecular Polymers with Orthogonal Interactions”
Maxim Oshchepkov, Moscow, Russian Fed. (PT7)
“Analysis of Benzodiazacrown-15-crown-5 Ether Derivative
Binding Properties by Potentiometric, Optical and Extraction
Methods”
Kajetan Dabrowa, Warsaw, Poland (PT8)
„Novel Photoresponsible Anion Receptors“
Artem Smolentsev, Novosibirsk, Russian Fed. (PT9)
"Crown-Containing Derivatives of Naphthopyrans:Cation Binding,
Photochemical and Fluorescent Properties“
Alena Yantemirova, Kazan, Russian Fed. (PT10)
"Thiacalix[4]Arenes: Synthesis and Molecular Recognition of some
Anions”
5.30 – 8 pm Posters with Bavarian Food, Beer and Pretzels

Wednesday, September 14 th
9 – 10.30 am Session VI (Functional Supramolecular Systems I)
Chair: Mir Wais Hosseini
10.30 – 11 am Coffee Break
9 – 9.30 am Lechoslaw Latos-Grazynski, Warsaw,
Poland (L12)
“Aromaticity Switching in Porphyrinoids and
Heteroporphyrinoids”
9.30 – 10 am Emmanuel Cadot, Versailles, France (L13)
“Rings and Capsules: Supramolecular Systems
based on the Mo2O2S2 Linker”
10 – 10.15 am Ina Krebs, Duisburg-Essen, Germany (ST9)
“Zwitterion-Chromophore Modules for White
Light Emitting Supramolecular Polymers”
10.15 – 10.30 am Pavel Panchenko, Moscow, Russian Fed. (ST10)
“Synthesis and Cation-Dependent Photophysical
Properties of Crown Containing 1,8
Naphthalimide Derivatives”
11 – 11.30 am Alexandre Varnek, Strasbourg, France (L14)
“Chemoinformatics Approaches to Virtual
Screening and in Silico Design”
11.30 – 12.30 am Session VII (Young Scientist Competition)
12.30 – 2.30 pm Lunch Break
Chair: Burkhard König / Kirsten Zeitler
National teams of participating young scientists will compete in
scientific challenges

2.30 – 4 pm Session VIII (Inorganic Self-Assembly)
Chair: Oliver Reiser
2.30 pm – 3 pm Vladimir Fedin, Novosibirsk, Russian Fed. (L15)
“Mikro- and Mesoporous Coordination
Polymers: Synthesis, Structure and Properties”
3 pm – 3.30 pm Manfred Scheer, Regensburg, Germany (L16)
“Phosphorous Ligands in Supramolecular
Chemistry”
3.30 – 3.45 pm Sébastian Floquet, Versailles, France (ST11)
“Synthesis, Characterizations and Applications
of Cyclic Oxothiomolybdenum Rings”
3.45 – 4 pm Elisabeth Isaak, Aachen, Germany (ST12)
“Lithium-Controlled Hierachical Assembly of
Ti(IV) Helicates”
4 – 5 pm Individual Transfer to Historic City Center
5 – 6.30 pm Guided City Tour
7 pm Conference Dinner

Thursday, September 15
th
9 – 10.30 am Session IX (Functional Supramolecular Systems II)
Chair: Igor Antipin
10.30 – 11 am Coffee Break
9 – 9.30 am Julia Gorbunova, Moscow, Russian Fed. (L17)
“Advances in the Supramolecular Chemistry of
Tetrapyrrolic Compounds”
9.30 – 10.15 am Luisa De Cola, Münster, Germany (L18)
“Self-Assembly for the Creation of New
(Electro)Luminescent Materials”
10.15 – 10.30 am Pawel Dydio, Amsterdam, The Netherlands
(ST13)
“Supramolecular Control of Catalyst Selectivity
in the Hydroformulation”
11 – 12.30 am Session X (Self-Assembly, Self-Organization)
Chair: Carsten Schmuck
11 – 11.15 am Roman Rodik, Kyiv, Ukraine (ST14)
“Cationic Amphiphilic Calixarenes: Self-
Assembly in Water Solutions and Virus-Sized
DNA Nanoparticles”
11.15 – 11.30 am Artemiy Mizerev, Moscow, Russian Fed. (ST15)
“Synthesis and Investigation of Complexing,
Optical and Electrochemical Activities of Crown-
Containing Oligothiophene Derivatives”

11.30 – 12.00 am Olga Federova, Moscow, Russian Fed. (L19)
“Supramolecular Devices Based on
Photoresponsive Assemblies of Cucurbit[7]uril
and Crown-Ether Derived Styryl and (Bis)styryl
Dyes”
12 – 12.30 am Mir Wais Hosseini, Strasbourg, France (L20)
„Molecular Tectonics: Design of
Enantiomerically Pure Tubular Crystals”
1 pm Closing Remarks, Departure, Optional Lunch
End of the Summer School

From supramolecular chemistry to nanofabrication
D.N. Reinhoudt
Laboratory for Supramolecular Chemistry and Technology
MESA+ Institute for Nanotechnology
University of Twente
The Netherlands
Like in microelectronics, the fabrication of nanomaterials and -devices will
most likely start with the patterning of surfaces at the nanoscale. Individual
nanostructures can be manufactured most easily when confined to a surface.
Host-guest systems have been developed that make use of supramolecular
chemistry in water. Nanopatterning on self-assembled monolayers of βcyclodextrine
receptors (molecular printboards) can be achieved by
supramolecular nano-imprint lithography or DPN nanolithography.
Using the concept of multivalency, molecules can be anchored permanently or
in a dynamic regime. Several examples of the immobilization of biomolecules
at such surfaces will be discussed.
A second way to pattern surfaces uses dynamic covalent chemistry. This
methodology has the same advantages as supramolecular patterning, but can
easily be combined with irreversible confinement, e.g. by reduction of an imine
linker. The patterning of surfaces with proteins that selectively recognize
cancer cells will be discussed. In this work it was discovered that under
conditions of microcontact printing or dip pen nanolithography ,covalent
reactions are much faster than from solution.
This observation has been used in click chemistry at surfaces and applied for
the generation of DNA arrays.

INNOVATIVE DEVELOPMENTS ON THE BASIS OF SUPRAMOLECULAR SYSTEMS
A.Yu. Tsivadze
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninsky Pr., 31/4, Moscow 119907 Russia, tsiv@phyche.ac.ru
Last years become more and more obvious that for developments of innovative technologies
on the basis of new classes of compounds it is necessary to reveal their features of supramolecular
organization. Many of important electrophysical, optical and sensor properties depend from
peculiarities of such organization. Supramolecular systems on a basis of metal complexes with
macrocyclic ligands possess unique physico-chemical properties allow to develop various unique
materials for the molecular electronics, alternative power industry, chemical technology, separation
of compounds, medicine. For creation of innovative technologies on the basis of the compounds it
is necessary to reveal their supramolecular organization depending on the various factors defining
important properties.
On the basis of the synthesized new classes of macrocyclic compounds are developed:
− electroluminescent materials and organic light-emitting diodes on their basis;
− photorefractive materials;
− electrocatalysts and fuel cells on their basis;
− extraction and sorption technologies for separation of isotopes and processing of radioactive
production wastes.
− organic solar cells.
Innovative problems on a way of application of the results of fundamental researches will be
discussed.

Synthetic vesicle membranes: Molecular recognition and reactivity at
the interface
Benjamin Gruber, Burkhard König*
University of Regensburg, Universitätsstraße 31, 93053 Regensburg
*e-mail: burkhard.koenig@chemie.uni-regensburg.de
Many fundamental biological processes take place at the membrane-water interface of
cells and involve membrane-proteins that act as receptors for external signaling
molecules or catalyze enzymatic reactions. Here we present some of our recent studies
about artificial receptors embedded in synthetic vesicle membranes [1-2] and vesicular
metal complexes promoting the hydrolysis of phosphodiester substrates. [3]
Figure 1. Vesicle membrane embedding of receptors and dyes for self-assembled
chemosensors (left) and metal catalysts for the cleavage of phosphodiesters (right).
____________________
[1] B. Gruber, S. Stadlbauer, K. Woinaroschy, B. König, Org. Biomol. Chem. 2010, 8,
3704.
[2] B. Gruber, S. Stadlbauer, A. Späth, S. Weiss, M. Kalinina, B. König, Angew. Chem.
Int. Ed. 2010, 49, 7125.
[3] M. Subat, K. Woinaroschy, C. Gerstl, B. Sarkar, W. Kaim, B. König, Inorg. Chem.
2008, 47, 4661.

Calixarenes: from molecular receptor to supramolecular systems
I.S.Antipin a,b , S.E. Soloveva a , I.I.Stoikov b , A.I.Konovalov a,b
a A.E.Arbuzov Institute of Organic & Physical Chemistry, 420088, Kazan, Russia,
Arbuzov str., 8. , b Kazan (Volga region) Federal University, 420008, Kazan, Russia,
Kremlevskaya str. 18, E-mail: iantipin@ksu.ru
Now one of the most perspective ways of the nanomaterials design is the "bottom-up"
technology in which the higher organized nanosystems are spontaneously formed due to
supramolecular self-organization and self-assembly from individual atoms and
molecules. A key element of supramolecular chemistry is the principle of the molecular
recognition. From this point of view, one of the actual problems of supramolecular
chemistry is the molecular design and synthesis of preorganized receptor and
amphiphilic molecules which are capable on the principles of molecular recognition and
multipoint interactions to form host-guest complexes as well as self-organized
supramolecular essembles and devices.
Nanotechnological approach "bottom-up" can be effectively implemented on the basis
of meta-cyclophanes: calix[4]arene 1, thiacalix[4]arene 2.
(1) (2) X= O, S, NH
Stereo and chemoselective functionalization of calix[4]arene platforms allows to change
significantly hydrophilic-lipophilic properties of macrocycles and to raise efficiency and
selectivity of the interaction with substrates. The regularities of aggregation and
complexation of calixarenes with substrates of different nature: non-electrolytes,
cations, anions will be discussed. Particular attention will be paid to the application of
calixarene derivatives for the construction of various supramolecular and nanosystems,
devices and "smart" materials: nanoparticles, metal-coordinated networks, Langmuir-
Blodgett nanolayers etc.
The support from RFBR (N 10-03-00728) is gratefully acknowledged.

Metathesis in Water – A Case Study for
Supramolecular Modification of Reactivity
Miriam Sessler, Jürgen Schatz
Organic Chemistry 1, Department Chemistry and Pharmacy,
University of Erlangen, Henkestr. 42, 91054 Erlangen / Germany
Generally, metathesis reactions are carried out in organic solvents and their potential
utilization in aqueous medium is largely unexploited. The majority of methods reported
for aqueous metathesis did not use pure water as a reaction medium but only organic
solvents with some percentage of water in it. [1] However, the idea of “green chemistry”
has encouraged us to develop a simple and environmentally benign ring-closing
metathesis (RCM) protocol based exclusively on aqueous media. [2]
Here, supramolecular, water-soluble additives based on e.g. calix[n]arenes exhibit a
beneficial influence on the RCM of non-polar substrates in pure aqueous medium using
standard Grubbs-type catalyst. Additionally to (micro)solubilization of both the catalyst
and starting material by the used macrocycles, ion-pair formation of the phosphonium
ion formed in aqueous solution and the added macrocycles seem to play a crucial role in
the ring-closing reaction.
[1] S. J. Connon, M. Rivard, M. Zaja, S. Blechert, Adv. Synth. Catal. 2003, 345, 572.
[2] Th. Brendgen, T. Fahlbusch, M. Frank, D. T. Schühle, M. Seßler, J. Schatz, Adv.
Synth. Catal. 2009, 351, 303.

Controlled and Targeted Drug Delivery Using Supramolecular System
Vladimír Král a,b , Jarmila Králová c , Martin Havlík b,c Kamil Záruba b , Pavel
Řezanka b , Zdeněk Kejík b , Tomáš Bříza b,d , Robert Kaplánek b,d , Pavel Martásek d
a Zentiva k.s., Part of the sanofi-aventis group, U Kabelovny 130, 102 37 Prague 10,
b Institute of Chemical Technology, Department Analytical Chemistry, Technická 5,
166 28 Prague 6, Czech Republic (email: vladimir.kral@vscht.cz),
c Institute of Molecular Genetics, AS CR, Flemingovo nam.2, Prague 6, Czech Republic,
d st
Charles University in Prague, 1 Faculty of Medicine, Kateřinská 32, Czech Republic.
Rational design of functional nanomaterials is of current interest because of a variety of
potential applications ranging from chemistry to biological sciences. One of the key
areas is selective drug delivery using supramolecular strategies. The uptake of
exogenous molecules such as drugs into cells can arise from a variety of mechanisms
that can be broadly classified as active and passive transport. Active uptake requires that
target molecules are recognized by specific intermolecular interactions, selected, and
shuttled across the cell membrane by receptors.
Porphyrin chemistry has undergone a renaissance over the past ten years due to
potential applications of these compounds in areas including supramolecular chemistry,
solar energy conversion and catalysis.
Here we describe application of porphyrin-conjugates for supramolecular targeted drug
delivery of cytostatic drugs and ODN in combination with photodynamic therapy.
Novel porphyrin-conjugates with oligoethyleneglycol, oligopeptide, alkaloid, mono-,
disaccharide, and cyclodextrin substitution showed significant binding properties as
well as photosensitizing potential in vitro and in vivo and displayed an increased
selectivity for malignant tissue. Moreover, polymethine and other polycationic
porphyrin derivatives exhibit not only very specific tumor localization, but also into-cell
antisense oligonucleotide transport properties as was demonstrated on the primary
leukemic cells.
Financial support from the Czech Grant Agency No. P303/11/1291, 203/09/1311,
P301/10/1426 and the Ministry of Education of the Czech Republic (projects No.
MSM6046137307 and LC06077) is gratefully acknowledged.

Novel calixarene- and biscalixarene-based heteroditopic receptors
Ivan Vatsouro, Kirill Puchnin, Boris Bolshchikov, Pavel Zaikin, Maria Logunova,
Vladimir Kovalev
Department of Chemistry, M.V. Lomonosov Moscow State University, Lenin’s Hills,
119991 Moscow, Russia
We present here the results of our research on the novel calix[4]arene-based
heteroditopic host for ion-pair recognition. The hosts of general type 1 are
functionalized calixtubes, which are easily available due to the use of 3-R-1-
adamantylcalix[4]arenes at the step of bis-calixarene preparation. The well established
cation binding site (especially for K +
) formed by eight calixtube oxygens is completed
with two of four urea groups for anion binging thus providing the heteroditopic action
of hosts 1.
Calix[4]arenes bearing one, two or four carboxymethyl groups at narrow rim
reacted with tryptamine or tryptophane methyl ester to give the heteroditopic hosts
through amide formation: the cation binging site is formed by amide oxygens while the
anion binding occurs at the indole NHs. The calixarenes with one or two distal indole
functionalities at narrow rim undergo inter/intramolecular dimerization when kept in
trufluoroacetic acid and then oxidized, thus giving the 2,2’-bisindole-bridged
calix[4]arenes 2 and bis-calix[4]arenes 3. The hosts of type 2 possess the more rigid
cation binding site if compared to their non-dimerized precursors and also the bisindole
fluorophore site for anion recognition.
This research was supported by Russian Foundation for Basic Research, grant
#09-03-00971.

What does the recognition of biomolecules and switchable nanoassemblies have
in common? Interacting Molecules!
Prof. Dr. Carsten Schmuck, Universität Duisburg-Essen, Universitätsstrasse 7,
45141 Essen, Germany
The lecture will focus on some recent achievements from our laboratory giving an
overview of the research going on in our group. Our research focuses on the
development, synthesis and evaluation of new supramolecular systems which function
in polar solvents and thus might have prospect for applications. Currently our work
mainly involves ionic interactions as a key non-covalent bond. We have introduced
guanidiniocarbonyl pyrroles as one of the most efficient oxoanion binding motifs known
so far relying on H-bond assisted ion pair formation. The systematic thermodynamic
study of knock-out analogues allows us to learn more about the importance of
individual non-covalent interactions for the overall binding affinity.
With the help of combinatorial approaches, we have used this binding motif to develop
sensors for amino acids or highly efficient stereoselective receptors for oligopeptides.
Currently, we are working on protein surface or DNA recognition. For example,
tetravalent peptide ligands identified from the screening of a combinatorial library were
shown to be highly efficient non-competitive enzyme inhibitors working by binding to
the protein surface thus blocking the access to the active site.
We are also interested in self-assembling zwitterions which form soft materials such as
vesicles, polymers or monolayers in polar solvents and on surfaces. For example, very
recently we developed a supramolecular polymer based on a monomer with two
orthogonal self-complementary binding sites using either metal-ligand or ionic
interactions. In a hierarchical self-assembly process this molecule first forms ion paired
dimers which can be polymerized by the addition of metal ions.

Variation around charge-assisted H-bonded molecular networks
Sylvie FERLAY, Mir Wais HOSSEINI
LCCO, Université de Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg, France.
ferlay@unistra.fr
Dicationic bisamidinium have been shown to be particularly well adapted to form, when
associated with polycyanometallates, perfectly robust molecular networks, by charge-assisted
H-bonds. In particular, upon combining hexacyanometallate anions [M III (CN)6] 3- (M = Fe, Co,
Cr) or, in certain conditions [Fe II (CN)6] 4-
, with bisamidinium molecules 1, 2, or 3, analogous
2-D networks are obtained in the solid state and have been studied from a structural point of
view (see scheme) [1-5]. With 1 or 2, the formed networks are porous, whereas they are filled
with the propyl chains beard by 3.
R
H H
H H
H H
N
N
N
N
N
N
+ ) ( + HO + ) ( + OH
+ )
( +
N
N
N
N
N
N
H H
H H
H H
1 2 3
CN
NC CN
M
NC CN
CN
+
H
H
N
+ )
N
( + R
N
N
H
H
Scheme: General formation of the two dimensional networks (X-2H + )3[M III (CN)6] 3- 2
(X=1, 2 or 3, and M = Cr, Fe or Co) or Y(3-2H + )3[Fe II (CN)6] 4- 2 (Y=Na, K, Rb, Cs)
The porosity of the formed system has been studied as well as the post synthetic
modification, and also the construction of singular units called "crystals of crystals".[6-8]
[1] S. Ferlay, O. Félix, M.W.Hosseini, J.-M. Planeix, N. Kyritsakas, Chem. Commun. , 2002, 702.
[2] S. Ferlay, V. Bulach, O. Félix, M. W. Hosseini, J-M. Planeix, N. Kyritsakas, CrystEngComm, 2002, 447.
[3] P. Dechambenoit, S. Ferlay, M.W.Hosseini, J.-M. Planeix, N. Kyritsakas, New J. Chem., 2006, 30, 1303.
[4] P. Dechambenoit, S. Ferlay, M. W. Hosseini, N. Kyritsakas J. Am. Chem. Soc., 2008, 130, 17106.
[5] P. Dechambenoit, S. Ferlay, M. W. Hsseini, N. Kyritsakas Chem. Comm., 2009, 1559-1561.
[6] P. Dechambenoit, S. Ferlay,, N. Kyritsakas and M. W. Hosseini Chem. Commun., 2010, 868-870.
[7] P. Dechambenoit, S. Ferlay,, N. Kyritsakas, M. W. Hosseini , Chem. Commun., 2009, 6798 - 6800.

Binding properties of calix[4]arene-amides and thioamides and their application in ion
selective electrodes
a
V. Hubscher-Bruder a , J. Kulesza a,b , F. Arnaud-Neu a b
, M. Bocheńska
Department of Analytical Sciences”, IPHC, UMR 7178 (CNRS-UDS), ECPM,
25 rue Becquerel, 67087 Strasbourg Cedex 02, France
b
Department of Chemical Technology, Technical University of Gdansk
ul. Narutowicza 11/12, 80-264 Gdansk, Poland
At present, the importance of detecting and controlling the toxic heavy metals (such as
Cd 2+ or Pb 2+
) in waters, is extremely important, being a challenge for chemists who design
and synthesize selective ligands for these cations.
We report here the study of calix[4]arene-thioamides as potential sensing material for
transition and heavy metal cations. By introducing soft sulphur atoms into the structure of the
calix[4]arene, the preference for binding heavy and transition metal cations, toxic for human
beings, was expected. Although some examples of calixarene-thioamides applications are
known from the literature, only few publications deal with, for instance, stability constants
1-3
determination which is important in studying new ligands properties.
The interactions of these ligands with several representative cations (Na + , Ca 2+ , Gd 3+ ,
Ag + , Cd 2+ , Pb 2+ , Zn 2+ and Cu 2+ ) were studied using different techniques: liquid-liquid
extraction, 1
H NMR, X-ray diffractometry, UV spectrophotometry, potentiometry and
microcalorimetry. The properties of calix[4]arene-thioamides were compared with their
corresponding calix[4]arene-amides. Some of these thioamides derivatives were used as
active materials in ion-selective membrane electrodes (ISEs).
[1] F. Arnaud-Neu, G. Barrett, D. Corry, S. Cremin, G. Ferguson, J. F. Gallagher, S. J. Harris, M. A. McKervey,
M. J. Schwing-Weill, J. Chem. Soc., Perkin Trans. 2, 1997, 575
[2] M. G. Drew, P. D. Beer, M. I. Ogden, Acta Cryst., 1997, C53, 472
[3] K. No, J. H. Lee, S. H. Yang, S. H. Yu, M. H. Cho, M. J. Kim, J. S. Kim, J. Org., 2002, 67, 3165

Photo-control of binding ability of crown-annelated chromenes
S.V.Paramonov, 1 V.Lokshin, 2 Yu.V.Fedorov, 1 O.A.Fedorova 1
1
A.N.Nesmeyanov Institute of Organoelement Compounds RAS,
28 Vavilova st., 119991 Moscow, Russia. E-mail: paramonov@ineos.ac.ru
2
Centre Interdisciplinaire de Nanoscience de Marseille (CINaM, CNRS UPR 3118),
163 Av. de Luminy, 13288 Marseille, France
Photochromic compounds were proved to be of high demand in
modern technologies due to their optical properties. One of the
interesting trends in developing of new photochromic systems consists
in preparation of multifunctional compounds with photo-controlled
properties. This work is focused on isomeric crown-annelated
chromenes and the use of UV irradiation to control photochemically
their binding ability towards metal ions and protonated amino acids.
We studied binding ability of 15-crown-5-annelated chromenes
towards magnesium (II), barium (II) and lead (II) ions. Prior to
irradiation the chromenes form stable complexes with all cations, the
composition and the structure depending on the ion nature. Upon
irradiation the photoinduced forms also formed complexes of lower
stability.
The similar effect was observed for the 18-crown-6-annelated chromenes with several
protonated amino acids. Without irradiation, all amino acids were bound by their ammonium group
to the crown ether moiety of the chromenes (1:1 complexes). Upon irradiation, the corresponding
merocyanines formed different types of complexes depending on the amino acid length. In all cases,
the stability of the 1:1 complexes after irradiation was lower.
The conclusions are supported by UV-Vis and NMR investigations. The synthetic approach
to the described systems is also discussed.
Acknowledgments to RFBR program (10-03-93105), International Research Group
«Photoswitchable Organic Molecules Systems and Devices (PHENICS) and Réseau Formation-
Recherche Franco-Russe du Ministère de la Jeunesse de l'Education Nationale et de la Recherche
for financial support.

“Light and Molecular Design in Biological Applications”
1
Piotr Bregestovski
INSERM U 751, 13385 Marseille, France
piotr.bregestovski@univmed.fr
Photochromic switches and genetically encoded biosensors become a
powerful tools for modulation activity of neurons and neuronal networks. Our
understanding the mechanisms underlying development and functioning of
the nervous system has greatly advanced in recent years due to the
development of these powerful molecular and genetic tools. Remote sensors
allow to probe localisation and function of various neuronal proteins, cells and
networks. Controlled by light molecular consctructs allow to switch on and off
the activity of specific proteins and to control the excitation of neurons with
high temporal and spatial resolution. A number of light-sensitive biosensors
for non-invasive monitoring of ions and enzymes has been developed. These
molecular designs expand extremely rapidly and a number of new
approaches for image analysis of various proteins in living cells has being
proposed. Resent observations and application of new tools for molecular
imaging and remote activation of receptors, ionic channels and synaptic
networks will be presented.

Identification of sensors and recognition mechanisms from ligand-
metal-analyte libraries
Evgeny Kataev
Institute of Chemistry, Chemnitz University of Technology, Strasse der Nationen 62,
09111 Chemnitz, Germany, E-mail: evgeny.katayev@chemie.uni-r.de
In this work we explore a novel approach for the search of selective sensors and
receptors for a given analyte using dynamic combinatorial chemistry. It is based on the
idea that selectivity of an analytical signal or a binding event can be gained by
diversifying the number of possible interactions between guest and components of a
dynamic library. The standard approach for the design of a sensor involves covalent
connection of a recognition site to an analytically reporting unit (e.g. fluorescent
molecule). In our approach we design several ligands bearing fluorophores that can't
directly interact with an analyte. Ligands can coordinate metal cations and only then,
the resulting complex can interact with an analyte. Two libraries which possess
described properties are shown below in the Figure. The first library is designed for the
fluorescent sensing of ATP in aqueous solution. In the second library we have observed
adaptable behaviour of the library "ligand+Zn 2+
" in response to the diamines.
References:
NH
N
N
L anthr L coum
+CuCl2
O
O
NH
N
Fluorescent sensing of ATP
O O
N
NH H HN
NH HN
N N
+ Zn(ClO 4) 2
Self-assembly is sensitive to
the amount of an amine
E. A Katayev, M. B. Schmid, Control of metal-directed self-assembly by metal-amine
interactions. Dalton. Trans. 2011, 40, 2778-2786

Supramolecular protein immobilization
A. González-Campo, J. Cabanas-Danes, L. Yang, D. Wasserberg, J. Huskens,
P. Jonkheijm*
Molecular Nanofabrication, University of Twente, P.O. Box 217, 7500 AE, Enschede,
Netherlands.
The immobilization of proteins onto surfaces is a continually growing area. 1 New
results to immobilize proteins, which are sensitive to remote electrochemical stimuli,
using cucurbituril (CB) and cyclodextrin (CD)-modified surfaces will be presented.
Site-selectively ferrocene-tagged fluorescent protein binds to self-assembled surfaces
through weak or strong interactions between the ferrocenyl guest and the host surface of
beta-CD or CB[7]. Upon reduction of the ferrocene unit, the protein was removed from
either surface, with the CD surface showing the fastest disassembly kinetics. The
stimuli-responsive attachment used will open new avenues for cell-responsive studies.

THE EFFECT OF CALIXARENE C-107 ON KINETIC
CHARACTERISTICS OF Nа + ,К +
-АТРase OF MYOMETRIUM
PLASMA MEMBRANE
Shkrabak O.A. 1 , Veklich T.O. 1 2
, Rodik R.V.
1 Palladin Institute of Biochemistry, NASU, Kyiv; e-mail: veklich@biochem.kiev.ua
2 Institute of Organic Chemistry, NASU, Kyiv; e-mail: manli@ioch.kiev.ua
We investigated the inhibitory action of calixarene C-107 (5,17-diamino(2-
pyridyl)methylphosphono-11,23-di-tret-butyl-26,28-dihydroxy-25,27-
dipropoxycalix[4]arene) on Na + ,K + -ATPase activity kinetic properties of myometrium
perforated plasma membrane. It was shown that this calixarene, inhibiting Na + ,K + -
ATPase, did not change the kinetic parameters (Km, nH) of reaction velocity dependence
on substrate concentration. The constant КMg of enzyme activation by MgCl2 had
complex dependence on calixarene C-107 concentration: increased twice from 173 ± 4
µM to 375 ± 43 µM with growth of calixarene concentration up to 50 nM and decreased
to control level with further growth of calixarene concentration to 100 nM. The Hill
cooperativity coefficient nH of activation by MgCl2 did not vary in the presence of
mentioned calixarene. Both ATP and MgCl2 had no influence on Na + ,K + -АТРase
constant of inhibition by calixarene C-107, but the concentration increase of mentioned
physiological compounds caused the growth of cooperativity coefficient nH of
enzymatic reaction inhibition by calixarene C-107. It was also shown that this
calixarene increased the affinity of the enzyme to the sodium pump conventional
inhibitor - ouabain: the magnitudes of the apparent constant of inhibition I0.5 changed
from 26.9 ± 1.3 µM to 10.9 ± 0.6 µM. However, the ouabain itself did not influence on
the affinity of the Nа + ,K +
-АТРase to сalixarene С-107.
Therefore, we can conclude that inhibitory action of calixarene C-107 on Na
ATPase has uncompetitive character and, perhaps, interaction of calixarene C-107 with
enzyme leads to decrease of enzyme turnover number.
+ ,K +
We are thankful to corresponding members of NASU V.I. Kalchenko and S.O.
Kosterin for helpful discussion and scientific cooperation.
-

Cucurbiturils at the interface between supramolecular chemistry and materials science
Our research interests include the development of controlled polymer architectures, 1 hybrid
nanoparticle assemblies, 2 and the integration of dynamic supramolecular systems onto surfaces. 3
Using cucurbit[n]urils (CB[n]s) we adopt a simple bottom-up approach to achieve sophisticated
designs which are directed at the preparation of novel photonic devices, high-density patterned
media, and chemical and biological sensors. 4 Our CB[n] based host-guest systems exhibit dynamic
self assembly and are capable of responding to stimuli (photochemical, chemical, and thermal)
which allow for external control and function to be built into the materials. Modification of solution
viscosity using multivalent polymers 5 and imidazolium based ionic liquids 6 have been
accomplished through dynamic crosslinking in water using CB[n]s to produce colorful hydrogels
and hierarchical architectures. Furthermore, polymer-inorganic composite materials can be readily
prepared based on the CB[8] coupling of multivalent gold nanoparticles to copolymers. 7 When
these systems are attached onto gold surfaces intricate control is achieved over the site-selective
immobilization of colloids 3 and peptides. This has great scope for the development of optical
materials, chemical sensors and biological separations.
hierarchical self assembly dynamic hydrogels
nanoparticle assembly self-assembled surfaces
1. Rauwald, U.; Scherman, O. A. Angew. Chem. Int. Ed., 2008, 47, 3950-3953.
2. Lee, T.C.; Scherman, O.A. Chem. Commun., 2010, 46, 2338-2440.
3. Tian, F.; Cheng, N.; Nouvel, N.; Geng, J.; Scherman, O.A. Langmuir, 2010, 26, 5323-5328.
4. Zayed, J.M.; Nouvel, N.; Rauwald, U.; Scherman, O.A. Chem. Soc. Rev., 2010, 39, 2806-2816.
5. Appel, E.A.; Rauwald, U.; Jones, S.; Zayed, J.M.; Scherman, O.A. J. Am. Chem. Soc., 2010,
ASAP, DOI: 10.1021/ja106362w.
6. Jiao, D.; Biedermann, F.; Tian, F.; Scherman, O.A. J. Am. Chem. Soc., 2010, ASAP, DOI:
10.1021/ja106716.
7. Coulston, R.; Jones, S.T.; Lee, T.C.; Appel, E.A.; Scherman, O.A. Chem. Commun., in press,
DOI: 10.1039/C0CC03250F.

SUPRAMOLECULAR CHEMISTRY OF CALIXARENES.
FUNDAMENTAL AND PRACTICAL ASPECTS
Vitaly Kalchenko
Institute of Organic Chemistry, National Academy of Sciences of Ukraine
02660, Kiev-94, Ukraine, vik@ioch.kiev.ua, www.ioch.kiev.ua/calix
Calixarenes are versatile molecular scaffolds for design of highly efficient and selective
receptors, self-assembling systems and well defined functional nanostructures. The
paper will report the molecular modeling, synthesis, structural investigations of
phosphorus, nitrogen and sulfur containing (thia)calixarenes and their supramolecular
complexes with a series of bio-relevant or ecologically hazardous molecules, cations
and anions.
The special attention will be paid to chiral and water-soluble calixarenes in
context of bio-medical investigations. An application of the P,N,S-containing
calixarenes toward radionuclides extraction, chemosensors constructions, functional
nanoparticles formations and drug design will be discussed.
References:
[1] For review see: Cherenok S., Dutasta J.-P., Kalchenko V. Current Organic
Chemistry. 2006.10. 2307-2331; Kalchenko V. UPAC. 2008. 80. 1449-1458; Rodik
R.V., Boyko V.I., Kalchenko V. I. Current Medicinal Chemistry. 2009. 16 (13), 1630-
1655. Cherenok S., Kalchenko V. Topics in Heterocyclic Chemistry. 2009. 20. 229-273.
[2] Kasyan O., Kalchenko V., Bolte V., Bohmer V. Chem. Commun. 2006. 1932–1934.
[3] Cherenok S., Vovk A., Muravyova I., Shivanyuk A., Kukhar V., Lipkowski J.,
Kalchenko V. Organic Letters. 2006. 8. 549-551.
[4] Notestein J.M., Andrini L.R., Kalchenko V.I., Requejo F.J., Katz A., Iglesia E.
J. Am. Chem. Soc. 2007. 129. 1123-1131.
[5] Cherenok S., Vovk A., Muravyova I., Shivanyuk A., Kukhar V., Lipkowski J.,
Kalchenko V.Organic Letters. 2006. 8. 549-552.
[6] Torgov V.G., Us T.V., Korda T.M., Kostin G.A., Miroshnichenko S.I., Klimchuk
O.V., Kalchenko V.I. J. Inclusion Phenomena and Macrocyclic Chemistry. 2008. 62.
51-58.
[7] Klyachina M.А., Yesypenkо O.A., Pyrozhenko V.V., Shishkina S.V., Shishkin
O.V., Boyko V.І., Kalchenko V.I. Tetrahedron. 2009. 65. 7085-7091.
[8] Ha J.-M., Katz A., Drapailo A.B., Kalchenko V. I. J. Phys. Chem. C. 2009. 113.
1137-1142.
[9] Vovk A.I., Kononets L.A., Tanchuk V.Yu, Cherenok S.O., Drapailo A.B.,
Kalchenko V.I., Kukhar V.I. Bioorg. Med. Chem. Lett. 2010. 20. 483–487.
[10] Solovyov A.V., Cherenok S.O., Kalchenko O.I., Atamas L.I., Kazantseva Z.I., Koshets I.A.,
Tsymbal I.F., Kalchenko V.I. Journal of Molecular Liquids. 2011. 159. 117–123.

Chiral Concave N-Heterocyclic Carbenes
Tim Reimers, Ulrich Lüning*
Otto-Diels-Institut für Organische Chemie, Olshausenstraße 40, 24098 Kiel, GER
treimers@oc.uni-kiel.de, luening@oc.uni-kiel.de
In the last two decades, N-heterocyclic carbenes (NHC) have gained large interest.
They are widely applied in organocatalysis and also as ligands in transition metal
catalyzed reactions, e.g. Grubbs’ Second Generation Catalyst. [1]
Due to their versatility,
a control of their reactivity and selectivity is desirable.
For example, the incorporation of an NHC in a concave bimacrocycle was realized
by Winkelmann (for precursor see structure A). The influence of the concave shape of
[2]
the catalyst in respective reactions has already been shown. In order to achieve
enantioselectivity, axial chirality was created by exchanging a phenyl bridgehead for a
naphthyl unit (structure B).
O
N
N
O
O O
Me
Me
O
O
* N N * * N N *
O O
O O
A B C
O O
Figure 1: Three concave NHC precursors: A is achiral, B and C are axially chiral,
but only C is configurationally stable.
If the backbone of the NHC precursor is not modified, a rotation of the N-heterocycle
along the CAr-N bond is observed. This leads to an equilibrium of the two
enantiomers at room temperature and separation is not possible.
This contribution shows an approach to avoid the rotation by adequate substitution
to reach configurational stability. The synthesis of a respective axially chiral bimacro-
[3]
cycle has been accomplished (structure C). The stabilization of the configuration has
been proven by NMR experiments and by chiral HPLC. The application of axially
chiral bimacrocyclic N-heterocyclic carbenes in enantioselective supramolecular
catalysis is the final goal.
[1] M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953-956.
[2] O. Winkelmann, U. Lüning, Supramol. Chem. 2009, 21, 223-229.
[3] T. Reimers, C. Näther, U. Lüning, Eur. J. Org. Chem. 2011, 1040-1046.
[2]

EUROPIUM(III) DOPED POLYELECTROLYTE
NANOCAPSULES. COLLOIDAL AND PHOTOPHYSICAL
PROPERTIES
R. Zairov, A.Mustafina, A.Konovalov
A.E.Arbuzov Institute of organic and physic chemistry KSC RAS,
Kazan, 420088, Russia, e-mail: rustem@iopc.ru
Novel highly luminescent europium(III) thenoyltrifluoroacetonate adduct with
phosphineoxide 1 was capsulated into polyelectrolyte (PE) capsule fabricated through
layer-by-layer procedure. The poly(sodium 4-styrenesulfonate) (PSS) was applied as the
first layer. Positively charged polyethyleneimine (PEI) has been deposited on PSS
coated particles resultin in their recharging from minus to plus. The further three layers
of the abovementioned oppositely charged polyelectrolytes were stepwise deposited on
PEI-PSS coated Eu(TTA)31 particles in the similar route. The multilayer PE shell
protects highly luminescent core from deactivation and decomposition (due to pH
changes or ligand substitution) and also provides colloidal stability of Eu(TTA)31
containing capsules in water.
Photophysical properties, size and
electrokinetic potential in aqueous
solutions were studied at the various
number of PE layers. AFM images of
dried samples were also obtained. The obtained core-shell nanoparticles exemplify
stimuli responsive colloids, which are able to give luminescent response on the
interfacial interactions with substrates. The quenching effect of organic (dye) and
inorganic (metal ions) is represented as the basis of sensing function.
The multifunctional core-shell nanoparticles were developed with luminescent
Eu(III) complex as the core and paramagnetic metal ions with high magnetic relaxation
rates (Cu(II), Mn(II) and Gd(III)) incorporated at the interlayer of the polyelectrolyte
multilayer shell.
Acknowledgement: RFBR (grant 10-03-00352a)

Aromaticity Switching In Porphyrinoids And Heterorphyrinoids
Lechosław Latos-Grażyński
University of Wrocław, Wrocław, POLAND, llg@wchuwr.pl
One of the ways to study the phenomenon of aromaticity is through the synthesis of new
molecules, which are often specifically designed to test various aspects of the theory or
to pose new problems. 1 Aromaticity of porphyrinoids can be influenced by a variety of
structural modifications, such
as peripheral substitution,
covalent linking of multiple
macrocycles, ring expansion
or contraction, and
introduction of non pyrrolic
subunits. The latter approach
is most readily realized by
replacing one of the pyrrole
rings of the porphyrin with a
different hetero- or carbocyclic fragment. Such a modification can have a profound
influence on the aromaticity of the macrocycle, as demonstrated by the investigated
family of porphyrinoids (1 – 7). The studies have been focused on the physical
manifestations of aromaticity, with a special emphasis on NMR spectroscopy. The aim
of the presentation is to provide a description of porphyrinoid aromaticity and its
connection with linking mode of arene moieties, tautomeric equilibria, intramolecular
rearrangements, reversible peripheral modifications, oxidation state or coordination. The
selected processes act as peculiar reversible switches of aromaticity. For instance a
figure-eight expanded porphyrinoid 5 exhibits an unprecedented controlled switching
between several Möbius and Hückel π-delocalization modes. 2 Similarly the palladium
complexes of vacataporphyrin 2 reveal Hückel aromaticity or Möbius antiaromaticity of
[18]annulene applying a butadiene fragment of vacataporphyrin as a topology selector. 3
(1) Stępień, M., Sprutta, N., Latos-Grażyński, L., Angew. Chem. Int. Ed. 2011, 50, 4288-4340.
(2) Stępień, M.; Latos-Grażyński, L.; Sprutta, N.; Chwalisz, P.; Szterenberg, L. Angew. Chem. Int. Ed.
2007, 46, 7869-7874.
(3) Pacholska-Dudziak, E.; Skonieczny, J.; Pawlicki, M.; Szterenberg, L.; Ciunik, Z.; Latos-
Grażyński, L. J. Am. Chem. Soc. 2008, 130, 6182-6195.

Supramolecular Polyoxothiometalates Paneling through
{Mo2O2S2 } coordination: Structure, dynamics and
Reactivity
Sébastien Floquet and Emmanuel Cadot
Institut Lavoisier de Versailles, UMR 8180, CNRS. Université de Versailles Saint Quentin, 45
Avenue des Etats-Unis, 78035 Versailles CEDEX
E.mail cadot@chimie.uvsq.fr
The early transition metal oxy-sulfide
clusters based on the {M2S2O2} (M=Mo or W)
building unit constitute a novel, original and
promising class of compounds [1] . Such molecular
materials, ranging in a sub-class of the transition
metal oxides, so-called polyoxometalates are of
both intrinsic and fundamental interests and their
properties are potentially attractive in diverse
fields such as analysis, biochemistry, catalysis
and medicine [2] . The acidic properties of the
oxothiocation [Mo2O2S2] 2+ toward bases such as lacunary polyoxotungstate anions or
hydroxide ion were investigated. [3,4]
Depending on subtle variations of the synthetic
conditions, large supramolecular assemblies were synthesized and characterized by single
crystal X-ray diffraction and multinuclear NMR in solution. Fundamental criteria governing the
stereochemistry of the self-assembly will be discussed with regard to the individual properties
(geometry, host-guest complementarities, coordination requirement) of the reactive moieties.
References
1. E. Cadot, F. Sécheresse, Chem. Commun. 2002, 2189-2199.
2. D-L. Long, R. Tsunashima, L. Cronin, Angew. Chem. Int. Ed. 2010, 49, 1736 – 1758
3 J-F. Lemonnier, S. Duval, S. Floquet and E. Cadot, Israel J. Chem. 2011, 51(2) 290.
4 S Duval, S. Floquet, C. Simonnet-Jégat, J. Marrot, R. Ngo Biboum, B. Keita, L. Nadjo, M. Haouas,
F. Taulelle and E. Cadot, J. Am. Chem. Soc. 2010, 132, 2069-2077.
1

Zwitterion-chromophore modules for
white light emitting supramolecular polymers
Ina Krebs and Carsten Schmuck
Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstraße 7, 45141
Essen, Germany
With my talk I intend to show the synthesis of chromophore-zwitterion modules for
supramolecular white light emitting polymers. These polymers would be formed via the selfassembly
of the zwitterionic subunits. Therefore I use the self-complementary
guanidiniocarbonylpyrrole-zwitterion developed by our group which has already been
successfully used to obtain water stable supramolecular polymers and other nanostructured
materials such as vesicles. [1,2] By combining this zwitterion with different fluorescent
chromophores, light emitting supramolecular polymers should be accessible.
Figure 1: Synthesized molecules.
As known from the theory behind different color spaces, white light emission is obtained by
mixing different colored dyes e.g. red, green and blue dyes. With the right mixing ratio of
different colored zwitterions-chromophore units it should be possible to get a white light
emitting solution. The main advantage of this zwitterion driven supramolecular aggregation,
besides its stability in aqueous solutions, is that the self-aggregation can be reversibly
switched on and off e.g. by pH adjustments.
[1] C. Schmuck, W. Wienand, J. Am. Chem. Soc. 2002, 125, 452 - 459.
[2] C. Schmuck, T. Rehm, K. Klein, F. Gröhn, Angew. Chem. 2007, 46, 1693 - 1697.

1
Synthesis and Cation-Dependent Photophysical Properties of
Crown-Containing 1,8-Naphthalimide Derivatives
P. A. Panchenko 1 *, Yu. V. Fedorov 1 , O. A. Fedorova 1 , G. Jonusauskas 2
Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilova 28,
Moscow, 119991, Russia. E-mail: pavel@ineos.ac.ru
2
Centre de Physique Moléculaire Optique et Hertzienne (CPMOH), UMR CNRS 5798,
Université Bordeaux 1, 351, Cours de la Libération, 33405 Talence, France
During the last years, much attention has been paid to the design, synthesis and
characterization of photochemical molecular devices, which combine chromophore
signaling units and receptor groups capable of binding of molecules and ions. Such
devices can find employment in many disciplines such as biochemistry, clinical and
medical sciences, analytical chemistry and environmental science.
Naphthalimide derivatives with EDG at the 4-th position of naphthalene ring are
well known organic chromophores and fluorophores showing good photostability and
strong emission and absorption bands in the visible region. Thus, this type of
compounds has been successfully used as signaling units for the design of ion-active
molecular systems.
R = H, Ac
RHN
Ar =
PET FRET
O
O
N Ar
O
H 2 N
O
O
N
O
O
O O
O
H
N
O
N
O
O
O
N
O O
The present paper reports synthesis and investigation of spectral properties of
naphthalimides containing crown ether substituents in N-aryl moiety. Compounds under
study were found to respond to the presence of metal ions in MeCN solution via the
enhancement of fluorescence intensity. The observed spectral effects were attributed to
inhibition of PET process between naphthalimide chromophore and electron donating
N-aryl group upon the complex formation. It was also demonstrated that the efficiency
of energy transfer (FRET, Förster Resonanse Energy Transfer) between naphthalimide
units in crown ether containing bis(chromophore) systems can be operated by the
addition of metal ions.
Ar

Chemoinformatics approaches to virtual screening and in silico design
Alexandre Varnek,
Laboratory of Chemoinformatics, UMR 7177 CNRS, University of Strasbourg
http://infochim.u-strsabg.fr
The goal of virtual screening is to discover putative hits in large databases of chemical
compounds (usually ligands for biological targets) and to remove molecules possessing
unfavorable properties. Thus, virtual screening significantly reduces the number of candidate
molecules to be synthesized and tested experimentally.
In drug design, two types of virtual screening are used: structure-based and ligandbased.
The former explicitly uses the three dimensional structure of a biological target, whereas
the latter uses only information about structure of organic molecules and their properties
(activities).
Here, we discuss an application of different theoretical approaches to computer-aided
design of new drugs and materials. Particular attention is paid to the discovery of (i) new ionic
liquids and (ii) some synthetic inhibitors of platelet aggregation.
References.
RGD-mimetic in the binding site of
the integrin αIIbβ3 receptor
G. Marcou, I. Billard, A.Ouadi and A. Varnek "In silico design of new ionic liquids (ILs) based on QSPR models
of ILs viscosity J. Phys. Chem. B, 2010, 115 (1), 93–98
A. Varnek and I. I. Baskin "Chemoinformatics as a theoretical chemistry discipline".
Mol. Informatics, 2011, 30, 20 – 32

Mirco- and Mesoporous Coordination Polymers: Synthesis, Structure
and Properties
Vladimir P. Fedin
Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Russia
Synthesis, structure and functional properties of microporous and mesoporous metal-
organic coordination polymers will be considered. Hybrid MIL-101/polyoxotungstate
materials were used for selective oxidation of a range of alkenes with aqueous hydrogen
peroxide. The selectivities toward epoxides were comparable or even superior to the
corresponding homogeneous polyoxotungstates and strongly depended on the alkene
nature. Under the reaction conditions employed, the hybrid materials were stable to
leaching, behaved as true heterogeneous catalysts and could be used repeatedly several
times without suffering a loss of the activity and selectivity.
Enantiopure (homochiral) porous absorbents provide great opportunities for
stereoselective sorption of chiral guest molecules and therefore highly demanded for
separation and purification of important substrates including drugs and other bioactive
molecules. Porous homochiral coordination polymers represent promising class of
porous chiral absorbents due to high versatility of structural design; however the
synthetic accessibility still remains a challenging problem here. Starting from
enantiopure lactic, mandelic, camphoric, malic and aspartic acids we obtained series of
homochiral porous coordination polymers with isoreticular topologies. These structures
share the same building chiral motif with rigid linkers controlling the important
structural properties (the pore sizes, free accessible volumes) and stability of the metal-
organic frameworks upon guest exchange. These structures were shown to possess
remarkable size- and enantioselective sorption properties toward chiral alcohols and sulfoxides.
More important, some chiral drug precursors also show notable enantioselectivity upon
inclusion into these homochiral porous coordination polymers.
The research was partially supported by the Russian Foundation for Basic Research
(11-03-00112) and Russian Academy of Sciences (program 5.6.1).

Polyphosphorus Ligands in Supramolecular Chemistry
M. Scheer, F. Dielmann, A. Schindler and S. Welsch
Prof. Dr. Manfred Scheer, Universität Regensburg, 93040 Regensburg (Germany)
In contrast to common approaches in supramolecular chemistry, our research is
focused on the use of substituent-free Pn-ligand complexes like the tetrahedrane
[CpMo(CO)2(η 3 -P3)], the cyclo-P4 containing complex [Cp''Ta(CO)2(η 4 -P4)] and the
sandwich complex [Cp*Fe(η 5 -P5)] as connecting units for different metal centres to
form oligomers, 1D and 2D coordination polymers, and fullerene-like aggregates. [1]
Furthermore, via molecular recognition it is possible to encapsulate fullerenes like C60
or carboranes by the [Cp*Fe(η 5 -P5)]/CuCl system (see below). [2]
In contrast, the reaction of different Pn-ligand complexes with the Ag I salt of the weakly
coordinating anion [Al{OC(CF3)3}4]ˉ leads to novel polycationic polymers, which show
extensive dissociation and exhibit dynamic behaviour in solution. [3]
The talk will focus
on the structure and properties of the spherical giant molecules as well as on the
dynamic behaviour of the polycationic polymers.
Literature:
[1] (a) J. Bai, A. V. Virovets, M. Scheer, Science 2003, 300, 781; (b) M. Scheer, J. Bai,
B. P. Johnson, R. Merkle, A. V. Virovets, C. E. Anson, Eur. J. Inorg. Chem. 2005, 4023;
(c) M. Scheer, Dalton Trans. 2008, 4372; (d) B. P. Johnson, F. Dielmann, G. Balázs, M.
Sierka, M. Scheer, Angew. Chem. Int. Ed. 2006, 45, 2473. [2] (a) M. Scheer, A.
Schindler, R. Merkle, B. P. Johnson, M. Linseis, R. Winter, C. E. Anson, A. Virovets, J.
Am. Chem. Soc. 2007, 129, 13386; (b) M. Scheer, A. Schindler, C. Gröger, A. V.
Virovets, E. V. Peresypkina, Angew. Chem. Int. Ed., 2009, 48, 5046; (c) S. Welsch, C.
Gröger, M. Sierka and M. Scheer, Angew. Chem. Int. Ed., 2011, 50, 1435–1438. [3] (a)
M. Scheer, L. J. Gregoriades, A. V. Virovets, W. Kunz, R. Neueder, I. Krossing, Angew.
Chem. Int. Ed. 2006, 45, 5689; (b) M. Scheer, L. J. Gregoriades, M. Zabel, J. Bai, I.
Krossing, G. Brunklaus, H. Eckert, Chem. Eur. J. 2008, 14, 282.

Synthesis, characterizations and applications of cyclic
oxothiomolybdenum rings
Sébastien Floquet, Akram Hijazi, Justin Kemmegne-Mbouguen, Jérôme Marrot
and Emmanuel Cadot
Institut Lavoisier de Versailles, UMR 8180, Université de Versailles, 45 av. des Etats Unis, 78035
Versailles, France. sebastien.floquet@chimie.uvsq.fr, cadot@chimie.uvsq.fr
In the last decade, we have derived the first members of a new family of
polyoxometalates (POM) compounds, the cyclic polyoxothiomolybdates, and started
exploring their properties. This fascinating class of compounds results from the selfcondensation
of [Mo2O2S2(H2O)6] 2+
building blocks around various types of ligands.
Among these ligands, the tremendous propensity of the Mo-rings to encapsulate
polycarboxylate anions as guest components allowed us to obtain a wide family of Morings
differing by their shape, their size and their charge. In the present contribution, we
will present the synthesis of some of these supramolecular compounds with a particular
attention for NMR characterizations and studies in solution and their electro-catalytic
properties toward the reduction of protons into hydrogen.
B. Salignac, S. Riedel, A. Dolbecq, F. Sécheresse, E. Cadot, J. Am. Chem. Soc., 2000, 122, 10381;
J.-F. Lemonnier, S. Floquet, J. Marrot, E. Terazzi, C. Piguet, P. Lesot, A. Pinto and E. Cadot,
Chem. Eur. J., 2007, 13, 3548; B. Keita, S. Floquet, J.-F. Lemonnier, E. Cadot, A. Kachmar, M.
Bénard, M.-M. Rohmer, L. Nadjo, J. Phys. Chem. C, 2008, 112, 1109-1114 ; S. Floquet, S. Brun,
J.-F. Lemonnier, M. Henry, M.-A. Delsuc, Y. Prigent, E. Cadot and F. Taulelle, J. Am. Chem. Soc.,
2009, 131, 17254-17259 ; S. Duval, S. Floquet, C. Simonnet-Jégat, J. Marrot, R. Ngo Biboum, B.
Keita, L. Nadjo, M. Haouas, S. Brun, F. Taulelle and E. Cadot, J. Am. Chem. Soc., 2010, 132,
2069-2077 ; J.-F. Lemonnier, S. Duval, S. Floquet, E. Cadot, Isr. J. Chem., 2011, 51, 290-302
(review).

Lithium-controlled hierarchical assembly of Ti(IV)-Helicates
Elisabeth Isaak,
Markus Albrecht
Institut für Organische Chemie, RWTH Aachen, Landoltweg 1, 52074 Aachen,
Germany
e-mail: Elisabeth.Isaak@rwth-aachen.de
Dinuclear triple-stranded titanium(IV) complexes are formed in hierarchical, lithiumtemplated
assembly from catecholate ligands and TiO(acac)2.
An equilibrium between
monomeric and dimeric units. For the formation of the dimer, two mononuclear
complexes are connected by non-covalent spacers.
The introduction of chiral information leads to diastereomers. In this study we changed
the position of chiral center and used the ligands from nature's chiral pool building
blocks for favoring one diastereomer.
The properties of the complexes are studied by NMR, ESI FT-ICR MS and CD
spectroscopy methods as well as X-ray diffraction.
References:
[1] M. Albrecht, S. Mirtschin, M. de Groot, I. Janser, J. Runsink,G. Raabe, M. Kogej,
C. A. Schalley and R. Fröhlich, J. Am. Chem. Soc. 2005, 127, 10371.
[2] M. Albrecht, E. Isaak, M. Baumert, V. Gossen, G. Raabe and R. Fröhlich, Angew.
Chem. 2011, 123, 2903; Angew. Chem. Int. Ed., 2011, 50, 2850.

ADVANCES IN THE SUPRAMOLECULAR CHEMISTRY OF
TETRAPYRROLIC COMPOUNDS
1,2
Gorbunova Yu.G.
1 A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow
2 N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia
yulia@igic.ras.ru
The first decade of the 21st century promoted an increase of the number of
research devoted to the chemistry of tetrapyrrole compounds. On the one hand, this is
due to the development and improvement of methods of investigation of compounds
and materials, so it becomes possible to determine the exact composition, structure and
purity of complex macrocyclic compounds. On the other hand, metal complexes with
tetrapyrrolic compounds possess unique properties and as a result they used in the
development of new functional materials 1-3
.
The report analyzes the approaches toward synthesis of tetrapyrrole compounds
(porphyrins and phthalocyanines) - homo-and heteroleptic, as well as homo-and
heteronuclear complexes. The construction of solid-state supramolecular architectures
on the basis of tetrapyrrolic compounds will be specially discussed.
Acknowledgements: We thanks European Research Association “SUPRACHEM”,
RFBR (grant 09-03-93117) and CNRS for financial support.
1. Phthalocyanines: Properties and Applications; Lever, A. B. P., Leznoff, C. C., Eds.;
VCH: New York, 1989; Vols. 1-4.
2. The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic
Press: San Diego, CA, 2000, 2003; Vols. 1-20.
3. Functional Phthalocyanine Molecular Materials; Jiang, J. Ed.; Springer: Berlin, 2010.

Luisa De Cola
Germany, Münster
"Self-Assembly for the Creation of New (electro)Luminescent Materials"

Supramolecular Control of Catalyst Selectivity in the
Hydroformylation
Paweł Dydio,
Wojciech I. Dzik, M. Lutz, Bas de Bruin, Joost N.H. Reek*
Van’t Hoff Institute for Molecular Sciences University of Amsterdam,
Science Park 904, 1098 XH, Amsterdam (The Netherlands)
e-mail: p.f.dydio@uva.nl, j.n.h.reek@uva.nl
A new approach in homogeneous catalysis involves the pre-organisation of a substrate
by specific recognition, affording unusually high selectivities. 1,2
Here we present DIMPhos (1), a new bidentate phosphorus ligand with an integral anion
3
recognition site. The supramolecular interactions between the binding pocket of the
Rh(1)-catalyst and alkenes containing anionic functionalities provide an excellent
design-concept to achieve remote control of the regioselectivity in hydroformylation.
DFT calculations show that the substrate anchoring highly restricts movement of the
reactive double bond, and hence favours one reaction pathway. This gives rise to the
observed highly selective hydroformylation of a variety of unsaturated carboxylic and
phosphonic acids. 4
This provides the first example of wide-ranging remote control of
catalyst selectivity by secondary substrate-ligand interactions. In this contribution we
discuss the mechanism and the substrate range of this multifunctional catylitic system.
1
Breuil, P-A.R.; Patureau, F.W.; Reek, J.N.H. Angew. Chem. Int. Ed. 2009, 2162.
2
Smejkal, T.; Breit, B. Angew. Chem. Int. Ed. 2008, 311; Chem. Eur. J. 2010, 2470.
3
Dydio, P.; Zieliński, T.; Jurczak, J. Chem. Commun. 2009, 4560; Org. Lett. 2010, 1076.
4
Dydio, P.; Dzik, W.I; Lutz, M.; de Bruin, B; Reek, J.N.H. Angew.Chem.Int.Ed. 2011, 396.

Cationic amphiphilic calixarenes:
self-assembling in water solutions and virus-sized DNA nanoparticles
Rodik, R.V., a Jain, N., b Miroshnichenko, S.I., a Richert, L., b Kalchenko, V.I., a Mely,
Y., b Klymchenko, A. S. b
a Institute of Organic Chemistry National Academy of Sciences of Ukraine;
Murmanska str.,5 02660, Kyiv-94, Ukraine E-mail: manli@ioch.kiev.ua
b Laboratory of Biophotonics and Pharmacology, Faculty of Pharmacy, University
of Strasbourg; 74, route du Rhin BP 60024 F-67401 Illkirch Cedex, France
E-mail: aklymchenko@pharma.u-strasbg.fr
The highly diverse biomedical applications of calixarene now include antibacterial,
anticancer, antiviral, selective enzyme blocking and mimicking, as well as protein
complexation 1 . On the other hand macro cycles (including calixarenes) were recently
used as scaffolds for the synthesis cationic agents for gene delivery. However, only a
few reports describe the interaction of cationic calix[4]arenes with DNA for gene
delivery applications 2 .
In this report, we present synthesis of cationic calixarenes and investigation of their
self-assembly in aqueous solutions. Moreover, DNA binding experiments were carried
out and good gene transfection properties of calixarenes were evidenced.
Cl
+
N
N+ N +
N +
OH
OHCl HO
HO
Cl
Cl
O O O O
1 2 2
R R R R
1
CX3 1 R= 2 R= C3 H 7 -n
CX6 1 R= 2 R=C 6 H 13 -n
CX8 1 R= 2 R=C 8 H 17 -n
CX12-8 1 R= C 12 H 25 -n, 2 R= C 8 H 17 -n
CX12 1 R= 2 R=C 12 H 25 -n
CX16 1 R= 2 R=C 16 H 33 -n
Cl
Cl Cl
O O O O
1 2 2
R R 1 R R
Cl
Cl
NH2 H N
NH2
2 H2N
Cl +
+ + Cl
N N Cl +
N
N
O O O O
1 2 2 1
R R R R
CX8N 1R= 2R=C8H17-n CX12-8N 1R= C12H25-n, 2R= C8H17-n We show that calix[4]arenes bearing long alkyl chains can form micelles of 6-9 nm
diameter at micromole concentration range, which can further condense different types
of DNA into small and stable particles of 40-100 nm diameter. These nano-particles,
which probably contain a single DNA molecule, exhibit promising transfection
properties in cell culture 3 .
+
N
N+ N +
N +
Cl OH
Cl OH
HO
Cl
HO
Cl
O O O O
+ + +
+
+
+
+
+
+
+
+ + +
+ + + + + +
++
++
+ + + + +
+ +
+
+
+
+
+
+
+
+ +
+
+ + +
+ + + +
++
++
-
+
+
+
+
+
+ ++
+ ++ ++ + + + +
+ +
+
+
+
+
- +
+ + +
+ - + + +
+ + + +
- - -
+
+
+
+
+
+ + + +
+ +
- - - - - +
-
+ + + +
++
++
+
+ +
+
+ + +
+
+
+
+
+
+
+
+
+
+
+
+ + +
+
+
+
+
+
+
+
+ + +
+
+
+ +
+
+
+
+
+
+
+
+
+ + +
++
++
+
+
+
+
-
-
-
-
-
a b c d
a: chemical structure of CX8; b: its schematic view; c: nanoscopic micelle formation
in aqueous solutions and d: nano-particles formed by CX8 and DNA molecule.
1
Rodik, R. V.; Boyko, V. I.; Kalchenko, V. I., Current Medicinal Chemistry 2009, 16, 1630.
2
Bagnacani, V.; Sansone, F.; Donofrio, G.; Baldini, L.; Casnati, A.; Ungaro, R., Organic Letters 2008,
10, 3953; Lalor, R.; DiGesso, J.L.; Mueller, A.; Matthews, S.E.: Chem. Commun., 2007, 4907.
3
Rodik, R.V., Jain, N., Miroshnichenko, S.I., Richert, L., Kalchenko, V.I., Mely, Y., Klymchenko, A. S.
Chemistry – A European Journal. In press.
+ + +
+ +
+ + + + ++ ++
+
+
+
+
+
+
+ + + +
+ +

Synthesis and investigation of complexing, optical and electrochemical activities of
crown-containing oligothiophene derivatives
Artemiy Mizerev a , Elena Lukovskaya a , Olga Fedorova a , Yury Fedorov b , Alla Bobylyova a , Anna
Moiseeva a , Aleksander Anisimov a
a
Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory, 119992 Moscow,
Russia, E-mail: lukov@petrol.chem.msu.ru; Fax: +7 (495) 932 85 68
b
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova
str., 119991, Moscow, Russia
Functional oligothiophenes have attracted comprehensive interest among researchers all over the
world and have actually been advanced to be among the most frequently used π-conjugated materials, in
particular as active components in organic electronic devices and molecular electronics.
Thiophene-containing donor-acceptor substituted systems show electron and energy transfer
processes. The changes in physical properties (e.g., absorption, fuorescence, electrochemistry, etc.) of
these derivatives strongly depended on the nature of both the π-conjugation and the type of donor-
acceptor substitution. We introduced in conjugated system thiophene carrying 15-crown-5-ether ring
directly linked to the 3- and 4-positions of the thiophene ring (1) or benzo-15-crown-5-ether (2) as a
donor and pyridine residue as an acceptor.
Fe +2 , Cd +2
N
electrochemical response
S
S
optical response
O
O
O
O
O
Mg +2 , Ca +2 , Ba +2
Presented molecules contains two centres of coordination: crown-ether and pyridin fragments. It is
known that 15-crown-5-ether in the solution of acetonitrile forms strong complexes with cations of
alkaline earth metals. Cations of heavy metals coordinate pyridin fragment with a formation of complex
compounds. Coordination of cations with crown-ether fragment causes hypsochromic shift of absorbance
spectra, but optical response is low. Coordination with pyridine fragment causes bathochromic shift. In
this case the response is remarkable.
Electrochemical activity of the complexes corresponds with the optical ones. Complex compounds
with crown-ether are electrochemical inactive and there is a notable response in case of pyridin fragment.
Acknowledgments to RFBR program (09-03-00550).

Supramolecular devices based on photoresposive assemblies of
cucurbit[7]uril and crown-ether derived styryl and (bis)styryl dyes
lga A. Fedorova, 1* Ekaterina Yu. Chernikova, 1 Yuri V. Fedorov, 1
lena N. Gulakova, 1 Gediminas Jonusauskas, 2 Lyle Isaacs 3*
1
A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of
Sciences, 28 Vavilova str., Moscow, 119991 Russia, fedorova@ineos.ac.ru,
2
Laboratoire Ondes et Matière d’Aquitaine – Bordeaux University I, UMR CNRS
5798, 351 Cours de la Libiration, 33405 Talence, France,
3
Department of Chemistry and Biochemistry, University of Maryland, College Park,
MD 20742, USA
The rigid structure, good water solubility, and ability to form tight complexes
with molecules and ions make CB[7] particularly attractive as a building block for the
construction of supramolecular architectures and devices. This report describes the
interaction of CB[7] molecular container with crown ether styryl and (bis)styryl dyes by
(1) cation-dipole interactions between the positively charged dyes and the ureidyl C=O
dipoles which line the CB[n] portals, and (2) hydrophobic interactions between the
guest and the CB[n] host cavity. We found that the composition of the formed
complexes depends on the relative stoichiometry of dye and CB[7].
For the monostyrylic dyes the photoinduced moving of exited dye in CB[7]
cavity was proved by analysis of the steady state and time-resolved fluorescence as well
as pump-probe experimental results. The behavior of the complexes of dyes with CB[7]
similar to moving of piston in cylinder which uses the light photon energy to move.
Acknowledgments to RFBR program (09-03-00241) and IRG “SUPRACHEM” for
financial support.

Molecular Tectonics: Design of Enantiomerically Pure Tubular Crystals
Mir Wais Hosseini, Institut Le Bel, University of Strasbourg (France). E-mail:
hosseini@unistra.fr
The preparation of chiral porous solids is of interest for chiral transformation. However, the
design of crystalline materials displaying enantiomerically pure cavities or channels still
remains a challenge. A possible strategy for the generation of such materials may be based on
crystals composed of helical strands provided that the dimension of the helical space can be
controlled and its handedness imposed. Several examples of helical metal-organic frameworks
have been reported. Although the majority of infinite helical architectures described is
composed of 1-D networks. Examples of 2-D and 3-D helical networks have been also
published.
Using the molecular tectonics approach [1], coordination networks [2] may be obtained by
combining metallatectons, i.e. metal centres or metal complexes offering at least two free
coordination sites oriented in a divergent manner , with organic coordinating tectons
possessing at least two divergently oriented ligating sites. For the design of helical
coordination networks, one may combine ZnSiF6, forming in the presence of organic tectons
an infinite pillar by bridging consecutive zinc cations by SiF62-, anions through Zn-F bonds
[3]. The formation of enantiomerically pure 2-D helical coordination networks based on
combinations of rigid enantiomerically pure bismonodentate tectons 1-4 (Scheme) with
ZnSiF6 will be presented and discussed.
[1] S. Mann, Nature, 1993, 365, 499; M. Simard, D. Su and J. D. Wuest, J. Am. Chem. Soc.,
1991, 113, 4696; M. W. Hosseini, Acc. Chem. Res., 2005, 38, 313.
[2] M. W. Hosseini, CrystEngComm., 2004, 6, 318.
[3] M.-J. Lin, A. Jouaiti, N. Kyritsakas, M. W. Hosseini, CrystEngCom., 2009, 11,189; M.-J.
Lin, A. Jouaiti, D. Pocic, N. Kyritsakas, J.-M. Planeix, M. W. Hosseini, Chem. Commun.,
2010, 46, 112; M.-J. Lin, A. Jouaiti, N. Kyritsakas, M. W. Hosseini, CrystEngComm., 2010,
12, 67; M.-J. Lin, A. Jouaiti, N. Kyritsakas, M. W. Hosseini, CrystEngCom., 2011, 13, 776.

The sensing of interfacial interactions of Tb-doped silica nanoparticles
with various substrates through the "on-off-on" switching of Tb-
centered luminescence. Mechanisms and applications.
V. Burilov a,b , A. Mustafina b , V. Skripacheva b , S. Fedorenko b , O. Bochkova b , R.
Zairov b , I. Antipin a,b , A. Konovalov a,b
.
a - Kazan Federal University, A.Butlerov Institute of Chemistry, Kremlyovskaya St.,
18, Kazan 420008; b - A.E. Arbuzov Institute of Organic and Physical Chemistry,
Arbuzov Street, 8, 420088 Kazan, Russia.
Silica nanoparticles have gained much attention during recent decades due to
their wide use in medicine and bioanalysis. Lanthanide complexes have gained a great
deal of attention owing to their unique spectroscopic characteristics, including long
fluorescence lifetime, large Stokes shift, and sharp line-like emission bands. Therefore
lanthanide complexes are applied as dopants into silica nanoparticles. Due to good
signal-to-noise ratio such nanoparticles are efficient biomarkers, while their application
in biosensing is more sparsely. The present report introduces luminescent core-shell
nanoparticles as the nanosized sensors, which recognize inorganic and organic
substrates through the “on-off” and “off-on” switching of the emission. Various
synthetic procedures have been used to modify the morphology of the core-shell
nanoparticles. The comparison of photophysical properties of nanoparticles with various
morphology reveals the effect of coating on the luminescence. The “on-off” switching
results from the interfacial interactions of the Tb(Eu)-doped nanoparticles with so called
quenching molecules and ions, such as dyes and transition metal ions. The “off-on”
switching can be achieved through the competitive interfacial binding of the quenching
versus nonquenching molecules. Both steady state and time resolved quenching
measurements have been analyzed to distinguish the contributions of static and dynamic
mechanisms in the quenching of the luminescent core through the interfacial
interactions of core-shell nanoparticles with quenching molecules. Though the dynamic
quenching through the energy transfer is the key mechanism, the static quenching
through the readsorption and light scattering should be also taken into account.

Thermodynamic Template Effect in DCC
Josè Augusto Berrocal, Roberta Cacciapaglia, Stefano Di Stefano,
and Luigi Mandolini.
IMC-CNR Sezione Meccanismi di Reazione and Dipartimento di Chimica,
Università “Sapienza”di Roma, piazzale Aldo Moro 5, 00185, Roma
joseaugusto.berrocal@uniroma1.it
Dynamic Combinatorial Chemistry (DCC) studies the generation of libraries of
compounds which are fully interchangeable under mild conditions. 1 The most appealing
feature of DCC is the chance to amplify the yield of one of the above compounds by
means of the addition of an appropriate template (an ion or a neutral molecule) which
selectively binds and offers stabilization to that specific compound.
The acid-catalyzed transacetalation of formaldehyde acetals is a suitable reaction for the
generation of well-behaved Dynamic Libraries of cyclophane formals. In the present
communication we report the experimental results related to a quantitative definition of
thermodynamic template effect 2 and the results obtained with a new well-behaved
dynamic library of cyclophanes based on the bis[4-(hydroxymethyl)phenyl]methane
unit (Fig 1). 3
Fig 1. Dynamic library based on the bis[4-(hydroxymethyl)phenyl]methane unit.
References
1
Corbett, P. T.; Leclaire, J.; Vial, L.; West, K. R.; Wietor, J.-L.; Sanders, J. K. M.;
Otto, S., Chem. Rev., 2006, 106, 3652�3711;
2
Berrocal, J. A.; Cacciapaglia, R.; Di Stefano, S.; Mandolini, L., manuscript in
preparation.
3
Berrocal, J. A.; Cacciapaglia, R.; Di Stefano, S.; Mandolini, L., manuscript in
preparation.

Molecular recognition of organic quests by thin layers of phosphorus-
a
containing dendrimer.
Gerasimov A.V., a Ziganshin M.A., a Gorbatchuk V.V., a Kovalenko V.I., b
Caminade A-M., c Majoral J-P. c
A.M. Butlerov Institute of Chemistry, KFU, 420008, Kazan, Kremlevskaya, 18,
e-mail: Alexander.Gerasimov@ksu.ru
b A.E. Arbuzov Institute of Organic and Physical Chemistry, KSC, RAS, 420088,
Kazan, Arbuzova, 8
c
Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France
Dendrimers are well applicable for the elaboration of sensors, and as
nanoparticle catalysts. Having tightly packed end groups, dendrimers of higher
generations are selective to the size and shape of guest molecules with a preference to
the smaller and less branched guests. In this respect, dendrimers are more selective than
liquid or rubbery polymers, which do not have a special molecular recognition
compared with ordinary liquid solvents.
In present work the sorption capacity for 30 volatile guests, binding reversibility,
guest desorption kinetics and guest exchange, glass transition behavior and ability to be
plasticized with guest were studied for phosphorus dendrimers of the first (G1), second
(G2), third (G3) and fourth (G4) generation with core >P(S)–, spacer unit p-(–O–C6H4–
CH=N–N(CH3)–), branch unit –P(S)< and terminal group p-(–O–C6H4 –CHO) using
quartz crystal microbalance sensor, FTIR microspectroscopy, atomic force microscopy,
simultaneous thermogravimetry and differential scanning calorimetry combined with
mass-spectrometry of evolved vapors. The dendrimers were found to have a different
selectivity for different homological series of guests, high glass transition points without
plasticization with guest even at high temperatures and saturation levels, moderate
guest-binding irreversibility and ability both for effective guest exchange and
independent guest sorption. These properties constitute an advantage of the studied
dendrimers as receptor materials in various applications.
This work was supported by RFBR 11-03-01215 and Federal Program
"Research and scientific-pedagogical personnel of Innovative Russia" for 2009-2013
(State number P2345).

Bioactive nanoscale supramolecular assemblies of ionic and non ionic
oligoperoxide based surfactants with drugs, DNA and RNA in water
O. Zaichenko 1 , N. Mitina 1 , T. Skorokhoda 1 , E. Filyak 2 , N. Boiko 2 , L. Ivanytska 2
,
1 1 1
A. Riabtseva , M. Moskvin , V. Novikov , R. Stoika
Lviv Polytechnic National University, 12 S. Bandera St., 79013, Lviv, Ukraine;
Lviv Institute of Cell Biology, 14/16 M. Dragomanov St., 79005, Lviv, Ukraine
E-mail: zaichenk@polynet.lviv.ua
Novel heterofunctional carbon chain oligoperoxides were used as multi-site radical
initiators for controlled synthesis of surface-active comb-like and block copolymers
combining links and branches of cationic, anionic or/and nonionic polyethylene glycol
(PEG) type. The surfactants were of controlled functionality, chain length, solubility,
surface activity and reactivity. There was shown the formation of non stoichiometric
intermolecular complexes via mechanisms of electrostatic interaction, due to formation
of hydrogen bonds as well as a result of hydrophobic interaction providing arising
nanoscale supramolecular structures in the media of various polarities. The formation of
highly stable nanoscale supramolecular assemblies of oligomers and polymers of ionic
and non ionic natures with low molecular weight and polymeric substances such as
anionic or cationic surfactants including polyelectrolytes, antimicrobial and anticancer
drugs, plasmid DNA and RNA were studied using conductometry, turbidimetry,
dynamic light scattering, NMR, IR-, UV- spectroscopy and other chemical and
physical-chemical techniques. The intermolecular complex formation accompanied by
sharp change of physical-chemical properties of the mixtures in narrow component
concentration range was observed. This witnesses the arising highly dispersed new
phase comprising of micelle-like hydrophobic zones as a result of oligoperoxide
surfactant and other component interaction stabilized by surfactant hydrophilic
fragments. The main driving forces of the phenomenon are electrostatic and
hydrophobic interactions. The formation of nanoscale hydrophobic zones in the system
was confirmed by both light scattering technique and water insoluble drug
solubilization. It was established that such water preparations provide essential
enhancement of antimicrobial and anticancer activity due to synergism of simultaneous
action of medicines and oligoperoxide based carriers.
2

Towards a molecular assembly based on
1,10-phenanthroline-functionalized phthalocyanines
Martynov A.G. 1,2 , Gorbunova Yu.G. 1,2 , Tsivadze A.Yu. 1,2 , Sauvage J.-P. 3
1
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow,
Russia, martynov.alexandre@gmail.com, 2 N.S. Kurnakov Institute of General and
Inorganic Chemistry RAS, Moscow, Russia yulia@igic.ras.ru,
3
Institut de Science et d'Ingénierie Supramoléculaires, Strasbourg, France,
jpsauvage@unistra.fr
With the aim to broaden the family of molecular assemblies based on
tetrapyrrolic scaffold, we designed and synthesized a novel phthalocyanine complex,
[(MC)4Pc]Zn, bearing four lateral macrocycles containing each a phenanthroline group.
The compound turned to be almost insoluble in common organic solvents due to strong
aggregation. However, introduction of Cu(I) in the macrocycle coordination sites
afforded soluble a complex which does not aggregate in chloroform-acetonitrile mixture
as evidenced by UV-Vis spectroscopy. The attempt was made to use this complex as a
precursor to synthesize a molecular assembly with novel topological properties – two
phthalocyanine platforms held together by four linear ditopic ligands – “rails”. Bulky
“stoppers” were introduced via click-chemistry to prevent dissociation of the assembly
to individual molecular components when copper ions are removed. The target [6]rotaxane
is particularly interesting as an adaptable receptor with variable size of the
binding site located between the two phtalocyanine "plates".
Acknowledgements: This work was performed in the framework of European Research
Association “SUPRACHEM” and supported by ARCUS Alsace - Russia/Ukraine
project, RFBR (grant 09-03-93117), CNRS and the Grant of the President of Russian
Federation (МК-3595.2011.3).

Metallosupramolecular Polymers with Orthogonal Interactions
Kerstin Anhuth and Carsten Schmuck
Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstraße 7,
45141 Essen, Germany.
We present the synthesis of supramolecular polymers with two orthogonal binding sites
based on metal-ligand binding and zwitterionic interactions. The first building block is
the zwitterionic pyrrol derivative 1 which was developed by Schmuck. This compound
is a self-complementary binding motive with a highly stable binding constant in DMSO
and water. [1] The second building block is the 2,2´:6´2´´-terpyridine 2 which forms very
stable transitional-metal-complexes with impressive photophysically properties variable
through the choice of the metal. [2]
Figure 1: 2-(guanidiniocarbonyl)-pyrrol-5-carboxylate-zwitterion 1 [1] and the 2,2´:6´2´´-terpyridine 2.
By linkage of those two different building blocks it is possible to change the structure
from the monomer through chemical signals to oligomers and polymers. Due to the
right pH-range (about 6) dimers can be formed by zwitterionic interactions. The
addition of metal ions provides the formation of linear or net-like supramolecular
polymers.
Figure 2: Schematic design of a supramolecular polymer based on three self-complementary binding-sites.
[1] C. Schmuck, W. Wienand, J. Am. Chem. Soc. 2003, 125, 452-459.
[2] U. S. Schubert, C. Eschbaumer, Angew. Chem. 2002, 114, 3016-3050.

Analysis of benzodiaza-15-crown-5 ether derivative binding properties
by potentiometric, optical and extraction methods
M. Oshchepkov , 1 O. Fedorova, 1,2,3 Yu. Fedorov 2 A. V. Anisimov 3
1
Mendeleev University of Chemistry and Technology of Russia,Russia, 125047 Moscow,
Miusskaya sqr., 9. E-mail: maxim.os@mail.ru
2
A. N. Nesmeyanov Institute of Organicelement Compounds of Russian Academy of
Sciences, Vavilova, 28, Moscow, 119991, GSP-1, Russia
2M. V. Lomonosov Moscow State University, Vorob’evi Gori, Moscow 119991, Russia
The coordination chemistry of macrocyclic ligands is a fascinating area of
current research in chemistry. There is a continuing interest in the binding properties of
polyazacompounds since these ambivalent ligands are able to interact with metal
cations.
R
O
O
Me
N
N
Me
O
Met
R=
C 17 H 35 NHC
=
HCO
Ag + , Cd +2 ,Hg +2, Ba +2 , Ca +2 , Co +2,
Cu +2 , Ni +2 , Pb +2 , Mg +2 , Zn +2
is able to form complexes in water
S
+
N
ClO -
4 Et
S
+
N
ClO -
4 Et
is chromophoric
diazacrown ether
compound
extractant
Our research concerns the analysis of the metal ion binding property of
benzodiaza-15-crown-5 ether when different substituents is introduced into the benzene
ring (derivatives 1-3 in scheme 1). Depending on the derivatives 1-3 properties the
potentiometric, optical and extraction methods were used for carrying out the research.
Compound 1 is formyl derivative of benzodiazacrown ether which is able to
form complexes in water. The complex formation study was done by potentiometric
method. The adding of chromophoric styrylic part to azacrown ether (compound 2)
opens the way to study the complex formation of compound by optical spectroscopy
method. So as compound 2 has got limitation in water solubility, the investigation of 2
was carried out in acetonitirile solution. The final sample 3 is chromophoric diazacrown
ether compound substituted by long akyl chain. Such structure allows the analysis of
complex formation by extraction method. The goals of these studies have been to
understand specific binding behaviour in different condition, to derive structure–
function relationships and to estimate useful applications
The research was support by RFBR grant and program of Russian Academy of Sciences

NOVEL PHOTORESPONSIBLE ANION RECEPTORS
Kajetan Dąbrowa a , Patryk Niedbała a,b , Janusz Jurczak a,b
a) Institute of Organic Chemistry PAS, Kasprzaka 44/52, 01-224 Warsaw
b)
The Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw
kajetan.dabrowa@icho.edu.pl
Coordination chemistry of anions is one of the most vivid fields of supramolecular
chemistry, since anions are essential components of biological systems. [1]
Despite the observed rapid development in this area over the past two decades only a
small number of neutral receptors capable of selective binding in demanding solvents
was developed. [2]
There are known only several methods of modifying the binding properties of
artificial anions receptors, i.e. changing pH, redox reactions and irradiation by light. The
latter is the most interest and promising since it does not influence the charge of the
receptor – it may remain neutral. After the absorption of light the geometry of receptor
undergoes profound and reversible changes. So far there are only few examples of the
use of light as a factor triggering the change of receptors affinity toward anions. [3]
To fill this gap we synthesized and examined binding properties of neutral receptor of
type 1 (a - para, b - meta substitution), which undergo reversible E-Z isomerization
process controlled by light.
Receptors E-1a-b and Z-1a-b show a significant change in affinity for anions in
highly demanding solvent (DMSO-water mixtures). The best E/Z selectivity was
achieved for carboxylate anions.
[1] Gale, P. A., Chem. Soc. Rev., 2010, 39, 3746-3771, 10.1039/c001871f;
[2] P. A. Gale, S.E. Garcı´a-Garrido, J. Garric, Chem. Soc. Rev., 2008, 37, 151–190, 10.1039/B715825D
[3] Wang Y.,Bie F., Jiang H., Org. Lett., 2010, 12 (16), 3630–3633, DOI: 10.1021/ol1014043

Crown-containing derivatives of naphthopyrans: cation
binding, photochemical and fluorescent properties
A.B. Smolentsev 1 , E.M. Glebov 1 , V.V. Korolev 1 , S.V. Paramonov 2 , O.A. Fedorova 2
1 – Institute of Chemichal Kinetics and Kombustion SB RAS, Novosibirsk , Russia
2 - Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia
S_art@ngs.ru
Photochromic molecules containing macrocyclic moiety have attracted much
interest in molecular chemistry as components of functional materials. Examples of
potential applications of these compounds include: photoswitching transport through
membranes, optical information storage, photoswitching extraction of metal cations.
A
O
O
O
O
O
O
B
O
O N
O O
O
Scheme 1
O
O
O
O O
Crown-containing naphtopyrans (chromenes) A, B, C (scheme 1) and their
crownless analogues were used in the work. All studied compounds, upon UV
irradiation, yield open colored forms. Then in the course of dark reaction open form of
chromenes turns into colorless closed form. Moreover, naphtopyrans A and B, upon UV
irradiation, undergo irreversible geometrical isomerisation.
All studied crown-containing compounds form host-guest complexes with Mg 2+ ,
and Ba 2+
cations. The presence of metal cations in the solution leads to partial
destabilization of the photoinduced form of С and consequently decreases its lifetime.
Nevertheless, complexation doesn’t effect on the spectroscopic and kinetic properties of
the colored forms of A and B.
Naphthopyran B fluoresces with maxima at 530 nm. It’s remarkable that only
trans- isomer of B is fluorescent, while cis- isomer is not. For this reason trans-cis
isomerisation of B leads to disappearance of fluoresce. The presence of metal cations in
the solution also leads to significant decrease of fluorescence quantum yield of B.
This work was supported by the Russian Foundation of Basic Research (grants
№11-03-00268 and №09-03-00283).
C
O

THIACALIX[4]ARENES: SYNTHESIS AND MOLECULAR
RECOGNITION OF SOME ANIONS
A.A. Yantemirova,
R.V. Nosov, A.N. Yagarmina, I.I. Stoikov, I.S. Antipin,
A.I. Konovalov
A.M. Butlerov Chemical Institute, Kazan (Volga Region) Federal University, 420008
Kremlevskaya, 18, Kazan, Russian Federation. E-mail: anelia_86@mail.ru
The potential uses of products of supramolecular chemistry and the ability of
these products to exhibit properties typical of highly organized biomolecules, e.g.
molecular recognition, catalysis, active and selective transport, has promoted research in
the chemistry of synthetic receptors. The design and synthesis of systems, capable of
recognizing anions, continues to be one of the challenging problems in supramolecular
chemistry. For the synthesis of anion receptors we had proposed to use derivatives of
thiacalixarene with different substituents at the lower rim. Regioselective
functionalization of the lower rim of the thia-analog of calixarene is significantly
complicated because of the difficulties in selection of the reaction conditions (ratio of
reagents, temperature and duration of the synthesis). Therefore, synthesis of
thiacalix[4]arenes with different substituents at the lower rim is commonly more
difficult than that of the other similar macrocycles substituted with identical fragments.
New thiacalix[4]arenes containing amide, hydroxyl and ester fragments differently
substituted at the lower rim were synthesized. For the synthesis of stereoisomers of p-
tert-butyl thiacalix[4]arene with ester and amide fragments at the lower rim, the
template effect of alkali metal cations was used. Receptor properties of the newly
synthesized thiacalix[4]arene derivatives toward some tetrabutylammonium salts n-
Bu4NX (X =F - , Cl - , Br - , I - , CH3CO2 - , H2PO4 - , NO3 -
) were studied by UV spectroscopy.
Selective receptors for fluoride ion and dihydrogen phosphate ion were found.
This work was supported by Federal Program "Research and scientific-
pedagogical cadres Innovative Russia" in 2009-2013 years (№ P1295 on 9 June 2010),
RFBR (09-03-00426, 10-03-92661-NSF) and the Program of the President of the
Russian Federation for the State support of young Russian scientists - Doctors of
Sciences (MD-2747.2010.3).

Tuning of Knoevenagel-type substrate reactivity and optical properties
by supramolecular interactions
Nadine Allendörfer & Jean-Marie Lehn*
Laboratoire de Chimie Supramoléculaire, ISIS
Université de Strasbourg
8 Allée Gaspard Monge, 67000 Strasbourg (France)
lehn@isis.u-strasbg.fr
Dynamic chemistry uses reversible reactions of molecular and supramolecular entities.
Here a covalent or non-covalent linkage of the components is possible. Dynamic
covalent chemistry (DCC) has become a useful tool in material science and drug design.
Some examples of reversible reactions used in DCC are amine/carbonyl condensations,
peptide exchange, disulfide exchange, trans-esterifications, Diels-Alder condensations
and olefin metathesis. In this work, we have focused on the Knoevenagel reaction,
which allows the dynamic formation and cleavage of C=C double bonds.
The reactivity of Knoevenagel-type substrates like benzylidenes, derived from
aldehydes and barbituric acid, can be influenced by their structure. Therefore, we
modified the aldehyde components to obtain polyene benzylidenes. Such donor-
acceptor polyenes have interesting linear and nonlinear optical properties and have
potential applications in telecommunications, optical data storage, and optical
information processing.
The reactivity and optical properties of Knoevenagel-type components can also be tuned
by supramolecular interactions. An H-bond-mediated molecular recognition of various
benzylidenes and receptors is observed. A comparative study of the reactivity and
optical properties of Knoevenagel-type substrates with and without supramolecular
influence was made.

Conducting polymers with anion binding sites for potential sensing
applications
Krzysztof Bąk, Michał J. Chmielewski *
Conducting polymers are highly promising materials for sensing applications, in part because
their conjugated, molecular wire-like structures offer high potential for signal amplification. Yet, their
potential in anion sensing is largely underdeveloped.
1,8-Diaminocarbazole is a new, particularly attractive building block for the construction of anion
receptors, developed in our laboratory. It combines enhanced hydrogen bonding ability (compared to
pyrrole), rigidity and outstanding synthetic versatility with the presence of chromophore and
fluorophore. Moreover, it undergoes facile electropolymerisation into a π-conjugated, conducting
polymer with highly promising properties. Thus, appropriately functionalised derivatives of 1,8diaminocarbazole,
having both an anion binding site and free amino group which is necessary for
polymerisation, may serve as precursors of conducting polymers with anion sensing properties.
Interestingly, such polymers may function as triple channel sensors, displaying colorimetric,
fluorescent and electrochemical response to anionic guests.
Selective protection of only one amino group of 1,8-diaminocarbazole was achieved in ca.
50% yield using (Boc)2O in THF. This opened an easy access to a variety of amide, urea and thiourea
derivatives with one amino group free and ready for polymerisation. Preliminary electrochemical
investigations confirmed successful electropolymerisation of a simple benzamide derivative.
i/A
8.0µ
7.0µ
6.0µ
5.0µ
4.0µ
3.0µ
2.0µ
1.0µ
0.0
-1.0µ
-2.0µ
-3.0µ
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
E/V
i/A
2.0µ
1.6µ
1.2µ
800.0n
400.0n
0.0
-400.0n
-800.0n
-1.2µ
-0.4 -0.2 0.0 0.2 0.4
E/V
On the left: voltamperogram received
during polymerization proving the
formation of conducting polymer.
On the right: electrical answer of the
system obtained during preliminary
electrochemical studies.

FRET based distance measurements on vesicle surfaces - Towards the
dynamic recognition of multivalent target molecules
Stefan Balk a , Benjamin Gruber a , Tobias Lang a , Burkhard König a, *
a
University of Regensburg, Universitätsstraße 31, 93053 Regensburg
e-mail: burkhard.koenig@chemie.uni-regensburg.de
Mimicking recognition processes at natural cell membranes we recently reported synthetic vesicles
with multi-receptor surfaces as chemosensors for small biomolecules. [1] Based on these results we
want to develop a simple model system for the dynamic recognition of multivalent target molecules by
multiple membrane-embedded receptors equipped with FRET labels.
Figure 1. A multivalent biomolecule with two different ligands binding to two fluorescent labeled
receptor molecules, embedded in a membrane and detected via FRET.
The influence of analyte binding towards the FRET distances was investigated by emission titrations.
The investigation of these dynamic interactions is part of an approach towards imprinted vesicles with
ordered surfaces that perfectly match a templating target molecule.
____________________
[1] B. Gruber, S. Stadlbauer, A. Späth, S. Weiss, M. Kalinina, B. König, Ang. Chem. Int. Ed. 2010, 49,
7125.

Rigid Luminescent Bis-Zinc (II)–Bis-Cyclen Complexes and Non-
Covalent Protein Labelling in Aqueous Solution
Mouchumi Bhuyan,
Evgeny Katayev, Stefan Stadlbauer, Itaru Hamachi,
Burkhard König
The selective luminescent labelling of proteins by markers is an important quest and an
ongoing challenge in molecular biology. Covalent labelling uses reactive dyes or
genetic fusion of fluorescent proteins, for example, green fluorescent proteins (GFPs).
Non-covalent labelling strategies employ antibodies or snap tags. Recently a new high
II
affinity peptide tag – artificial probe pair orthogonal to the His tag– Ni –NTA pair has
been developed by Hamachi group for protein labeling, employing coordination
chemistry and multivalent interaction between a genetically encodable oligoaspartate
sequence (D4-tag) and a corresponding oligonuclear Zn II –Dpa complex. Because
artificial zinc dipicolylamine (Zn II –Dpa) receptors and zinc-1,4,7,10-
tetraazacyclododecane (Zn II –cyclen) complex derivatives are both known for their
application as phosphate binders under physiological conditions, we considered using
Zn II –cyclen derivatives as alternative artificial probes for the developed artificial probes
for oligoaspartate (D4- tag) and oligoglutamate (E4-tag) tag sequences. Although the
coordination geometry of Zn II –Dpa and Zn II –cyclen is rather different, Zn II –cyclen
derivatives show a comparable high binding affinity and fluorescence response and may
therefore be used as an alternative artificial non-covalent protein marker. The binding
affinity studies of the synthesized receptors to the genetically encodable tag proteins
will be presented in detail. i
i M. Bhuyan, E. Katayev, S. Stadlbauer, H. Nonaka, A. Ojida, I. Hamachi, B. König, Eur. J. Org. Chem.
2011, 2807–2817

Synthesis and supramolecular association of heteroleptic
terbium (porphyrinato)(crownphthalocyaninates)
Birin K.P. , Kamarova K.A., Gorbunova Yu.G., Tsivadze A.Yu.
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS
N.S. Kurnakov Institute of General and Inorganic Chemistry RAS
Leninsky pr., 31, Moscow, Russia, 119991.
E-mail: yulia@igic.ras.ru, kirill.birin@gmail.com
Sandwich type lanthanide complexes with porphyrins and phthalocyanines are
attractive as rigid cores for development of selective receptors. Modification of
compounds with crown-ether moieties allows binding of alkali cations and formation of
supramolecular architectures. The only one paper is devoted to design of such type of
heteroleptic receptors, - europium (porphyrinato)((15-crown-5)-phthalocyaninates) [1].
In present work we report on the synthesis of alkali cations receptors based on terbium
triple-decker (porphyrinato)((15-crown-5)-phthalocyaninates).
[Br4TPP]Tb[(15C5)4Pc]Tb[Br4TPP] (1) [Br4TPP]Tb[(15C5)4Pc]Tb[(15C5)4Pc]
(2)
The triple-decker terbium complexes Tb2[Br4TPP]2[(15C5)4Pc]
(1) and
Tb2[Br4TPP][(15C5)4Pc]2 (2) were synthesized by interaction of terbium
monoporphyrinate with double-decker compounds with yields of 48% and 63%,
respectively. The spectrophotometric titration of the heteroleptic triple-deckers with
K[BPh4] revealed that receptor 1 is unable to bind K +
because of sterical hindrances.
The unsymmetrical complex 2 shows hypsochromic shift of absorption bands upon
titration, which can be attributed to formation of supramolecular dimers, similar to [1].
Acknowledgements. The authors are grateful to Foundation of Russian President
for support of young scientists (grant MK-212.2010.3), RFBR (grant 11-03-00968) and
Russian Academy of Sciences for financial support.
1. M. Bai, M. Bao, C. Ma, et al. J. Mater. Chem. 2003, 13 (6), 1333-1339.

Photophysical properties of surfactant modified luminescent Tb-doped
silica nanoparticles in presence of dyes as quenchers of Tb luminescence.
O.D. Bochkova,
A.R. Mustafina, V.V. Skripacheva, Yu.G. Elistratova, A.R.
Mukhametshina, S.E. Solovieva, A.I. Konovalov.
A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Center
of RAS, Kazan, Russia.
Lanthanide-doped silica nanoparticles have gained a great deal of attention owing to
lanthanides unique spectroscopic characteristics, including long fluorescence lifetime,
large Stokes shift, and sharp line-like emission bands. The metal complex-doped
nanoparticles have an advantage over a single complex, since the silica shell protects the
metal complex from photodegradation, while the surface of the nanoparticle can be
functionalized by various anchoring groups. The silica surface decoration is aimed to
increase the colloidal stability of nanoparticles, as well as to develop their receptor
properties towards biotargets. The decoration of the silica surface through the noncovalent
interactions represents more convenient alternative to covalent anchoring due
to the lack of multistep purification procedures.
The approach to sense the adsorption of various surfactants onto silica surface of Tbdoped
nanoparticles will be discussed. It is based on quenching of Tb luminescence by
dyes. A universality of this approach will be shown. Regularities of change of surfactant
modified Tb-doped silica nanoparticles luminescence and quenching mechanisms of
Tb-luminescence by dye molecules will be reported. The methods of dynamic light
scattering and luminescent spectroscopy were used.
We thank RFBR
(projects N 09-03-12260
Ofi_M and 10-03-
00352-а) for financial
supporting.

The features of the coordination networks formation of meso-mono-
and di-phosphorylated zinc porphyrins
Yu.Yu. Enakieva a,b , Yu.G. Gorbunova a,b , A. Bessmertnykh c , S.E. Nefedov b , C. Stern c ,
A.Yu. Tsivadze a,b and R.Guilard c
a A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Moscow
b N.S. Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow
c
Universite de Bourgogne ICMUB UMR CNRS 5260, 9 avenue Alain Savary, 21078
Phosphorylated porphyrins are promising models for elaboration of highly
ordered supramolecular systems of various architectures due to features of P=O-groups
and number, nature and arrangement of other peripheral functional groups of porphyrin.
N
X
N N
`Y Zn
X
Previously we have developed a general method to prepare new phosphoryl-
N
Y
Y=Y`= PO(OEt) 2, X= C6H5 (1a) ; Y`= H (2a)
Y=Y`= PO(OEt) 2, X= C6H5CN (1b) ; Y`= H (2b)
Y=Y`= PO(OEt) 2, X= C6H5CH3 (1c) ; Y`= H (2c)
Y=Y`= PO(OEt) 2, X= C6H5OCH3 (1d) ; Y`= H (2d)
Y=Y`= PO(OEt) 2, X= C6H5COOCH3 (1e) ; Y`= H (2e)
studied by means of X-Ray diffraction analysis.
substituted porphyrin receptors (1a-
e, 2a-e). The optimal conditions of
crystal growth for these compounds
were found and its structures were
It was shown [1] that the self-assembly of 1а leads to the formation of 2D
coordination network. Introduction of linear CN-group (1b) doesn`t change the
architecture of final network. However, when bulky electron-donating CH3-group
is
introduced (1c), dramatic changes of crystal structure occur leading to the formation of
pseudo-3D assembly constructed from alternating molecules, containing zinc ions with
coordination numbers equal to 5 and 6. Analogous self-assembling architecture was
observed for the complex 1d. Further increasing of the bulkiness of the phenyl-group
substitutes in 1e leads to even more sophisticated structure.
It should be note that the self-assembling of mono-phosphorylated porphyrins
(2a-e) also depends on the nature of peripheral substituent. Thus, the complex 2a forms
1D linear polymer, while the complex 2b forms dimers where the phosphoryl-group of
one molecule binds to the zinc ion of the other one. Self-assembling of complexes 2c-e
leads toward “calyxarene-like” structure including 4 zinc-porphyrinato-units.
Acknowledgements: This work was performed in the framework of French-Russian Associated
Laboratory “LAMREM” and “SUPRACHEM”, supported by ARCUS 2007 Burgundy-Russia project,
Russian Foundation for Basic Research, the CNRS and Russian Academy of Sciences.
[1] Enakieva Y.Y., Bessmertnykh A.G., Gorbunova Y.G., et. al. Org. Lett., 2009, 11, 3842-3845.

Thiacalix[4]arenes with triple bonds on the lower rim : synthesis
and reactivity.
N.A. Epifanova a , E.V.Popova a , S.V. Kharlamov a , Sh.K. Latipov a , S.F. Vasilevsky
b
a
R
b , S.E. Solovieva a , I.S. Antipin a .
A.E. Arbuzov Institute of Organic and Physical Chemistry KazCS RAS, Russia,
420088, Kazan, Arbuzov str. 8. E-mail:
S
4
O-CH2-C CH
OCH2C C
R1 1 2 3
epifanova@iopc.ru
Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian
Academy of Sciences, 630090, Novosibirsk, Russian Federation.
(Thia)calix[4]arenes are useful platforms for obtaining of three-dimensional
structures – building blocks for construction of supramolecular systems. They are well-
known as molecular receptors for bounding of different type guests: metal ions, organic
substrates and metal complexes. Multiple bonds make (thia)calix[4]arene able to form
“click-chemistry” products, which could be used for making of new generation
biologically active compounds, selective complexing agents and building blocks for
obtaining of metal-organic structures (MOF’s), probes for biomedical applications.
In the present work alkylation reactions thiacalix[4]arenes by propargyl bromide
in the presence of alkali metal carbonates were systematically studied. Regularity of
different stereoisomeric forms formation in dependence of used base nature were
established. It was shown, that classical alkylation with using of propargyl bromide
gives the possibility to obtain tert-butyl-thiacalix[4]arene and thiacalix[4]arene
derivatives (1) with triple bonds at the lower rim in different conformations in one step.
(Thia)calix[4]arenes with propargyl groups were used in Sonogashira cross-
coupling (2) as well as in“click-chemistry” (3) reactions.
Structure and stereoisomeric forms of new compounds were characterized with the use
of 1D and 2D NMR, IR spectroscopy and mass-spectrometry.
R
X 4
The work was supported by the Russian Foundation for Basic Research (grant no. 10-
03-00728).

Catalysts within Dynamic Combinatorial Libraries
Hugo Fanlo Virgós,
Sijbren Otto*
Centre for Systems Chemistry, Stratingh Institute for Chemistry, University of
Groningen, Groningen, The Netherlands.
How to predict the structure of catalysts that selectively target specific substrates is one
of the biggest challenges that chemistry currently faces. Very often, the catalystsubstrate
affinity needs a combination of structurally and chemically complementary
features between both molecular entities that are difficult to anticipate. Our approach to
identify catalysts by using Dynamic Combinatorial Chemistry simplifies catalyst design
by letting the molecules choose to interact according to their own “preferences”. By
mixing a combination of molecular building blocks able to form reversible hydrazone
bonds (-C(O)-N(H)-N=C-, see scheme) a set of potential catalysts can be selfassembled.
The interactions of these potential catalysts with the substrate will determine
the stability of the host-guest adducts (thus their relative population) and are a first
requirement for catalysis. By screening the combinatorial libraries for affinity for a
Transition-State Analog we should be able to predict if a transition state of a catalyzed
reaction could also interact and therefore be stabilized.
=
O
N
N C
H H

2
ROLE OF SPACER IN THE PHASE-TO-PHASE LAYER
OF POLYMERIC MICROSPHERES AT CONSTRUCTING OF
BIOTEST-SYSTEMS
1 Fedorova O.V., 1 Zayarnyuk N.L., 2 Stanishevskiy Ya.M.,
2 Gritskova I.A., 1 Novikov V.P.
1
National University “Lviv Politechnic”
79013, Lviv, Bandery str., 12, e-mail: vnovikov@polynet.lviv.ua
Moscow State Academy of Fine Chemical Technology n. of M.V. Lomonosov
When constructing biotest-systems on viral and infectious diseases specific
immunoglobulins G (Ig G) have been used as bioligands. The immobilization of these
immunoglobulins on the surface of functional polymeric microspheres proposed to
through spacer, protein A (S. aureus). The choice of spaser is conditioned by its
capability of the affine interaction with Fc - fragment of molecule. In this case Fab -
fragment of Ig G provides more effective availability of binding to antigen’s
determinants with potential causative agent of a disease.
Optimal concentrations of protein A (0,05 mg/ml) on the surfaces of polymeric
microspheres and minimum dilutions of serums, at which particles of conjugates
"polymeric microsphere - protein A" spontaneously aggregate, have been determined.
The orientation of Ig G molecule with hydrophilic Fab-fragment into the water
phase results in lyophilization of a surface of a particle, which is the condition of the
development of structural - mechanical factor by Rebinder. The creation of such type of
diagnostic biotest-systems doesn’t require a preliminary selection and purification of
specific molecules of Ig G, which are contained in γ- globulin’s fraction required.
Stability of the conjugate "polymeric microsphere (PM) - protein A" allows using it
more than 6 months.
Biotest-systems of different specificity for the following diseases have been
developed using highly titratable serums and universal conjugate "PM - protein A":
yersiniosis (Y. enterocolitica); salmonellosis (S. pullorum); leptospirosis (L. conicula);
for the chicken infectious bronchitis virus stamm Н120.

SYNTHESIS AND COMPLEXATION ABILITIES OF
HYPERBRANCHED STRUCTURES BASED ON
THIACALIX[4]ARENE
Galukhin A.V., Mostovaya O.A., Antipin I.S., Stoikov I.I., Kazan Federal
University, 18 Kremlyovskaya st., Kazan, e-mail: and_galuhin@mail.ru
Hyperbranched macromolecules functionalized by polydental fragments are widely
used for highly effective molecular recognition of various biologically relevant
compounds, including biopolymers. Dendrimers based on p-tert-butylthiacalixarene
have such interesting properties as high concentration of binding sites, highly developed
surface and porosity. Thiacalixarene derivatives´ ability for molecular recognition of
biologically relevant molecules´ surface is provided by conformational mobility of
dendrimer´s “branches” and spatial organization of functional groups, forming
complementary binding sites.
In this work various dendrimers based on thiacalixarene in 1,3-alternate
configuration were synthesized. Structures of obtained compounds were characterized
by 1D and 2D NMR-spectroscopy, IR-spectroscopy, mass-spectrometry and elemental
analysis. Complexation abilities of synthesized macrocycles with DNA of salmon sperm
and calf thymus DNA were investigated by complex of spectroscopic methods: UV- and
fluorescent spectroscopy, dynamic light scattering method.
The financial support from Federal Program "Research and scientific-pedagogical
cadres Innovative Russia" in 2009-2013 years (№ P1295 on 9 June 2010), RFBR (09-
03-00426, 10-03-92661-NSF) and the Program of the President of the Russian
Federation for the State support of young Russian scientists - Doctors of Sciences (MD-
2747.2010.3) is gratefully acknowledged.

Silica Nanoparticles with Proton Donor and Proton
Acceptor Groups: Synthesis and Aggregation
Gorbachuk Vl.V., Meleshina M.V., Yakimova L.S.,
Antipin I.S., Stoikov I.I., Zharov, I.
Kazan (Volga Region) Federal University, 18 Kremlyovskaya St., Kazan,
e-mail: vladimirgorbachuk@gmail.com
Silica particles attract much attention due to their useful properties, which open numerous
opportunities for the preparation of functional nanomaterials. Functionalized silica particles are
relatively easy to prepare in a wide range of sizes and morphology, they can be functionalized with
various organic groups, and possess high stability. Materials based on these particles have unique
mechanical, thermal, optical, electronic and biological properties and find application in catalysis,
drug delivery, sensors, etc.
The effects of precursor structure and polycondensation conditions on the properties of hybrid
nanoparticles synthesized from organo-trimethoxysilanes were studied. Hybrid nanoparticles
containing groups capable of forming hydrogen bonds were synthesized from functional derivatives
of 3-aminopropyltrimethoxysilane.
We have demonstrated that all these nanoparticles form aggregates in solution, and that the size of
these aggregates depends on solution pH, ionic strength and solvent polarity. Therefore, by changing
the pH of the solutions, it is possible to control the size of the nanoparticle aggregates. For
phenylurea-functionalized nanoparticles, three different synthetic methods have been used, allowing
to relate the composition of these nanoparticles to their aggregation behavior.
. Structures of obtained compounds and particles were characterized by NMR-, IR-spectroscopy,
mass-spectrometry, elemental analysis and combined TG-DSC. Aggregation behavior was studied
by DLS and AFM methods.
Acknowledgments: The financial support from RFBR (10-03- 92661-NSF), the Program of the
President of the Russian Federation for the State support of young Russian scientists—Candidates of
Sciences (MK-6390.2010.3) and NSF MWN grant (DMR-1008251) is gratefully acknowledged.

Towards a Light Driven Proton Pump
Britta Hesseler,
Melanie Zindler, Ulrich Lüning*
Otto-Diels-Institut für Organische Chemie, Olshausenstr. 40, 24098 Kiel, GER
bhesseler@oc.uni-kiel.de, luening@oc.uni-kiel.de
Light driven uphill transport of protons is an essential process in nature. In the
photosynthetic apparatus, light energy is used to pump protons across a cell membrane.
Scheme 1 depicts our model system. The proton transfer is realized by a photoswitchable
acid, like 2-(2,4-dinitrobenzyl)pyridine (DNBP), attached to a rotaxane.
Scheme 1: Uphill proton transfer by a rotaxane. Due to electrostatic repulsion the macrocycle moves
along the axle.
Upon irradiation, the photo-switchable acid tautomerizes to a more acidic form and
switches back in a thermal reaction (scheme 2).
Scheme 2: Tautomers of DNBP with different acidity.
Several novel DNBP derivatives were successfully synthesized and for this, a new
method to obtain di- and trinitrobenzyl substituted pyridine derivatives was
developed. [1] Furthermore several axles and macrocycles [2]
were synthesized to build a
[2]rotaxane via a slipping process.
R
R
R
I
H
N
N
O
Scheme 3: Synthesized axles and macrocycles for the rotaxane formation.
O
O
R
R
R = H, t-butyl
[1] A. Frey, C. Goeschen, C. Näther, U. Lüning, R. Herges, J. Phys. Org. Chem. 2010, 23, 1093-1098.
[2] U. Lüning, E. Mak, M. Zindler, B. Hartkopf, R. Herges, Eur. J. Org. Chem. 2010, 4932-4940.
R
‚
R
O
N
27
-
39
O
O O
R‘= H, OMe

An efficient [3]catenane formation in a dynamic combinatorial library
Jianwei Li and Sijbren Otto
University of Groningen, Centre for System Chemistry, Stratingh Institute, Nijenborgh 4, 9747 AG
Groningen, The Netherlands
E-mail: Jianwei.li@rug.nl
Catenanes, consisting of two or more interlocked macrocyclic rings, often exhibit
markedly novel properties 1 . Although there are several strategies to synthesize this kind
of molecules, synthetic challenges still remain 1 . Dynamic combinatorial chemistry is a
useful tool to explore synthetic receptors and ligands for biomolecules 2 . Dynamic
combinatorial libraries (DCLs) are produced by linking building blocks together using a
reversible reaction, resulting in a thermodynamically controlled product distribution.
Addition of a guest or a biomolecule shifts the distribution to those library members that
bind best to the external target; a process referred to as templating. Considering the
interaction between cyclodextrin homologues and azobenzene derivatives is strong, we
set up a library using β-cyclodextrin and a dithiol-azobenzene derivative. We have
found that two molecules of β-cyclodextrin were interlocked on one disulfide bonds
linking tetramer macrocycle. The yield of the [3]catenane formation is 95%. This
efficient synthesis of catenane by is proved by HPLC/MS and 1
H NMR. These results
provide a new strategy for synthesizing catenane.
1. O. S. Miljanic, J. R. Heath and J. F. Stoddart, J. Am. Chem. Soc., 2007, 129, 8236-8246.
2. (a) P. T. Corbett, J. Leclaire, L. Vial, K. R. West, J. L. Wietor, J. K. M. Sanders and S. Otto, Chem.
Rev. 2006, 106, 3652-3711. (b) R. A. R. Hunt and S. Otto, Chem. Commun. 2011, 47, 847-858.

HPLC study of the complexation of calix[4]arenephosphonic
acids with amino acids
O
HO
P
HO
Kalchenko O.I., Cherenok S.O., Yushchenko O.A., Kalchenko V.I.
OH
OH
OPr PrO
OH
Institute of Organic Chemistry, National Academy of Sciences
of Ukraine02660, Kiev-94, Ukraine, E-mail vik@ioch.kiev.ua
Calix[n]arenes [1] composed of phenolic units linked via methylene groups
have been studied as cavity-shaped host molecules able to recognize a wide range of
guest molecules. It was shown by HPLC method calixarenes form supramolecular
complexes with amino acids [2-4].
Binding constants of calixarenephosphonic acids 1-5 complexes with amino
acids (Gly, Pro, Arg, Ala, Phe, Tyr, Trp) and tetrapeptide (Gly-Pro-Arg-Pro) in solution
had been determined by high-performance liquid chromatohraphy (HPLC) in water-
organic solution.
O
HO
P
HO
OH
OH
OPr PrO
OPr
3
HO
HO
O
HO
P
HO
OH
OH
OPr PrO
OH
P OH
O
HO
HO
O
HO
P
HO
OH
OPr
OPrPrO
OPr
P OH
1 2 3 4 5
Binding constants of the calixarene complexes (1:1) with аmіno acids were
within the region 16000-48000 M -1 . Molecular modelling of the calixarene complexes
were performed. The factors influencing the calixarene complexation: a) Conformation
and hydrophobicity of calixarene-Host cavity; b) Nature and quantity of the substituents
at the upper and the lower calixarene rim; c) Nature, size and quantity of the
substituents in the Guest molecules, size and structure of the Guest molecules. It was
established the correlation between KA
amino acids.
1. Gutsche, C.D. (2008). Calixarenes revisited; The Royal Society of Chemistry, Cambridge, England.
2. Kalchenko O.I., Perret F., Coleman A.W. J. Chem. Soc. Perkin Trans. 2. 258 (2001).
3. Kalchenko O.I., Da Silva E., Coleman A.W. J. Incl. Phenom., 43, 305 (2002).
4. Kalchenko O.I., Cherenok S.O., Rodik R.V., Drаpаilo A.B., Міrоshnichеnkо S.I.,
Kаlchеnkо V.I. Phosphorus, Sulfur, and Silicon, In press.
O
O
HO
P
HO
HO O
O
OH
HO P
HO P
HO
O
OPr
OPr PrO
OPr
P OH
OH
P
OH
of the calixarene complexes and properties of
HO
HO
P
O
O
P O H
OH
OH
P
OH
O

UO2 2+ /XO4 - /Tf2N -
System (X=Re, Tc) in Various Ionic Liquids and
Comparison with Water and Acetonitrile
O. Klimchuk a, c , A. Ouadi a , S. Georg a , I. Billard a , C. Gaillard
a) IPHC, DRS/CHNU, 23 rue du Loess, 67037 Strasbourg Cedex 2, France
b) Institut de Physique Nucléaire de Lyon, 4 rue Enrico Fermi, 69622
Villeurbanne, France
c) Institute of Organic Chemistry, Ukraine, Murmanska str., 502660, Kyiv-94,
Ukraine
Room Temperature Ionic Liquids (RTILs) are a class of “green” solvents which
have been intensively studied in the past 10 years in different fields of extraction and
nuclear chemistry. Their physico-chemical properties are easily tunable by changes in
their chemical structure, so that they are often called “design solvents”. Although such
aspects are indeed rather interesting in view of potential industrial applications, to our
opinion, the unusual solvation properties of these media are a much more appealing
advantage.
The complexation of perrhenate (ReO4 - ) and pertechnetate (TcO4 - ) anions by the
uranyl (UO2 2+ ) cation is investigated by spectroscopic (UV-Vis, luminescence and
EXAFS) means in water, acetonitrile and three different hydrophobic ionic liquids (ILs)
(tributylmethylammoniumTf2N, trimethylbutylammoniumTf2N and 1-methyl-3butylimidazoliumTf2N,
where Tf2N – stands for (CF3SO2)2N -
).
The results of complexation and extraction will be presented. It will be shown
that XO (X = Re, Tc) behaves as a weak ligand in aqueous solution and as strong
ligand in acetonitrile and in the ILs.
4 -
b

Novel fluorescent sensors based on crown ether containing derivatives
of 2-styrylphenanthroline
Kolosova O.Yu. 1 , Gulakova E.N. 1 , Shepel’ N.E. 1 , Fedorov Yu.V. 1 , Jonusauskas G. 2 ,
Fedorova O.A. 1
1
A. N. Nesmeyanov Institute of Organoelement compounds of RAS, 28 Vavilova str.,
Moscow, 119991, Russia, kolosova@ineos.ac.ru
2
Bordeaux 1University, 351 Cours de la Libération, 33405 Talence, France.
The development of compounds for measuring of distribution and concentration of
biologically important metal ions, e.g. zinc, displays a particular interest for sensor
technology.
It was shown that the presence of two coordinating sites in 2-styrylphenanthroline,
which contains crown ether moiety, leads to the formation of supramolecular assembles
of different structure. The binding of metal cations with different coordinating sites of
the ligand resulted in different optical responses.
The complex formation of the ligands with metal cations leads to changes of their
fluorescent intensity. Thus, self-organization of the ligands into dimer complexes of
cell-type in the presence of Zn 2+ accompanied by fluorescence quenching. The addition
of cations Pb 2+ or Ca 2+ to the solution of the dimer complexes, which formed by
benzocrown ether containing ligands, leads to buildup of fluorescence.
The binding of metal cations with ligands in PVC-films shown the fluorescence
response, which depends on cation nature. It definitely testifies about the possibility of
practical usage of the PVC plasticized sensor membranes for the modification of fiberoptic
sensor devices.
This work was supported by financial assistance from the RFBR and the Ministry of Education and
Science of the Russian Federation.

Molecular Recognition on multi-Receptor Synthetic Membranes – Towards
Imprinted Vesicular Surfaces
Tobias Lang a , Benjamin Gruber a , Stefan Balk a , Burkhard König a, *
a
University of Regensburg, Universitätsstraße 31, 93053 Regensburg
e-mail: burkhard.koenig@chemie.uni-regensburg.de
Non-covalent interactions of receptors and ligands at liposomal surfaces are very similar to
recognition processes at biological membranes. Molecular recognition on such membranes is
often governed by dynamic multivalent interactions. Based on previously reported vesicular
chemosensors for the recognition of small biomolecules, [1] we currently focus on more
complex liposomal systems with different artificial binding sites for the dynamic recognition
of multivalent target molecules. The visualization and structuring of such multi-receptor
surfaces could give access to an interesting imprinting strategy:
Figure 1. Schematic drawing of an imprinting approach of a receptor embedded vesicular surface to
improve the binding affinity towards a multivalent ligand.
Surface-exposed binding sites could be patterned by heating the membranes above their main
phase transition temperature in the presence of multivalent template molecules and
subsequent cooling and removal of the templates. The Visualization of such functionalized
surfaces requires special techniques and could be achieved by AFM, STM or SFG for
instance.
[1] B. Gruber, S. Stadlbauer, A. Späth, S. Weiss, M. Kalinina, B. König, Ang. Chem. Int. Ed. 2010,
49, 7125.

SYNTHETIC TETRAAMIDES ANION RECEPTORS WITH AZULENE MOIETIES
Dawid Lichosyt, a,b Paweł Dydio b , Janusz Jurczak a,b
a) Institute of Organic Chemistry PAS, Kasprzaka 44/52, 01-224 Warsaw
b)
The Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw
dlichosyt@gmail.com
Anions play crucial role in many fields of chemistry, therefore research on anion
receptors is very important area of supramolecular chemistry.[1] Hydrogen bonds are
the most common among interactions which can be used in anion binding process. Their
accessibility and directionality enables assembly of binding sites adjusted for specific
anionic species.[2,3] In this communication we would like to present our studies on new
ligand 1 with four donors of hydrogen bonds in macrocyclic structure. In this compound
we use azulene moiety, which potentially offers optical anion sensor properties. Our
research show strong affinity 1 towards anions in DMSO + 5% H2O mixture.
To determine how important macrocyclic effect is we synthesized receptor 2.
Furthermore, we obtained diffraction grade crystals of receptor 1 and its complexes with
anions. We will discuss results of their structural analysis.
[1] Sessler J. L.; Gale P. A.; Cho W. S. Anion Receptor Chemistry, The Royal Society of Chemistry,
Cambridge, 2006.
[2] Dydio P.; Lichosyt D.; Jurczak J. Chem. Soc. Rev., 2011,40, 2971-2985
[3] Gale, P. A., Chem. Soc. Rev., 2010, 39, 3746-3771

PENDANT AZOBENZOCROWN ETHERS
IN POTASSIUM SENSORS
Mirosław Szarmach, Juliusz Makowski, Ewa Wagner-Wysiecka, Elżbieta Luboch
Gdansk University of Technology, Faculty of Chemistry,
Department of Chemical Technology, Narutowicza 11/12, 80-233 Gdansk, Poland
Due to wide possible applications in different fields azobenzocrown ethers are
interesting object of the studies. Structure modifications lead to compounds which may
be used as ionophores in ion selective electrodes (ISE) and may also work as a
chromogenic reagents for metal cation determination in solution [cf. 1-3]. Previously we
have presented the synthesis and properties of hydroxybenzocrown ethers’ derivatives
with ether or ether-ester side chain. Ligands were used as ionophores in ISE.
16-Membered azobenzocrown ether and its derivatives are well known potassium
ionophores in ISE. Here we present the ionophoric properties of newly synthesized 16membered
bisazobenzocrown and azobenzocrown ethers with disulfide or thiol residue
among the others. Obtained compounds were used for miniature potassium sensors
construction i.e. screen printed graphite and silver electrodes (ionophores with S-H or
S-S function). The influence of membrane composition, additives (carbon nanotubes)
for the sensor response were studied.
Obtained compounds were also tested as a material for surface plasmon sensors based
on gold nanoparticles for potassium recognition in water.
1. E. Luboch, E. Wagner-Wysiecka, J. F. Biernat : J. Supramol. Chem., 2, 2002, 279.
2. E. Luboch., E. Wagner-Wysiecka, Z. Poleska-Muchlado, V.Ch. Kravtsov: Tetrahedron, 61, 2005,
10738
3. E. Luboch, E. Wagner-Wysiecka, T. Rzymowski Tetrahedron, 65, 2009,10671

Development of Vesicle-based Chemosensors: Directed Assembly
of Receptors on Vesicle Surfaces
Andreas Müller,
Benjamin Gruber, Burkhard König*
Institute of Organic Chemistry, University of Regensburg, Universitätsstraße 31,
93053 Regensburg, Germany
e-mail: burkhard.koenig@chemie.uni-regensburg.de
For the development of highly specific vesicle-based chemosensors, a well
defined two-dimensional assembly of different binding sites on the spherical vesicle
surface would be necessary. Based on previous works from our group, [1] we are
currently focusing on two different strategies for receptor structuring. Considering the
unpolar environment in the vesicle membrane, utilizing mutual hydrogen bonding
interactions of the embedded binding sites could pose the method of choice for that
goal (Figure 1a). A second approach relies on imprinting techniques of receptor-
modified vesicles. The required mobility of the binding sites on the vesicle surface is
intended to be achieved either by interactions with membrane-embedded hydrogen
bonding anchors (Figure 1b) or by reorganization of the membrane above the
vesicular transition temperature (Figure 1c).
Figure 1: Different approaches for receptor structuring on vesicle surfaces.
Here, we present preliminary results from our investigations towards a defined
receptor structuring on vesicle surfaces.
[1] B. Gruber, S. Stadlbauer, A. Späth, S. Weiss, M. Kalinina, B. König, Angew. Chem. Int. Ed.
2010, 49, 7125–7128.

Synthesis of monocrown-substituted p-tert-butyl(thia)calix[4]arenes
A.A. Muravev, S.E. Solovieva, S.K. Latipov, I.S. Antipin, A.I. Konovalov
A.E. Arbuzov Institute of Organic and Physical Chemistry KazCS RAS, Russia
420088, Kazan, Arbuzov str. 8. E-mail: anton_muravyov@rambler.ru
One of the extensively developing fields of organic chemistry is the design,
synthesis, and study of the properties of nanosized molecular systems, which
incorporate some structural blocks performing various functions, such as receptor and
signal (sensor). For example, the combination of calixarenes and crown-ether fragments
in one molecule gave rise to the formation of novel class of receptors, calixcrown
ethers, which have an outstanding selectivity of recognition of alkali metal cations.
For this reason, in this work, the synthetic route to the preparation of
thiacalixmonocrown-ethers in 1,3-alternate conformation was given., which have
bromo- 1, thioaceto- 2 (4), and mercapto- 3 groups. With an aim to prevent the
formation of biscrown-ethers, we performed the distal substitution of two phenolic
groups of calixarene by ω-haloalcohols.
Currently new bromoderivatives of thiacalix[4]arene 1 and 5 have been
synthesized under Mitsunobu protocol and the methods of preparation of known
derivatives were improved. Bromo-substituents were substituted for thioaceto-groups
and, then, mercapto-groups with high yields. Structures of compounds were elucidated
by 1D and 2D NMR spectroscopy (HSQC, HMBC, COSY, NOESY), MALDI TOF
MS, IR spectra, and elemental analysis.
The work was supported by the Russian Foundation for Basic Research (grant
no. 11-03-00985).

Catechol derivatives of thiacalix[4]arenes: new building blocks for
MOF’s design.
R.I. Nougmanov, S.E. Soloveva, I.S. Antipin, A.I. Konovalov
A.E.Arbuzov Institute of Organic & Physical Chemistry.
420088 Kazan, Arbuzov str. 8, nougmanoff@hotmail.com
Thiacalixarenes represent readily available three-dimensional structures used as
useful building blocks in the design of supramolecular systems. They are well known
receptors to various types of guests: metal ions, organic substrates and metal complexes.
Catechol derivatives are perspective for applications in medicine, analytics, catalysis,
and for metal-coordination frameworks creation.
1,3-alternatethiacalix[4]aren derivative Metal cation
In the present work the possibility of combination two interesting class of precusors
1,3-alternate thiacalix[4]arenes with omega mercapto groups and catechol derivatives
for new nanoscale size macrocycles formation were established.
The structure and conformation of firstly obtained compounds were characterized
by the means of 1D 1 Н and 13 С NMR spectroscopy and methods of 2D NMR spectroscopy,
IR spectroscopy, mass spectrometry.
The work was supported by the Russian Ministry of Education and science (grant no.
0384).

Synthesis and Investigations of Multiple Hydrogen Bonded
Supramolecular Host - Guest Complexes
Philipp Otte,
Ulrich Lüning*
Otto-Diels-Institut für Organische Chemie, Olshausenstraße 40, 24098 Kiel, GER.
potte@oc.uni-kiel.de, luening@oc.uni-kiel.de
In supramolecular chemistry, molecular recognition via non-covalent binding sites
such as hydrogen bonds is common. It is necessary to have complementary hydrogen
bond acceptor (A) and hydrogen donor (D) patterns. A single hydrogen bond is
relatively weak, but the combination of multiple hydrogen bonds can lead to stable
host - guest complexes. [1]
nBu
O
N
H
O
nBu
N N
H H
N N
N H N
CN
O
N
H
O
R
nBu
R = (CH 2CH 2O) 3OEt
nBu
N
H
X
N N N R
H
H
H
N N N O
O
H3C CH 3
X = O, S
R = CO(CH2CH2O) 3Et
(CO)CH3 H
It is reasonable to synthesize molecules whose preferred conformation is the one
which can form the highest number of hydrogen bonds. If an intramolecular bond has to
be broken to get the needed binding pattern, a loss of energy at the expense of the
complex stability would be the consequence. [2] Therefore, the aim should be to stabilize
[3]
the preferred conformation by using, for example, intramolecular hydrogen bonds.
nBu
N
H
X
N N N R
H
H
H
X
N
N
X = O, S nBu
R = CO(CH2CH2O) 3Et
N N R
H
Due to the orthogonality of the binding sites, highly specific dendrimeric systems
could be generated.
[1] J. Taubitz, U. Lüning, Eur. J. Org. Chem. 2008, 5922-5927.
[2] S. Brammer, U. Lüning, C. Kühl, Eur. J. Org. Chem. 2002, 4054-4062.
[3] E.W. Meijer et al. Science 1997, 278, 1601-1604.
H
nBu
N
H
O
H
N
H
N
CH 3
N
O

Victor Pavlovsky
Ukraine, Odessa
"Structure of Derivates of 1,4-Benzodiazepine and their Affinity for Central
and Peripheral Benzodiazepine Receptors"

Chiral Concave 1,10-Phenanthrolines for Enantioselective Catalysis
Lisa Reck, Ulrich Lüning*
Otto-Diels-Institut für Organische Chemie, Olshausenstr. 40, 24098 Kiel, GER
lreck@oc.uni-kiel.de, luening@oc.uni-kiel.de
In the development of new catalysts for asymmetric synthesis, enzymes are often used
as a model. The three-dimensional concave environment of the active centre is
responsible for the high selectivity. Against this background, concave macrocyclic,
mostly bimacrocyclic, compounds have been developed which can be compared to a
“lampshade” with the concave environment as the “shade” and the active centre as the
“light bulb”. [1] Structurally, these concave reagents are much less demanding than
enzymes but they are also much more stable concerning different influences like pH or
temperature.
One group of concave reagents are the concave 1,10-phenanthrolines whose achiral
variants were successfully used for diastereoselective metal catalysis. [2,3] To enable
enantioselective catalysis, it is necessary to build a chiral cavity which can be realized
by the use of naphthyl units.
O
O
N
X
A
N
O
O
O
O
N N
X
B
O
O
X=(CH 2) n
Figure 1: Achiral concave 1,10-phenanthroline (A), axially chiral concave 1,10-phenanthroline (B).
This contribution will show the synthetic procedure to obtain chiral concave 1,10phenanthrolines
as well as possible separation techniques for the enantiomers which are
the prerequisites for their final usage as enantioselective catalysts.
1 U. H. Brinker, J.-L. Mieusset, Molecular Encapsulation, John Wiley & Sons 2010, 175-199.
2 F. Löffler, M. Hagen, U. Lüning, Synlett. 1999, 1826-1828.
3 M. Gelbert, U. Lüning, Supramol. Chem. 2001, 12, 435-444.

Synthesis of disubstituted by mercapto groups (thia)calix[4]arenes
T.A. Rovnova, A.A. Muravev, S.K. Latipov, S.E. Solovieva, I.S. Antipin, A.I.
Konovalov
A.E. Arbuzov Institute of Organic and Physical Chemistry KazCS RAS, Russia
420088, Kazan, Arbuzov str. 8. E-mail: leksa330@list.ru, svsol@iopc.knc.ru
Thiacalix[4]arenes (TCA) are next member of calixarene family. Special interest
has focused on using TCAs as suitable building blocks, multidentate preorganized
macrocyclic type ligands, precursors for creation of supramolecular architectures and
many other applications in nanotechnology and chemistry.
(Thia)calixarenes with narrow rim mercapto-substituents are potential precursors
for further modification with various functional groups and can be immobilized on a
solid surface, giving rise to sensors for heavy metal ions.
In this report, the synthesis of terminal disubstituted allyl- 3, 5; thioaceto-5, 6, 9;
and mercapto-7 (thia)calixarenes will be discussed. Interesting behavior of TCA
counterparts unsubstituted by upper rim was confirmed by MALDI TOF spectrometry
and 1 H NMR spectroscopy.
During the disubstitution of allyl-4 and bromoalkyl-8 thiacalix[4]arenes for
thioaceto-groups, the partial dealkylation of the lower rim was observed, when there
was an excess of potassium thioacetate or thioacetic acid, thus resulting in the mixture
of mono- and disubstituted products. Disubstitution was observed only when
stoichiometric amount of reagent was used.
The work was supported by RFBR grant № 11-03-00985.

Dynamic covalent chemistry: A facile room temperature reversible Diels-
Alder reaction between anthracene derivatives and N-phenyl-triazolinedione
Abstract:
Dr. N. Roy, Prof. J.-M. Lehn
Laboratoire de Chimie Supramoléculaire, ISIS
Universite´ de Strasbourg
8, allée Gaspard Monge
67000, Strasbourg (France)
A series of readily accessible dynamic Diels-Alder reactions reversible at room temperature
have been developed between anthracene derivatives as dienes and N-phenyl-1,2,4-triazoline-
3,5-di-one as dienophile. The adducts formed undergo reversible component exchange
forming dynamic libraries of equilibrating cycloadducts. Furthermore, reversible adduct
formation allows for temperature dependent modulation of the fluorescent properties of
anthracene components, a feature of potential interest for the design of opto-dynamic
polymeric materials by careful selection and manipulation of these simple dienes and
dienophiles.

SUPRAMOLECULAR POLYMERS OF OLIGO-DYNAMERS
Gaël Schaeffer & Jean-Marie Lehn
Laboratoire de Chimie Supramoléculaire, ISIS, Université de Strasbourg, France
lehn@isis.u-strasbg.fr
Unlike traditional ones, supramolecular polymers are macromolecular entities where
monomers are held together by noncovalent interactions. The labile nature of the
interactions leads to dynamic properties for this type of polymers.
Similarly it is possible to use reversible covalent bonds to obtain labile interactions
between monomers (molecular dynamicity). One can thus define a group of polymers of
different nature (supramolecular and molecular) displaying the same dynamic feature.
These polymers, named dynamers, [1]
display adaptive and exchange properties due to
the lability of the interactions between their monomers.
In the work presented here, we show that it is possible to design double dynamers where
the molecular and supramolecular dynamicity are in a non-stoichiometric ratio. This has
been achieved by the:
- formation of oligomers where the monomers are held together by covalent
reversible interactions
- functionalization of the reactive end chains of these oligomers by hydrogen bonding
units
- connection of these functionalized oligomers by supramolecular interactions
This leads to the formation of an entity that can be seen as a supramolecular polymer of
molecular oligo-dynamers. It displays two types of dynamicity that are active on a
different scale. The molecular dynamicity can be used for exchange at the monomeric
level, whereas the supramolecular one acts on a larger scale by exchange of oligomeric
blocks.
[1] J.-M. Lehn, Prog. Pol. Sci., 2005, 30, 814-831

Ekaterina Semenishyna
Ukraine, Odessa
"Synthesis of 5-Aryl-3-Acyloxy-7-Bromo-1,2-Dihydro-3H-1,4-Benzodiazepine-
2-ones, their Pharmaceutical Properties and Affinity for Central
Benzodiazepine Receptors"

Investigation of self-assembling abilities of Cu(II), Cd(II) and Ni(II)
complexes with 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin
Sinelshchikova A.A. a , Enakieva Y.Y. a , Gorbunova Y.G. a , Nefedov S.E. b ,
Bessmertnykh-Lemeune A. c , Tsivadze A.Y. a , Guilard R. c
a
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS
b
N.S. Kurnakov Institute of General & Inorganic Chemistry of RAS,
Leninskiy pr.31, Moscow, 119991 Russia e-mail: asinelshchikova@gmail.com
c
Université de Bourgogne - ICMUB UMR CNRS
5260, 9 avenue Alain Savary - BP 47870, 21078 Dijon, France
Earlier we have developed an efficient synthetic methodology toward meso-
polyphosphoryl-substituted porphyrins and showed that self-assembling of Zn complex
with 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin leads toward 2D
coordination polymer in the solution as well as in the solid state 1,2
. Such self-assembling
occurs due to formation of P=O…Zn bonds between adjacent porphyrin molecules.
In the present work we studied interaction of other d-metals with 5,15-
bis(diethoxyphosphoryl)-10,20-diphenylporphyrin and self-assembling properties of
target compounds. Complexes of Cu(II), Cd(II) and Ni(II) were obtained by the reaction
of corresponding acetate or acetylacetonate with free-base porphyrin. Complexes were
characterized by UV-vis, IR,
1 H, 31
P NMR spectroscopy, MALDI-TOF MS analysis.
Self-assembling abilities of complexes were studied by means of UV-vis, IR
spectroscopy and X-ray monocrystal and powder diffraction. It was shown that
cadmium and copper complexes demonstrate self-assembling in chloroform solution
similar as zinc complex. In contrast nickel complex does not form supramolecular
arrays in solutions. IR data confirm that in solid state self-assembling of cadmium
complex occurs due to formation of coordination bonds P=O…Cd while nickel complex
does not form such coordination bonds. The formation of 2D-coordination network in
the case of Cu(II) and Cd(II) porphyrinates was also proved by means of X-ray
diffraction analysis of mono- and polycrystalline complexes. At the same time Ni(II)
porphyrinate crystalises without formation of P=O…M bonds.
Acknowledgements: This work was performed in the framework of French-Russian Associated
Laboratory “LAMREM” supported by ARCUS 2007 Burgundy-Russia project, Russian Foundation for
Basic Research, the CNRS and Russian Academy of Sciences.
REFERENCES
1. Enakieva Y.Y., Bessmertnykh A.G., Gorbunova Y.G., Stern C., Rousselin Y., Tsivadze A.Y., Guilard R. Org.
Lett., 2009, 11, 3842-3845.
2. Kadish K.M., Chen P., Enakieva Y.Y., Nefedov S.E., Gorbunova Y.G., Tsivadze A.Y., Bessmertnykh-Lemeune
A., Stern C., Guilard R. J. of Electroanalytical Chemistry, 2011, available online 08/02/2011,
doi:10.1016/j.jelechem.2011.01.011.

Core-Modified Porphyrinoid: Syntheses and Characterization of
Disilahexaphyrinoid
Janusz Skonieczny,
Lechosław Latos-Grażyński, Ludmiła Szterenberg
Department of Chemistry
University of Wrocław
14 F. Joliot-Curie St., Wrocław 50 383, Poland
e-mail: LLG@wchuwr.pl
Formal replacement of two pyrrolic nitrogen atoms in the hexaphyrin ring with
heteroatoms (O, S, Se) yields a class of diheterohexaphyrins. [1]
In this work the
modified silole has been used as building block in the synthesis of silicon-containing
hexaphyrinoid.
1
A 2,5-bis(p-tolylhydroxymethyl)-3,4-diphenylosilole [2]
reacts with pyrrole
affording 16-silatripyrrane 1. Subsequent an acid catalyzed condensation of 1 and
aldehyde afforded a silole-containing hexaphyrin 2 which contains two built-in silole
units. This is the first example of a silole ring incorporated into the hexaphyrinoid
frame.
All compounds have been characterized using multinuclear NMR spectroscopy
and mass spectrometry. The density functional theory (DFT) has been applied to model
the molecular structure of disilahexaphyrinoid consistent with constrains imposed by
NOE experiments.
_____
[1] R. Misra, R. Kumar, T. K. Chandrashekar, B. S. Joshi, J. Org. Chem. 2007, 72, 1153.
[2] J. Skonieczny, L. Latos-Grażyński, L. Szterenberg, Chem. Eur. J. 2008, 4861.
2

Conjugates of thiacalixarenes and clathrochelates - new inclusion
M n+
Hal
Hal
Clathrochelate
precursor
+
HS
HS
O
O
S
S
S S
O
O
SH
SH
Thiacalix[4]arene in the
1,3-alternate conformation
compounds
S.E. Soloveva a , A.A.Tyuftin a , Y.Z.Voloshin b , M.Gruner c , W. Habicher c , I.S.Antipin a ,
A.I.Konovalov a
a A.E.Arbuzov Institute of Organic & Physical Chemistry, 420088, Kazan, Russia,
Arbuzov str., 8. , b A.N.Nesmeyanov Institute of Organoelement Compounds RAS,
119991, Moscow, Vavilova str. 28, Russia, c
Technical University, Institute of Organic
Chemistry, Technical Univercity, Bergstr.,66c D-01062 Dresden, Germany/
E-mail: svsol@iopc.knc.ru
Nanosized polytopic molecular systems are usually formed from several
relatively independent building blocks, which are bounded either covalently or via weak
intermolecular interactions. The most effective strategy to obtain such systems is based
on the “bottom – up” principle that uses the appropriate molecular precursors.
Thiacalixarene scaffolds can be regarded as the precursors of more complex nanosized
systems, in particular, hybrid and polytopic molecules.
M n+
Tris-dioximate clathrochelates
are the macrobicyclic compounds with a metal ion encapsulated in a three-dimensional
macropolycyclic ligand cavity. These complexes demonstrate unique thermodynamic
and kinetic stabilities and have unusual redox and photochemical properties. Here we
report the synthesis and the characterization of the first hybrid calixarenoclathrochelates.
Their synthesis was performed by the macrocyclization of the tetra-O-
substituted thiacalix[4]arenes in 1,3-alternate conformation and monoribbedfunctionalized
clathrochelate iron(II). These hybrids contain of two novel macrocyclic
cavities.
S
S
O
Guest
O
S
S
S S
O
O
Hybrid complex
The support from RFBR (N 11-03-00985) is gratefully acknowledged.
S
S
M n+

A Facile Palladium-Mediated Contractions of Benzene to
Cyclopentadiene: Transformations of Palladium(II) p-Benziporphyrin
Bartosz Szyszko, Lechosław Latos-Grażyński and Ludmiła Szterenberg
Department od Chemistry
University of Wrocław
14 F. Joliot-Curie St., 50-383 Wrocław, Poland
Palladium(II) p-benziporphyrin provides the unique macrocyclic vessel to afford the
contraction of benzene to cyclopentadiene embedded in the first instance of 21carbaporphyrin
complexes. Addition of palladium(II) and a hydroxide ion to a C–C
double bond, β elimination, and competing cheletropic extrusion of carbon oxide and
1,2-hydride shift reactions lead to the contraction of p-phenylene to form a
cyclopentadiene unit. This reaction results in the formation of a 21-carbaporphyrin from
a palladium(II) p-benziporphyrin. In the case of chloropalladium 1,4-naphthiporphyrin
similar reactivity pattern allowed to obtain 21-benzocarbaporphyrin on the course of
naphthalene to isoindene contraction.

Chromogenic Anion Receptors Based on s-Triazine Skeleton.
Synthesis and Properties.
Ewa Wagner-Wysiecka,
Karolina Mazur, Kamila Muchowska
Gdansk University of Technology, Faculty of Chemistry,
Department of Chemical Technology, Narutowicza 11/12, 80-233 Gdansk, Poland
However the design of the new anion receptors is not always easy [1], it is a growing
field of research due to the key roles played by anions in biology, environment and
chemistry [e.g. 2, 3]. Rapid information about anion-receptor interaction may be
achieved by incorporating a chromophore residue(s) into the ligand structure. Thanks it,
anion recognition is well seen with a “naked eye” and quantitative studies of
complexation process are possible with the use of simple and no expensive analytical
method - UV-Vis spectroscopy. Promising building block for anion sensors is 1,3,5triazine
ring [4]. It can be involved in all categories of supramolecular interactions e.g.
coordination bonds, hydrogen bonding, electrostatic, charge transfer and aromaticstacking
interactions. Even compounds of very sophisticated structure may be easily
obtained using cyanuric chloride as a substrate. Here, the synthesis of chromogenic
derivatives based on 1,3,5-triazine ring is presented. Obtained compounds differ in type,
size and number of substituents joined with heterocyclic residue. The distinctive feature
of the introduced substituents is the presence of additional functional groups which can
act as proton donors in anion recognition via hydrogen bond formation. Anion
complexation studies were carried out with the use of UV-Vis and NMR spectroscopy
in organic solvents and their mixtures with water. The effect of the counter ion was also
taken under investigation.
Acknowledgments: Author kindly acknowledged support from sources for science in years 2010-2011,
Grant No. N N204 137438.
[1]. F. P. Schmidtchen, Coord. Chem. Rev. 250 (2006) 2918.
[2]. T. Gunnlaugsson, M. Glynn, G. M. Tocci, P.E. Kruger, F. M. Pfeffer, Coord. Chem. Rev. 250 (2006) 3094.
[3]. C. Caltagirone, P. A. Gale, Chem. Soc. Rev. 38 (2009) 520.
[4]. T. J. Mooibroek, P. Gamez, Inorg. Chim. Acta 360 (2007) 381.

Family Name First Name Title Position Institution Country, City
Allendörfer Nadine - Postdoc ISIS, Laboratoire de Chimie Supramoleculaire, Université de Strasbourg France, Strasbourg
Anhuth Kerstin - Ph.D.Student Organic Chemistry, University of Duisburg-Essen Germany, Essen
Antipin Igor Sergeevich Prof. Head of Department Kazan (Volga-Region) Fedefal Univercity Russia, Kazan
Bak Krzysztof - BSc. Student Faculty of Chemistry, University of Warsaw Poland, Warsaw
Balk Stefan - Ph.D.Student Institute of Organic Chemistry, University of Regensburg Germany, Regensburg
Berrocal Josè Augusto - Ph.D.Student University of Rome - Sapienza Italy, Rome
Bhuyan Mouchumi - Ph.D.Student Institute of Organic Chemistry, University of Regensburg Germany, Regensburg
Birin Kirill - Researcher A.N. Frumkin Institute of Physical Chemistry and Electrochemistry (RAS) Russia, Moscow
Bochkova Olga Dr. Postdoc A.E. Arbuzon Institute of Organic and Physical Chemistry of KSC of RAS Russia, Kazan
Bregestovsky Piotr Prof. Director of Research National Institute of Medical Research (INSERM) France, Marseille
Burilov Vladimir - Ph.D.Student A.E. Arbuzon Institute of Organic and Physical Chemistry of KSC of RAS Russia, Kazan
Cadot Emmanuel Prof. Researcher Institut Lavoisier, University of Versailles France, Versailles
Dabrowa Kajetan - Ph.D.Student Institute of Organic Chemistry, Polish Academy of Sciences- Faculty of Chemistry, University of Warsaw Poland, Warsaw
De Cola Luisa Prof. Westfälische Wilhelms-University Münster
Germany, Münster
Ph i l I i d C f N h l
Dydio Pawel - Ph.D.Student University of Amsterdam The Netherlands, Amsterdam
Enakieva Yulia Dr. Senior Researcher A.N. Frumkin Institute of Physical Chemistry and Electrochemistry (RAS) Russia, Moscow
Epifanova Natalia - Junior Researcher, PhD Student Institute of Organic and Physical Chemistry Russia, Kazan
Fanlo Virgós Hugo - Ph.D.Student Stratingh Institute The Netherlands, Groningen
Fedin Vladimir Prof. Director Nikolaev Institute of Inorganic Chemistry SB RAS Russia, Novosibirsk
Fedorova Olga Prof. Head of Laboratory A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences Russia, Moscow
Fedorova Olena Dr. Assistant Professor National University - Lviv Polythechnik Ukraine, Lviv
Ferlay Sylvie Maître de Conférences Laboratoire de Tectonique Moléculaire du Solide, Institut Le Bel France, Strasbourg
Floquet Sébastien Dr. Assistant Professor Institut Lavoisier, University of Versailles France, Versailles
Galukhin Andrey - Ph.D.Student Kazan (Volga Region) Federal University Russia, Kazan
Gerasimov Alexander - Engineer Kazan (Volga Region) Federal University Russia, Kazan
Gorbachuk Vladimir - Ph.D.Student Kazan (Volga Region) Federal University Russia, Kazan
Gorbunova Yulia Prof. Leading Researcher A.N. Frumkin Institute of Physical Chemistry and Electrochemistry (RAS) Russia, Moscow
Gruber Benjamin - Ph.D.Student Institute of Organic Chemistry, University of Regensburg Germany, Regensburg
Hesseler Britta - Ph.D.Student Christian-Albrecht-University of Kiel Germany, Kiel
Hosseini Mir Wais Prof. Professor Institut Le Bel France, Strasbourg
Hubscher Veronique Dr. Assistant Professor Ecole européenne d'ingénieurs en chimie (EPCM) - UDS/IPMC France, Strasbourg
Isaak Elisabeth - Ph.D.Student Institute of Organic Chemistry, University of Regensburg Germany, Aachen
Jianwei Li - Ph.D.Student Stratingh Institute The Netherlands, Groningen
Jonkheijm Pascal Dr. Assistant Professor Institute for Nanotechnology, University of Twente The Netherlands, Enschede
Kalchenko Vitaly Prof. Active Director Institute of Organic Chemistry of NAS of Ukraine Ukraine, Kyiv
Kalchenko Olga Dr. Senior Researcher Institute of Organic Chemistry, National Academy of Sciences of Ukraine Ukraine, Kyiv
Kataev Evgeny Dr. Junior Professor Tecnical University of Chemnitz, Institute for Chemistry Germany, Chemnitz
Klimchuk Olga Dr. Postdoc Institut Pluridisciplinaire Hubert Curien, CNRS-IPHC/DRS, UMR 7178 Chimie Nucléaire France, Strasbourg
Kolosova Olga Yu Dr. Researcher A.N. Nesmeyanov Institute of Organoelement Compounds of RAS Russia, Moscow
Král Vladimir Institute of Chemical Technology, Department Analytical Chemistry Chech, Prague
Krebs Ina - Ph.D.Student Organic Chemistry, University of Duisburg-Essen Germany, Essen
Lang Tobias - Ph.D.Student Institute of Organic Chemistry, University of Regensburg Germany, Regensburg
Latos-Grazynski Lechoslaw Prof. Department of Chemistry, University of Wroclaw Poland, Wroclaw
Lichosyt Dawid - Student Institute of Organic Chemistry Polish Academy of Sciences- Faculty of Chemistry University of Warsaw Poland, Warsaw

Family Name First Name Title Position Institution Country, City
Luboch Elzbieta Prof. Gdansk University of Technology Poland, Gdansk
Martynov Alexander - Senior Researcher A.N. Frumkin Institute of Physical Chemistry and Electrochemistry (RAS) Russia, Moscow
Mizerev Artemiy - Ph.D.Student M.V. Lomonosov Moscow State University Russia, Moscow
Müller Andreas - Ph.D.Student Institute of Organic Chemistry, University of Regensburg Germany, Regensburg
Muravev Anton - Junior Researcher, PhD Student Institute of Organic and Physical Chemistry Russia, Kazan
Nougmanoff Ramil - Ph.D.Student A.E.Arbuzov Institute of Organic and Physical Chemistry Russia, Kazan
Novikov Volodymyr Prof. Head of Department National University - Lviv Polythechnik Ukraine, Lviv
Oshchepkov Maxim Dr. Postdoc D.Meneleyev University of Chemical Technology of Russia Russia, Moscow
Otte J.Philipp - Ph.D.Student Otto-Diels-Institute for Organic Chemistry, University of Kiel Germany, Kiel
Panchenko Pavel - Ph.D.Student A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences Russia, Moscow
Paramonov Sergey Dr. Junior Researcher A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences Russia, Moscow
Pavlovsky Victor Dr. Deputy Head of Department A.V.Bogatsky Physico-Chemical Institute of NAS of Ukraine Ukraine, Odessa
Reck Lisa - Ph.D.Student Christian-Albrecht-University Kiel Germany, Kiel
Reimers Tim - Ph.D.Student Otto-Diels-Institute for Organic Chemistry, University of Kiel Germany, Kiel
Reinhoudt David Prof. Laboratory for Supramolecular Chemistry and Technology, MESA+ Institute for Nanotechnology
The Netherlands, Twente
U i i f T
Rodik Roman Dr. Senior Researcher Institute of Organic Chemistry, National Academy of Sciences (NAS) of Ukraine Ukraine, Kyiv
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Schatz Jürgen Prof. Department of Chemistry and Pharmacie, Institute for Organic Chemistry, Friedrich-Alexander-University Germany, Erlangen
Scheer Manfred Prof. Institute for Inorganic Chemistry, University of Regensburg Germany, Regensburg
Scherman Oren Dr. Department of Chemistry, University of Cambridge UK, Cambridge
Schmuck Carsten Prof. Chair of Organic Chemistry Organic Chemistry, University of Duisburg-Essen Germany, Essen
Semenishyna Ekaterina - Ph.D.Student A.V.Bogatsky Physico-Chemical Institute of NAS of Ukraine Ukraine, Odessa
Shkrabak Alexandr - Ph.D.Student O.V. Palladin Institute of Biochemistry of National Academy of Sciences (NAS) of Ukraine Ukraine, Kyiv
Sinelshchikova Anna - Researcher A.N. Frumkin Institute of Physical Chemistry and Electrochemistry (RAS) Russia, Moscow
Skonieczny Janusz Dr. Research Associate University of Wroclaw Poland, Wroclaw
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