ISMSC 2007 - Università degli Studi di Pavia

nd International Symposium 

on Macrocyclic and 

Supramolecular Chemistry 

2 nd 

Salice Terme (Pavia), Italy 

June 24-28, 2007 

Program and 

Abstracts

Welcome to ISMSC 2007 

The University of Pavia is pleased to host the 2nd International Symposium on 

Macrocyclic and Supramolecular Chemistry, ISMSC 2007, in Salice Terme (Pavia) 

from 24 to 28 June, 2007. More than 250 delegates are participating in the 

conference, which is articulated in 9 Plenary Lectures, 12 Invited Lectures, 21 

Oral Communications, and 200 Poster Presentations, divided in 2 Sessions. The 

high standard of the scientific contributions promises for the success of the 

Symposium. The Organizing Committee wishes all the delegates a pleasant stay 

in Salice Terme and, beyond the scientific sessions, to profit from the gifts of the 

land, from the point of view of culture, art and history and, also, from the more 

material side of food and wine. 

Pavia, June 2007 

About the logo 

The logo combines the official symbol of Terme di Salice (a spring of thermal water topped by the red 

flower of hibiscus) and the partially hidden structural formula of a 14-membered macrocycle. 

Although the 14-membered saturated ring is one of the most represented cyclic structures among 

natural substances, the present combination intends to pay a tribute to cyclam. Cyclam, and the 

related family of tetra-aza macrocycles, stand at the basis of macrocyclic chemistry, thanks to the 

pioneering work of Busch and Curtis in the 1960's, and their synthesis is strictly associated to the 

development of the template effect, a leading concept of supramolecular chemistry. 

About the cover 

The cover presents a fresco (partially transferred on canvas) by Bernardino Lanzani and his school 

(1522) in the Basilica of San Teodoro in Pavia. The painting features one the Patron Saints of Pavia, 

Sant’Antonio Abate, and a view of the of the town of Pavia from the right bank of Ticino river (the 

most ancient picture of Pavia available today). The fresco was painted only three years before the 

Battle of Pavia (24 February, 1525), in which the Spanish-German army of Charles V, Emperor of 

the Holy Roman Empire, defeated the army of Francis I, King of France. The battle took place in the 

park beyond the Castle, featured in the background of the fresco, lasted less than 4 hours and 

caused more than 10 000 casualties, most on the French side. Francis I was made a prisoner and 

brought to Spain. When the fresco was painted, Pavia was under the Spanish rule and was the 

object of occasional attacks by the French. This explains the presence of knights and armigers in the 

streets and around the Castle, as shown in Bernardino Lanzani’s fresco.

Eric Anslyn 

University of Texas at Austin 

Dept. of Chemistry and Biochemistry 

Austin, TX 78712 USA 

Luigi Fabbrizzi 

Università di Pavia 

Dipartimento di Chimica Generale 

I-27100 Pavia, Italy 

Makoto Fujita 

University of Tokyo 

Department of Applied Chemistry 

Tokyo 113-8656, Japan 

Thomas M. Fyles 

University of Victoria 

Department of Chemistry 

Victoria, BC, Canada 

Philip A. Gale 

School of Chemistry 

University of Southampton 

Southampton, SO17 1BJ, UK 

Karsten Gloe 

Institut für Anorganische Chemie 

Technische Universität Dresden 

D-01062 Dresden, Germany 

George W. Gokel 


University of Missouri 

Saint Louis, MO 63121, USA 

Roger G. Harrison 


Brigham Young University 

Provo, UT 84602 

International Scientific Committee 

Yoshihisa Inoue 

Osaka University 

Department of Applied Chemistry 

Suita 565-0871, Japan 

Reed M. Izatt 




Richard Keene 

School of Pharmacy & Molecular 

Sciences, James Cook University 

Townsville, Queensland, Australia 

John D. Lamb 




Roeland J. M. Nolte 

Radboud University Nijmegen 

NL-6500 HC Nijmegen 

The Netherlands 

Jonathan L. Sessler 


University of Texas 

Austin, TX 78712, USA 

Bradley D. Smith 

University of Notre Dame 

Dept. of Chemistry and Biochemistry 

Notre Dame, IN 46556, USA 

Giuseppe Arena 

Università di Catania 

Vincenzo Balzani 

Università di Bologna 

Francesco Barigelletti 

I.S.O.F. C.N.R., Bologna 

Antonio Bianchi 

Università di Firenze 

Luigi Fabbrizzi 

Università di Pavia 

Luigi Mandolini 

Università di Roma 

National Organizing Committee 

Mauro Micheloni 

Università di Urbino 

Silvio Quici 

I.S.T.M. C.N.R., Milano 

Gianfranco Savelli 

Università di Perugia 

Umberto Tonellato 

Università di Padova 

Rocco Ungaro 

Università di Parma 

Pietro A. Vigato 

I.C.I.S. C.N.R., Padova 

ISMSC Local Organizing Committee 

Valeria Amendola 

Maurizio Licchelli 

Carlo Mangano 

Luigi Fabbrizzi (chairman) 

Piersandro Pallavicini 

Antonio Poggi 

Angelo Taglietti

International Izatt-Christensen Award in Macrocyclic Chemistry 

The International Izatt-Christensen Award in Macrocyclic Chemistry is awarded by 

the International Advisory Committee of the Symposium in honour of Professor 

Izatt and the late Professor Christensen, who conceived the International 

Symposia concept and organized the first five Symposia starting in 1977. 

The winner of the 2007 Izatt-Christensen Award is: 

Professor David A. Leigh 

University of Edinburgh 

David Leigh was born in Birmingham (UK) and obtained both his BSc and PhD 

from the University of Sheffield (the latter with Sir J. Fraser Stoddart, the 1993 

Izatt-Christensen Awardee). After 

postdoctoral research at the NRC of 

Canada in Ottawa (1987-1989) he 

returned to the UK as a lecturer at the 

University of Manchester Institute of 

Science and Technology (UMIST). In 1998 

he moved to the University of Warwick and 

in 2001 he took up the Forbes Chair of 

Organic Chemistry at the University of 

Edinburgh. 

He currently holds both an EPSRC Senior 

Research Fellowship and a Royal Society- 

Wolfson Research Merit Award, and is a 

Fellow of the Royal Society of Edinburgh, 

Scotland's National Academy of Science 

and Letters. His research achievements 

include the development of several high 

yielding hydrogen bonding and metal 

template strategies to catenanes and 

rotaxanes which, in recent years, have 

enabled the synthesis of increasingly 

sophisticated and functional molecular 

switches and motors. His most recent contributions include the introduction of 

concepts from statistical physics, such as ratcheting, balance and escapement, 

into synthetic molecular machine theory and design. 

In the occasion of the presentation of the Award, in the afternoon session of 28 

June, Professor Leigh will deliver his lecture Exercising demons: synthetic 

molecular motors and machines. 

Call for Nominations for the 2008 International 

Izatt-Christensen Award in Macrocyclic Chemistry 

The International Advisory Committee invites nominations for the International 

Izatt-Christensen Award in Macrocyclic Chemistry. Professor Izatt and the late 

Professor Christensen conceived the International Symposia concept and 

organized the first five Symposia starting in 1977. 

IBC Advanced Technologies, Inc., of American Fork, Utah, USA, is the sponsor of 

the award. The winner will receive a $2,000 honorarium and up to $1,000 for 

travel expenses. 

The award is open to anyone working in the area of macrocyclic chemistry who 

has not received an international award of $25,000 or more. 

Six copies of nomination materials, which should include curriculum vitae, a 

publication list, a five page nomination statement, and up to three letters of 

recommendation from other scientists who know of the nominee’s work, should be 

sent by email if possible no later than 1 February 2008 to: 

Reed M. Izatt 

Professor Emeritus 




USA 

Tel.: int.l + 1 801 422 3667 (Secretary) 

Email: reed_izatt@byu.edu 

A panel of five international macrocyclic chemists representing the sub-areas of 

the field will select the winner. The winner will be announced in the spring of 2008. 

He/She will receive the award and present an invited lecture at the Third 

International Symposium on Macrocyclic and Supramolecular Chemistry 

(ISMSC2008) to be held in Las Vegas, Nevada, USA, from 13-18 July 2008.

1 

Map of Salice Terme 

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President Hotel Terme 

Via Perosi 5 tel 0383 91941 

conference venue, registration 

desk, welcome buffet, lunch, spa 

Hotel Clementi 

via Diviani 17 tel 0383 947150 

Nuovo Hotel Terme 


Park Hotel 


Hotel Genova 

viale Terme 105 tel 0383 91227 

Hotel Villa dei Tigli 

via Chiesa Vecchia 2 tel 0383 944566 

Albergo Buenos Aires 


Hotel Salus 

viale terme 31 tel 0383 91561 

Hotel Milano 


Locanda Stazione di Salice 

via Diviani 5/7 tel 0383 944501 

Terme di Salice (SPA) 

Golf Club 

Pharmacy, bank, info point, 

Via Marconi

Rivanazzano 

1 

Salice Terme 

1 

President Hotel Terme 

Via Perosi 5 tel 0383 91941 

conference venue, registration 

desk, welcome buffet, lunch, spa 

Albergo Ristorante Selvatico 

Via Silvio Pellico 5 tel 0383 944720 

Rivanazzano 

Golf Club 

Terme di Salice (SPA) 

Pharmacy, bank, info point, 

Via Marconi

Symposium Program 

All sessions will take place at President Hotel Terme, Via Perosi, Salice Terme. 

Sunday, 24 June - Afternoon Session 

Conference Registration From 12:00 until 19:00 

17:30 – 18:00 Conference Opening 

Chair: L. F. Lindoy 

18:00 – 18:50 Plenary Lecture: Th. A. Kaden: 40 years of poly-azamacrocycles. 

A personal historical view PL 1 

19:30 Welcome Buffet 

Monday, 25 June - Morning Session 

Chair: A. Arduini 

8:45 – 9:35 Plenary Lecture: S. Shinkai: Shape-controlled functional 

materials created by modification of preorganized assemblies 

PL 2 

9:35 – 10:05 Invited Lecture: D. M. Rudkevich: Carbon dioxide and supramolecular 

chemistry IL 1 

10:05 – 10:25 Oral Presentation: T. Gottschalk: Host Molecules with 

Switchable Portals: Reversibly Controllable Guest Encapsulation 

OP 1 

10:25 – 10:50 coffee break 

Chair: J. W. Steed 

10:50 – 11:20 Invited Lecture: A. E. Rowan: Mechanistic aspects of threading 

of polymers in processive rotaxane catalysts IL 2 

11:20 – 11:40 Oral Presentation: M. Barboiu: Constitutional sol-gel transcription 

of nucleobases self-assembly codes OP 2 

11:40 – 12:00 Oral Presentation: J. Price: Control Of Molecular Architecture 

By Steric And Electronic Factors: Dinuclear Side-By-Side Vs 

Tetranuclear [2x2] Grid-Type Silver(I) Complexes OP 3 

12:00 – 12:20 Oral Presentation: W. M. Nau: Supra-Biomolecular Tandem 

Assays OP 4 

12:30 Lunch 

Monday 25 June - Afternoon Session 

Chair: A. Bianchi 

14:30 – 15:20 Plenary Lecture: K. Bowman–James: Macrocyclic hosts for 

supramolecular and traditional coordination chemistry PL 3 

15:20 – 15:40 Oral Presentation: F. Mancin: Self-Organized Fluorescent 

Nanosensors For Ratiometric Pb(II) Detection OP 5 


Chair: V. Heitz 

16:10 – 16:40 Invited Lecture: E. Alessio: Synthetic strategies and structural 

aspects of metal-mediated multi-porphyrin assemblies IL 3 

16:40 – 17:00 Oral Presentation: R. Nishiyabu: Nucleotides as Building 

Blocks for Lanthanide Based Nanoparticles OP 6 

17:00 – 17:20 Oral Presentation: L. Prins: Catalyst discovery using dynamic 

combinatorial chemistry OP 7 

Poster Session A From 17:30 until 19:30 

21:30 Social Program: non-scientific Lecture 

Luigi Fabbrizzi: Communicating with Symbols – From 

Alchemy to Chemistry 

Tuesday, 26 June - Morning Session 

Chair: K. N. Raymond 

8:45 – 9:35 Plenary Lecture: J. F. Stoddart: Covalent and coordinative 

dynamic chemistry PL 4 

9:35 – 10:05 Invited Lecture: A. Harada: Cyclodextrin-based supramolecular 

architectures and dynamics IL 4 

10:05 – 10:25 Oral Presentation: T. M. Fyles: Structure-activity studies on ion 

oligoester channels OP 8 


Chair: P. A. Tasker 

10:50 – 11:20 Invited Lecture: J. R. Nitschke: Complexity from simple parts 

via subcomponent self-assembly IL 5

11:20 – 11:40 Oral Presentation: F. Denat: Efficient tools for the synthesis of 

cyclen and cyclam derivatives OP 9 

11:40 – 12:00 Oral Presentation: L. F. Lindoy: New Discrete Metallo- 

Structures Incorporating 5,5"'-Dimethylquaterpyridine and 

Expanded Derivatives OP 10 

12:00 – 12:20 Oral Presentation: L. Isaacs: Cucurbit[n]uril Molecular 

Containers OP 11 

12:30 Lunch 

Tuesday, 26 June - Afternoon Session 

Chair: J. L. Sessler 

14:30 – 15:20 Plenary Lecture: P. D. Beer: Anion-templated assembly of 

interpenetrated and interlocked structures PL 5 

15:20 – 15:50 Invited Lecture: G. W. Gokel: Chloride ion transport and 

complexation by amphiphilic heptapeptides IL 6 


Chair: E. Akkaya 

16:20 – 16:50 Invited Lecture: J. W. Steed: Anion binding as a conformational 

and self-assembly trigger IL 7 

16:50 – 17:10 Oral Presentation: A. M. Costero: Biphenylthioureas as 

organo-catalysts for electrochemical reductions OP 12 

17:10 – 17:30 Oral Presentation: P. Anzenbacher: Anion sensing in 

consumer products: from multi-electrolytes to toothpaste 

OP 13 

Poster Session B From 17:30 until 19:30 

Wednesday, 27 June - Morning Session 

Chair: T. M. Fyles 

8:45 – 9:35 Plenary Lecture: J.-P. Sauvage: Transition metal-complexed 

catenanes, rotaxanes and molecular machines PL 6 

9:35 – 10:05 Invited Lecture: J. L. Sessler: Oligopyrrole-based chemosensors 

for potentially hazardous materials IL 8 

10:05 – 10:25 Oral Presentation: A. Guenet: A molecular gate based on a 

porphyrin and a silver lock OP 14 


Chair: F. Arnaud 

10:50 – 11:20 Invited Lecture: E. V. Rybak-Akimova: Pyridine-containing 

macrocycles for oxygen activation and anion recognition IL 9 

11:20 – 11:40 Oral Presentation: P. Metrangolo: From Non-Mesomorphic 

Nature To Liquid Crystallinity Via Halogen Bonding OP 15 

11:40 – 12:00 Oral Presentation: P. A. Tasker: Buttressing effects in pseudomacrocyclic 

metal extractants OP 16 

12:00 – 12:20 Oral Presentation: Y. Voloshin: Biochemical and medicinal 

applications of polytopic super- and supramolecular systems 

based on the cage transition metal complexes OP 17 

12:30 Lunch 

Wednesday, 27 June - Afternoon 

15:00 – 21:00 Social Program 

Visit to Pavia with Reception at the University 

Thursday, 28 June - Morning Session 

Chair: G. Arena 

8:45 – 9:35 Plenary Lecture: R. Ungaro: Calixarenes in action: from anion 

recognition to DNA condensation and RNA cleavage PL 7 

9:35 – 10:05 Invited Lecture: J. D. Lamb: A comparison of mobile phase and 

stationary phase. Macrocycle based ion chromatography IL 10 

10:05 – 10:25 Oral Presentation: K. N. Raymond: Catalysis in Chiral Supramolecular 

Flasks OP 18 


Chair: E. V. Rybak-Akimova 

10:50 – 11:20 Invited Lecture: O. Reinaud: Supramolecular control of a metal 

center embedded in a biomimetic hydrophobic cavity: the 

Funnel Complexes IL 11 

11:20 – 11:40 Oral Presentation: S. Roelens: Pyrrolic Tripodal Receptors For 

Molecular Recognition Of Monosaccharides: Tuning Selectivity 

OP 19

11:40 – 12:00 Oral Presentation: V. Heitz: Threading of molecular handcuffs 

to obtain new interlocked two-dimensional species OP 20 

12:00 – 12:20 Oral Presentation: P. Tecilla: Selective Transmembrane Anion 

Conductances Of Polycationic Calix[4]Arenes OP 21 

12:30 Lunch 

Thursday, 28 June - Afternoon Session 

Chair: J. D. Lamb 

14:30 – 14:45 Izatt-Christensen Award 2007: presentation by R. M. Izatt 

14:45 – 15:35 Izatt-Christensen Award 2007 Lecture: D. A. Leigh: Exercising 

demons: synthetic molecular motors and machines ICA 

15:35 – 16:05 Invited Lecture: S. Kubik: Why are certain cyclopeptides so 

efficient anion hosts? IL 12 


Chair: L. Fabbrizzi 

16:30 - 16:40 Presentation of ISMSC 2008 (Las Vegas): J. L. Sessler 

16:40 - 16:50 Presentation of ISMSC 2009 (The Netherlands): A. E. Rowan 

16:50 – 17:40 Plenary Lecture: J.-M. Lehn: From Supramolecular Chemistry 

to Constitutional Dynamic Chemistry PL 8 

17:40 – 18:00 Conference Closing 

20:00 Gala Dinner

Poster session A 

Monday, 25 June 17:30-19:30 

PSA 1 Efficient synthesis of pseudopeptidic macrocycles through anion 

templation 

Ignacio Alfonso, Miriam Bru, M. Isabel Burguete, Santiago V. Luis, 

Jennifer Rubio 

PSA 2 Synthesis And Solid State Structure Of A Double Calix[6]Arene Nanotube 

Arturo Arduini, Giovanni Faimani, Andrea Pochini, Andrea Secchi, Franco 

Ugozzoli, Chiara Massera 

PSA 3 Thermodynamics Of The Selective Incapsulation Of Aqueous Cationic 

Guests Into A Supramolecular Tetrahedral Anionic Host 

Giuseppe Arena, Carmelo Sgarlata, Valeria Zito, Kenneth N. Raymond, 

Bryan E. F. Tiedemann 

PSA 4 Synthesis and Characterization of Novel Unsymmetrical Phthalocyanines 

with Crown Ether Unit 

Yasin Arslanoglu, Esin Hamuryudan 

PSA 5 Tetra-Cationic phthalocyanines 

Yasin Arslanolu, Esin Hamuryudan 

PSA 6 Water Soluble, NIR Emitting Boradiazaindacene Dyes As Fluorescent Ion 

Sensors 

Serdar Atilgan, Tugba Ozdemir and Engin U. Akkaya 

PSA 7 Self-Assembly of N,C-Linked Peptidocalix[4]Arenes 

L. Baldini, G. Faimani, A. Casnati, F. Sansone, R. Ungaro 

PSA 8 Acyclic Pyrrole-Based Anion Receptors: Design, Synthesis, And Anion 

Binding Properties 

Jonathan L. Sessler, Natalie M. Barkey, G. Dan Pantos, Vince M. Lynch 

PSA 9 Cell Penetrating Borosilica Nanoparticles: Potential Delivery Agents For 

BNCT 

Maria Arduini, Giuliana Battanolli, Luca Baù, Fabrizio Mancin, Umberto 

Tonellato, Chiara Compagnin, Lucia Celotti, Maddalena Mognato, Elena 

Reddi 

PSA 10 Screening of 1,3,4-oxadiazoles by narrow-bore HPLC with various 

peptidomimetic calixarene-bonded stationary phases 

G. Bazylak, A. A. Haidar 

PSA 11 Copper(II) Complexes of Aza Pyridinophanes and Terpyridonophanes as 

SOD Mimics 

Salvador Blasco, Jorge González, Enrique García-España, Pablo Gaviña, 

Hermas Jiménez, Raquel Belda, Conxa Soriano, José M. Llinares, 

Carmen Terencio 

PSA 12 Hydrazone Exchange Dynamic Combinatorial Libraries In Aqueous And 

Organic Solvents 

Ana Belenguera, Jingyuan Liua, Christoph Naumannb, Jeremy K.M. 

Sandersa 

PSA 13 Halide anion interactions with dicopper(II) and dicobalt(II) bistren cryptates 

Greta Bergamaschi, Valeria Amendola, Luigi Fabbrizzi, Antonio Poggi 

PSA 14 Dynamic Combinatorial Chemistry- a Selection Based Approach to 

Catalysis 

Enda Bergin, David Lewis, Zoe Pikramenoub, Sijbren Otto 

PSA 15 Can electron-deficient aromatic rings be used to bind anions by design? 

Orion B. Berryman, Jeffrey S. Meisner, David P. Stay, Darren, W. 

Johnson, Vyacheslav S.,Bryantsev, Benjamin, P. Hay 

PSA 16 Dimerization of a hydrogen-bonded 2,6-alkynylpyridyl scaffold is induced 

by both water and anions. 

Orion B. Berryman, Charles A. Johnson, Michael M. Haley, Darren, W. 

Johnson 

PSA 17 Sensing With Cavitand: Moving From Selectivity To Specificity 

Paolo Betti, Gionata Battistini, Luca Prodi, Enrico Dalcanale 

PSA 18 The Construction of Coordination Networks Incorporating {M(tpy)2}n+ (tpy 

= 2,2:6,2-terpyridine) Groups 

Jonathon E. Beves, Edwin C. Constable, Catherine E. Housecroft, 

Cameron J. Kepert, Markus Neuburger, David J. Price, Silvia Schaffner 

PSA 19 DNA Binding By A New Metallointercalator Containing A Proflavine Group 

Bearing A Hanging Chelating Unit 

Carla Bazzicalupi, Andrea Bencini, Antonio Bianchi, Tarita Biver, Alessia 

Boggioni, Sara Bonacchi, Andrea Danesi, Claudia Giorgi, Fernando 

Secco, Barbara Valtancoli, Marcella Venturini 

PSA 20 Exploration of p-Extended Interactions: Discopus as a new class of 

molecular receptor 

Cécile Givelet, Laura M. Scott, Brigitte Bibal 

PSA 21 Lead complexation by calix[4]-hydroxamates. Synthesis, X-ray structure 

and potentiometric studies in ion selective electrodes 

Maria Bocheska, Urszula Lesiska

PSA 22 Anion Receptors Based On The Cooperation Of Metal Coordination And 

Hydrogen Bonding 

Renato Bonomi, Fabrizio Mancin and Umberto Tonellato 

PSA 23 Self-Assembled Rosette Nanotubes with Increased Inner Diameter 

Gabor Borzsonyi, Andrew Myles and Hicham Fenniri 

PSA 24 New Fluorescent Sulphonamides Receptors For Selective Anion Sensing 

Claudia Caltagirone, Philip A. Gale, Mark E. Light 

PSA 25 Functional [2×2] Grids 

Xiao-Yu Cao, Jack Harrowfield, Jean-Marie Lehn, Augustin Madalan, 

Jonathan R.Nitschke 

PSA 26 Binding studies of a protonated dioxatetraazamacrocycle with anionic 

guests 

Sílvia Carvalho, Rita Delgado, Michael M. G. Drew, Vânia Calisto, Vítor 

Félix 

PSA 27 Structural And Thermodynamic Investigations On The Formation Of 

Porphyrin Metallacycles 

Massimo Casanova, Elisabetta Iengo, Pablo Ballester, Enzo Alessio 

PSA 28 The synthesis and characterisation of a porphyrin functionalized with 

2,2’:6’,2”-terpyridine ligands 

Paulina Chwalisz, Edwin C. Constable, Catherine E. Housecroft. 

PSA 29 Neutral supramolecular systems incorporating bis--diketonato 

metallocyclic building blocks: a remarkable reversible single crystal-single 

crystal bond breaking/bond forming transformation under pressure 

Jack K. Clegg, Katrina A. Jolliffe, Leonard F. Lindoy, Simon Parsons, 

David Schilter, Peter Tasker, Fraser J. White 

PSA 30 A ditopic biomimetic receptor: role of the 1st, 2nd and 3rd coordination 

spheres. 

D. Coquière, T. Prangé, J. Marrot, B. Colasson, O. Reinaud 

PSA 31 Anion-promoted deprotonation processes in urea-metallocyclam 

conjugates 

Guido Colucci, Luigi Fabbrizzi, Mauro Garolfi, Maurizio Licchelli 

PSA 32 Novel Jellyfish-Shaped Amphiphilic Cyclic Oligosaccharide Analogues: 

Synthesis And Self-Aggregation Properties 

Cinzia Coppola, Lorenzo De Napoli, Giovanni Di Fabio and Daniela 

Montesarchio 

PSA 33 Ratiometric Ion Sensors By Rational Design: Modulated Resonance 

Energy Transfer In Fluorescence Sensing Of Cations 

Ali Coskun, Ruslan Guliyev and Engin U. Akkaya 

PSA 34 Artificial Transmembrane Ion Channels From Commercial Surfactants 

Khayzuran S. J. Iqbal, Marcus C. Allen, Flavia Fucassi, Peter J. Cragg 

PSA 35 Molecular design of macrocyclic receptors containing two phenanthroline 

units and evaluation of their binding ability 

Carla Cruz, Rita Delgado, Michael G. B. Drew, Vítor Félix 

PSA 36 Controlled uptake-release of the citrate anion in a system capable of pH 

driven triple Cu 2+ translocation 

Giacomo Dacarro, Piersandro Pallavicini, Angelo Taglietti 

PSA 37 A photocontrollable receptor for CuII 

Giacomo Dacarro, Paola Ricci, Angelo Taglietti 

PSA 38 Synthesis Of Biomimicking Receptors By The Molecular Imprinted 

Polymers (MIP) Technique, For Application In Chemical Sensors 

Maria Pesavento, Girolamo D’Agostino, Antonella Profumo, Giancarla 

Alberti, Raffaela Biesuz, 

PSA 39 Cucurbit[n]uril as Supramolecular Structures and Drug Delivery Vehicles 

Yunjie Zhaoa, Linta Chalisserya, Beth Campbella, Damian Bucka, Gant 

Collinsa, Anthony Day 

PSA 40 Gas phase computational and experimental characterization of a 

tetraphosphonate “aquarius” cavitand that carries water and alcohols 

Chris Harmon, Jason Furlow, Chadin Dejsupa, Enrico Dalcanale, David V. 

Dearden 

PSA 41 New emitters for mass spectrometric observation of supramolecular 

complexes: sonic spray and porous polymer monolith electrospray 

Nannan Fang, Joseph S. Gardner, Roger G. Harrison, John D. Lamb, 

David V. Dearden 

PSA 42 Dynamic Covalent Chemistry of Formaldehyde Acetals. A Facile 

Synthesis of Macrocycles 

Roberta Cacciapaglia, Stefano Di Stefano, Luigi Mandolini 

PSA 43 Self-assembled fluorescent micellar sensors for pH windows: how to 

easily tune the window position along the pH axis 

Piersandro Pallavicini, Yuri Diaz Fernandez, Carlo Mangano, Luca Pasotti 

and Stefano Patroni 

PSA 44 A Directed Four-Component Self-Sorting System 

Roy D’souza, Werner M. Nau 

PSA 45 A fast-moving electrochemically-driven molecular shuttle: the 

biisoquinoline effect. 

Fabien Durola, Jean-Pierre Sauvage 

PSA 46 Efficient synthesis of copper(I)-rotaxane complexes via « click chemistry » 

Stéphanie Durot, Pierre Mobian, Jean-Paul Collin, Jean-Pierre Sauvage

PSA 47 Bishydrazide derivatives of isoindoline – the simple anion receptors 

selective for carboxylates 

Pawe Dydio, Tomasz Zieliski, Janusz Jurczak 

PSA 48 Protonated Macrobicycle Hosts Containing Pyridine Head-Units for the 

Recognition of Anions 

David Esteban-Gómez, Carlos Platas-Iglesias, Teresa Rodríguez-Blas 

Andrés de Blas. 

PSA 49 Macrocyclic Porphyrin-Bidentate Chelate Conjugates 

Jonathan A. Faiz, Fabien Durola and Jean-Pierre Sauvage 

PSA 50 Supramolecular assemblies of heterostylbene molecules: structure and 

properties 

O. A. Fedorova, Yu. V. Fedorov, N. E. Shepel, E. N. Gulakova, M. M. 

Mashura, G. Jounauskauskas 

PSA 51 A Novel Pyrenyl Appended Tricalix[4]Arene With Enhanced Fluorescence 

For Al 3+ Sensing. 

Amel Ben Othman, Jeong Won Lee, Rym Abidi, Jong Seung Kim, 

Jacques Vicens 

PSA 52 Intramolecular FRET triggered Hg 2+ ion sensing in tricalix[4]arene system 

Amel Ben Othman, Jeong Won Lee, Rym Abidi, Jong Seung Kim, 

Jacques Vicensa 

PSA 53 Electronic spectroscopy of emissive cryptophane-based molecules and 

their Xe containing complexes 

Heather A. Fogarty, Thierry Brotin and Jean-Pierre Dutasta 

PSA 54 Insights on the binding recognition of novel Dioxatetraaza macrocycle by 

G-Quadruplex telomeric DNA: a molecular dynamics investigation. 

N. Fonseca, P. J. A. Ribeiro-Claro, V. Félix 

PSA 55 Molecular Recognition Of Carbohydrates: New Synthetic Tripodal 

Receptors Featuring Pyrrolic Binding Groups. 

Cristina Nativi, Martina Cacciarini, Oscar Francesconi, Alberto Vacca, 

Gloriano Moneti, Andrea Ienco, Stefano Roelens. 

PSA 56 Synthesis of Peptoid-containing Macrocycles by Multiple Ugi-type 

Multicomponent Macrocyclizations 

Daniel G. Rivera, Ludger A. Wessjohann 

PSA 57 Self-Assembly Of Calixarene/Csi/Diiodoperfluorocarbon Supramolecular 

Salts: Structural Studies And Fluorous Phase Extraction 

Giuseppe Gattuso, Andrea Pappalardo, Melchiorre F. Parisi, Pierangelo 

Metrangolo, Giuseppe Resnati, Tullio Pilati, Sebastiano Pappalardo 

PSA 58 Properties of Deep-Cavity Cavitands 

Corinne L. D. Gibb, Srinivasan Kannupal, Bruce C. Gibb 

PSA 59 Aryl calix[4]pyrroles. Scaffolds to obtain evidences of anion-pi interaction 

Guzman Gil-Ramirez, M Angeles Sarmentero, Pablo Ballester. 

PSA 60 Hexa-Phosphorylated Triphenylenes (HPT) for aromatics and 

carbohydrates recognition 

Cécile Givelet, Brigitte Bibal 

PSA 61 Piperazine Containing Polyamino and Polyamino-amido Receptors of 

Open-Chain and Cyclic Topology 

José M. Vistos, J. M. Llinares, Jorge González, E. García-España, C. 

Sorianob, K. Rissanen. 

PSA 62 Cooperativity of inclusion by macrocyclic receptors for vapor sensing and 

storage 

Valery V. Gorbatchuk, Marat A. Ziganshin 

PSA 63 A fluorescent-indicator displacement assay for detection of ATP and GTP 

employing the cyclobisintercaland-type receptors 

Anton Granzhan, Marie-Paule Teulade-Fichou 

PSA 64 The Supramolecular Architecture Of A Guanosine Derivative As A 

Scaffold For Persistent Radicals 

Carla Graziano, Stefano Masiero, Silvia Pieraccini, Marco Lucarini, Gian 

Piero Spada 

PSA 65 Synthesis Of Self-Assembly Systems Through Multiple Hydrogen Bonding 

Interactions Between Dna Modified Bases For Supramolecular 

Applications 

Elisabetta Greco, Abil E. Aliev, Kason Bala, Peter Golding, Helen C. 

Hailes 

PSA 66 A New Schiff Base Expanded Porphyrin Derived from Carbazole 

Jonathan L. Sessler, Dustin E. Gross, Vincent M. Lynch 

PSA 67 Hierarchical Self-Assembly Of Dimeric Coordination Cages 

Francesca Gruppi, Marco Busi, Enrico Dalcanale 

PSA 68 Circular Polarization of Fluorescence Emitted from a Supramolecular 

Complex of Achiral Conjugated Polymers and Neutral Polysaccharides 

S. Haraguchi, M. Numata, C. Li, M. Fujiki, K. Sakurai, S. Shinkai 

PSA 69 Assembly of Metallomacrocycles from Ditopic 2,2':6',2"-Terpyridine 

Ligands with Flexible Spacers 

Edwin C. Constable, Kate Harris, Catherine E. Housecroft, Markus 

Neuburger and Silvia Schaffner 

PSA 70 Metal-Assembled Cages Observed by Sonic Spray Mass Spectrometry 

Roger G. Harrison, Joseph S. Gardner, John D. Lamb, David V. Dearden 

PSA 71 Constrained cyclam derivatives as ligands for copper(II) 

Jan Plutnar, Jana Havlíková, Petr Hermann, Jan Kotek, Vojtch Kubíek

PSA 72 Molecular Tectonics: STM Study of 2D Nanostructures and Design of 

Chiral Networks 

Fatima Helzy, Adam Duong, James D. Wuest. 

PSA 73 Supra-Biomolecular Tandem Assays - Application Examples 

Andreas Hennig, Hüseyin Bakirci, Werner M. Nau 

PSA 74 Synthesis of large polyazamacrocycles by the [3+3] cyclocondensation 

Jana Hodaová, Petr Hadrava, Jií Hlinka 

PSA 75 Binding of uranyl and lanthanide cations by azacalix[n]arenes : 

thermodynamic and kinetic approach. 

V. Hubscher-Bruder, F. Arnaud-Neu, C. Ambard, P. Jost, G. Wipff 

PSA 76 Anion recognition by triurea based macrocycles 

E. Jobin, V. Hubscher-Bruder, F. Arnaud-Neu, S. Michel, V. Böhmer, D. 

Meshcheryakov, M. Bolte 

PSA 77 Synthesis and molecular recognition studies of new enantiopure BODIPY 

linked monoaza-18-crown-6 ligands 

Ildikó Móczár, Péter Huszthy, Mihály Kádár, Klára Tóth 

PSA 78 Copper(I) Complexes with Reversibly-Formed Imine Bonds: Synthetic 

Control via Self-Assembly 

Marie Hutin, Gérald Bernardinelli, Jonathan R. Nitschke 

PSA 79 Multi-Chromophoric Assemblies Obtained Via Metallo-Porphyrins And 

Bisimide Dyes Coordination 

Elisabetta Iengo, Gregory J. E. Davidson, G. Dan Pantos, Jeremy K. M. 

Sanders 

PSA 80 Enantiodiscrimination of Carboxylic acid Anions by Abiotic Guanidinium 

Receptors 

Vinod D. Jadhav, Franz P. Schmidtchen 

PSA 81 Reaction of phthalic aldehydes with a,w-diamines for generation of 

Dynamic Combinatorial Libraries 

Magdalena Jarosz, Janusz Jurczak 

PSA 82 Chemical Detection of Explosives 

Jan O. Jeppesen, Kent A. Nielsen, Lise G. Jensen, Andrew D. Bond, 

Won-Seob Cho, Vincent M. Lynch, Jonathan L. Sessler 

PSA 83 New amido-Based Multicyclic Hosts for anions 

Sung Ok Kang, Victor W. Day, Kristin Bowman-James 

PSA 84 Prodigiosin Analogues and Related Polypyrrolic Anion Receptors; 

Thermodynamic and Kinetic Studies 

Jonathan L. Sessler, Elizabeth T. Karnas, Dustin E. Gross, Leah R. Eller, 

Won-Seob Cho,Sergios Nicolaou, Apolonio Aguilar, Jeong Tae Lee, 

Vincent M. Lynch, Darren J. Magda, Kenneth A. Johnson 

PSA 85 Binding of perrhenate and pertechnetate anions by bipyrrole based 

receptors 

Evgeny A. Katayev, Patricia Melfi, Nikolay V. Boev, Grigory V. Kolesnikov, 

Ivan G. Tananaev, Jonathan L. Sessler 

PSA 86 Host-Assisted Guest Protonation With Cucurbit[7]Uril 

Apurba L. Koner, Na'il Saleh, Werner M. Nau 

PSA 87 Luminescence of terbium and dysprosium complexes with psulfonatothiacalix[4]arene 

in aqueous and surfactant media 

Svetlana Kost, Natalya Rusakova, Asiya Mustafina, Rustem Amirov, 

Rustem Zairov, Svetlana Solovieva, Igor Antipin, Alexander Konovalov, 

Yuriy Korovin 

PSA 88 Photo-Responsive Structure of Supramolecular Polymers Constructed by 

a Stilbene Cyclodextrin Dimer 

Paul Kuad, Yoshinori Takashima, Hiroyasu Yamaguchi, Akira Harada 

PSA 89 Supramolecular assemblies of the crown-containing 2-styrylpyridine with 

amino acids 

Labazava I.Ya, Mashura M.M, Gulakova E.N, Fedorov Yu.V, Fedorova 

O.A, Alfimov M.V, J.Saltiel 

PSA 90 Self-Assembly Of A Guanosine Derivative Bearing A Terthienyl Pendant 

Stefano Lena, Stefano Masiero, Silvia Pieraccini, Paolo Samorì, Gian 

Piero Spada, Mathieu Surin 

PSA 91 Application of a new classes podands in solid-liquid phase transfer 

catalysis 

Bogusawa ska, Radosaw Pankiewicz, Grzegorz Schroeder 

PSA 92 New DOTP analogue for possible medical applications 

Luís M. P. Lima, Rita Delgado, Petr Hermann, Jan Kotek 

PSA 93 Polytopic Ligands for the Recovery of Metal Chlorides 

Tai Lin, Vesna Gasperov, Peter A. Tasker 

PSA 94 Comparative Dissociation Kinetics Study of Copper(II) Complexes with 

do3a-like Macrocyclic Ligands 

I. Svobodová, J. Pasulka, Z. Stelcováa, P. Lubal, P. Hermann, J. Kotek 

PSA 95 Nitroxide Radicals as Probes for Exploring the Binding Properties of 

Cucurbit[n]Uril Hosts 

Elisabetta Mezzina, Elisabetta Mileo, Gian Franco Pedulli, Marco Lucarini

PSA 96 Supramolecular complexes of polythiophene derivatives with different 

types of metal cations 

Elena V. Lukovskaya, Alla A. Bobylyova, Olga A. Fedorova ,Yury V. 

Fedorov, Emely Marmois, Gediminas Jonusauskas, Sergey V. Kardashev, 

Anton L. Maksimov, Y. Didane, Hugues Brisset, Frederic Fages, Artem A. 

Mizerev, Aleksander V. Anisimov 

Poster session B 

Tuesday, 26 June 17:30-19:30 

PSB 1 Rosette Nanotubes as Scaffolds for Stacked Multi-Porphyrin Assemblies 

Darren A. Makeiff and Hicham Fenniri 

PSB 2 Preparation and characterization of [60]fullerene fibrillar superstructures 

and those polymerization by g-ray irradiation 

Sudip Malik, Norifumi Fujita, Seiji Shinkai 

PSB 3 Enhanced kinetic inertness in the electrochemical interconversion of Cu(I) 

double helical to Cu(II) monomeric complexes 

Piersandro Pallavicini, Massimo Boiocchi, Giacomo Dacarro and Carlo 

Mangano 

PSB 4 Lanthanide ion binding properties of homooxacalixarene diethylamide 

derivatives 

Paula M. Marcos, José R. Ascenso, Manuel A. P. Segurado, Peter J. 

Cragg 

PSB 5 Towards the development of new molecular nano-gates controlled via 

ionic and optical inputs 

Elena Aznar, Rosa Casasús, María Comes, María Dolores Marcos, 

Ramón Martínez-Máñez, Félix Sancenón, Juan Soto, Luis A. Villaescusa, 

Pedro Amorós, Joan Cano, Eliseo Ruiz 

PSB 6 Noble metal complexes with sulfur-containing calixarenes: extraction, 

complexation and structure 

Mashukov V.I., Kostin G.A., Torgov V.G., Korda T.M., Kalchenko V.I 

PSB 7 Properties of metal complexes of a new dioxadiaza macrocycle containing 

a dibenzofuran unit and acetate pendant arms 

Pedro Mateus, Judite Costa, Feng Li, Rita Delgado 

PSB 8 The cleavage of cyclic substituents in derivatives of closo-decaborate 

anion by diaza-crown-ether 

E.Matveev, K.Zhizhin, N.Kuznetsov 

PSB 9 A Quantitative [2]Rotaxane Synthesis via “Active-Template” Pd-Catalyzed 

Michael Addition 

Stephen M. Goldup, David A. Leigh, Paul J. Lusby and Roy T. McBurney 

PSB 10 Binding properties of two amides derivatives of p-phenyl 

tetrahomodioxacalix[4]arene towards alkali and alkaline-earth metal ions 

B. Mellah, R. Abidi, H. Herschbach, K. No, F. Arnaud-Neu

PSB 11 Dual binding properties of polycyclic receptors incorporating 5,12dioxocyclam 

units: the interplay between amines and amides 

Michel Meyer, Guy-Yves Vollmer, Laurent Frémond, Enrique Espinosa, 

Roger Guilard 

PSB 12 Synthesis And Characterization Of The First Paramagnetic [1]Rotaxane 

Michela Fanì, Paola Franchi, Elisabetta Mezzina, Marco Lucarini 

PSB 13 Metal Complexes of the Polyether Ionophore Antibiotic Monensin A : 

coordination mode, spectroscopic study, X-ray structures and 

antimicrobial activity 

Mariana Mitewa, Ivayla N. Pantcheva, Petar Dorkov, Rumyana Zhorova, 

Boris Shivachev, William S. Sheldrick 

PSB 14 Different types of Supramolecular Structures Resulting from Synthetic 

Procedures 

Atsuhisa Miyawaki, Yoshinori Takashima, Hiroyasu Yamaguchi and Akira 

Harada 

PSB 15 Novel Copper(II) and Nickel(II) [2×2] Molecular Grids based on a 

Polynucleative Oxime-containing Shiff Base Ligand 

I. S. Moroz, M. Haukka and I. O. Fritsky 

PSB 16 4-(4-Thiocarbamoyl-1,2,3-triazol-1-yl)benzoannelated Crown Ethers as 

Amino Acid's Receptors. 

Yuri Yu. Morzherin, Polina E. Kropotina, Tatiana V. Glukhareva, 

Nadezhda A. Itsikson, Anatoly I. Matern 

PSB 17 Metal controlled anion interaction at the thiourea subunit: low-spin iron(II)- 

2-formylpyridine-thiosemicarbazone complexes 

Lorenzo Mosca, Valeria Amendola, Massimo Boiocchi, Luigi Fabbrizzi, 

Antonio Poggi 

PSB 18 Peptides transport through liquid membrane by calix[n]arene derivatives 

Lucia Mutihac, Hans-Jürgen Buschmann, Radu-Cristian Mutihac, Eckhard 

Schollmeyer 

PSB 19 Some analytical applications of modified cyclodextrins 

Lidia Kim, Cristian Baltariu, Ana Delia Stancu, Radu-Cristian Mutihac, 

Elena Diacu, Hans-Jürgen Buschmann, Lucia Mutihac 

PSB 20 4-(3-(Phtalhydrazide)azo)N-phenylaza-15-crown-5. Synthesis and 

properties 

Rodica D. Baratoiu, Radu Socoteanu, Lucia Mutihac, Titus 

Constantinescu 

PSB 21 Crown Ether-tert-Ammonium Salt Complex Fixed as Rotaxane and It’s 

Derivation to Neutral Rotaxane 

Kazuko Nakazono and Toshikazu Takata 

PSB 22 Supramolecular Receptor Design – Anion Triggered Differentiation 

Between Substrates 

Kent A. Nielsen, Won-Seob Cho, Ginka Sarova, Bo M. Petersen, Jan 

Becher, Frank Jensen, Dirk M. Guldi, Jonathan L. Sessler, and Jan O. 

Jeppesen 

PSB 23 Template-assembled synthetic G-quartets (TASQs) 

Mehran Nikan, David Perrin, John C. Sherman 

PSB 24 Application of Dynamic Combinatorial Chemistry to the synthesis of 

polyazamacrocycles containing furan or thiophene units 

Aleksandra Obrocka, Krzysztof Ziach, Janusz Jurczak 

PSB 25 A Minimalist Design for Self-Assembled Rosette Nanotubes based on 

Mascal’s Motif. 

Martins Oderinde, Grigory Tikhomirov and Hicham Fenniri 

PSB 26 Chemically-Responsive Sol-Gel Transition of Supramolecular Single- 

Walled Carbon Nanotubes (SWNTs) Hydrogel Made by SWNTs- 

Cyclodextrins Hybrids 

Tomoki Ogoshi, Tada-aki Yamagishi, Yoshiaki Nakamoto, and Akira 

Harada 

PSB 27 High Order Bistable [n]Rotaxane Architectures 

Ivan Aprahamian, William Dichtel, Travis Gasa, John-Carl Olsen, J. Fraser 

Stoddart 

PSB 28 Polymerization of Lactones and Lactides Initiated by Cyclodextrins in Bulk: 

Effects of Cyclodextrins on the Initiation and Propagation 

Motofumi Osaki, Yoshinori Takashima, Hiroyasu Yamaguchi, Akira 

Harada 

PSB 29 Control of Translation of the Cyclic Component onto the Rotaxane bearing 

2-Pyridinium Moieties 

Tomoya Oshikiri, Hiroyasu Yamaguchi, Yoshinori Takashima, Yasushi 

Okumura, Akira Harada 

PSB 30 A fluorescent micellar lipophilicity-meter for carboxylates 

Giacomo Dacarro, Franck Denat, Yuri Diaz Fernandez, Piersandro 

Pallavicini, Luca Pasotti, Stefano Patroni, and Yoann Rousselin 

PSB 31 Interconversion Between A Supramolecular Polymer And A Discrete 

Octameric Species From A Guanosine Derivatives At Surfaces 

Omar Pandoli, Stefano Masiero, Silvia Pieraccini, Paolo Samorì and Gian 

Piero Spada 

PSB 32 Spectroscopic study of of lasalocid ester with 2-thio-1-ethanol and its 

complexes with monowalent cations 

Radoslaw Pankiewicz, Grzegorz Schroeder, Bogumil Brzezinski

PSB 33 Multinuclear NMR, ESI MS and PM5 studies of a new derivative of 

Gossypol with 2-thiophenecarbohydrazide as well as its complexes with 

monovalent cations 

P. Przybylski, R. Pankiewicz, W. Schilf, G. Schroeder, B. Brzezinski 

PSB 34 Polycapsular assembly of exo-ditopic xylyl bridged bicalix[5]arenes with 

long chained alfa,omega-alkanediammonium ions 

Yoram Cohen, Sarit Slovak, Giuseppe Gattuso, Anna Notti, Andrea 

Pappalardo, Melchiorre F. Parisi, Ilenia Pisagatti, Sebastiano Pappalardo 

PSB 35 Chiral chemosensors for enantiomeric recognition of aspartate 

Ana M. Costero, Manuel Colera, Pablo Gaviña, Margarita Parra, Miklós 

Kubinyi, Krisztina Pál, Mihály Kállay 

PSB 36 Residual and exploitable fluorescence in micellar self-assembled ON-OFF 

sensors for Copper(II) 

Piersandro Pallavicini, Carlo Mangano, Luca Pasotti and Stefano Patroni 

PSB 37 New Anthracene-based cyclophane: complexation of organic cations and 

formation of Diels-Alder adducts. 

Bernardo Masci, Sara Pasquale 

PSB 38 Lariat-type polyamide receptors for anion binding 

Marcin Pawlak, Adam Sobczuk, Jaroslaw Kalisiak, Janusz Jurczak 

PSB 39 Amplification of a Molecular Solomon Knot 

Cari D.Pentecost, Nicholas Tangchaivang, Kelly S. Chichak, Andrea J. 

Peters, Stuart J. Cantrill and J. Fraser Stoddart 

PSB 40 Self-Assembled Resorcinarene Monolayers on Gold 

Jade Pettersen, Mauro Mocerino, Mark Ogden, Andrew Ross, Peter 

Eadington 

PSB 41 1,3,5-Tris(2-aminophenyl)benzene: a novel platform for anion receptors. 

Piotr Piatek 

PSB 42 Ds-oligonucleotide-peptide conjugates featuring peptides from the leucine 

zipper region of Fos as switchable receptors for the oncoprotein Jun. 

Cecilia Portela, Fernando Albericio, Ramón Eritja, Luis Castedo and José 

Luis Mascareñas 

PSB 43 Crown Ether Functionalized Texaphyrins: Approaches to Improved 

Biolocalization Properties. 

Jonathan L. Sessler, Andreas Hirsch, Darren Magda, Christian Preihs 

PSB 44 Double-threading of two strings through a ring: use of an octahedral metal 

as template 

Fabien Durola, Alexander I. Prikhod’ko (Oleksandr Prykhodko), Jean- 

Pierre Sauvage 

PSB 45 Simple Isophthalamide Derivatives As Transmembrane Cl- Transporters 

Paul V. Santacroce, Jeffery T. Davis, Mark E. Light, Philip A. Gale, José 

Carlos Iglesias-Sánchez, Pilar Prados, Roberto Quesada 

PSB 46 Diphosphonate-macrocycle Conjugates – Probe Complexes for a Sorption 

Investigation 

T. Vitha, V. Kubícek, I. Rehor, P. Hermann, Z. I. Kolar, H. T. Wolterbeek, 

J. A. Peters, I. Lukeš 

PSB 47 Dynamic Combinatorial Chemistry Applied to the Synthesis of 

Cyclopeptidic Receptors for Anion Recognition in Aqueous Solutions 

Zaida Rodriguez-Docampo, Carsten Reyheller, Stefan Kubik and Sijbren 

Otto 

PSB 48 A [2]Rotaxane from a Nickel Active Metal Template 

Pauline Fitzsimmonds, Stephen. M. Goldup, Nicholas. D. Gowans, David. 

A. Leigh and Vicki E. Ronaldson 

PSB 49 On Sokolov’s approach to a Molecular Knot using Ring Closing Metathesis 

Pirmin Rösel, Christopher Smith, Catherine E. Housecroft, Edwin C. 

Constable 

PSB 50 New route for the C-functionnalisation of macrocyclic polyamines 

Yoann Rousselin, Franck Denat, Frédéric Boschetti, Roger Guilard 

PSB 51 Preparation and Properties of Rotaxanes Formed by Dimethyl-betacyclodextrin 

and Oligo(thiophene)s with beta-Cyclodextrin Stoppers 

Kazuya Sakamoto, Yoshinori Takashima, Hiroyasu Yamaguchi, Akira 

Harada 

PSB 52 Host-Guest Chemistry of Tetramethoxy Resorcinarene Crowns: Bis- 

Crown-5 vs. Tribenzo-Bis-Crown-6 

Kirsi Salorinne and Maija Nissinen 

PSB 53 New chromogenic sensors using hybrid organic-inorganic nanomaterials 

Elena Aznar, Pilar Calero, Carmen. Coll, Maria Dolores Marcos, Ramón 

Martínez-Máñez, Félix Sancenón, Juan Soto, Pedro Amorós, Jose Manuel 

Lloris, Celia Silvestre 

PSB 54 Computational Studies on the Cooperative AND Ion-Pair recognition by 

Heteroditopic Calix[4] diquinone Receptors 

Sérgio Santos, Michael D. Lankshear, Paul D. Beer and Vítor Félix 

PSB 55 Molecular inclusion of organometallic sandwich complexes within hybrid 

cavitand-resorcin[4]arene receptors 

María Ángeles Sarmentero, Guzmán Gil, Pablo Ballester 

PSB 56 Subcomponent Exchanges in Self-Assembled Metallo-Organic Structures 

David Schultz, Jonathan R. Nitschke

PSB 57 Removal Of Heavy Metal Ions From Waste Waters By Molecular 

Recognition Technology 

Giuseppe Arena, Elisa Longo, Carmelo Sgarlata, Richard A. Bartsch, 

Dongmei Zhang and Yanfei Yang 

PSB 58 Synthesis, Metal Ion Complexation And Polymeric Membrane Ion- 

Selective Electrode Studies Of Some Novel Calix[4]Arene-Crown 

Macrocycles 

M. Shamsipur, M. Taghdiri, M. K. Rofouei, S. Sahari, K. Alizadeh, Z. 

Asfari, M. Leroy 

PSB 59 Supramolecular mixed complexes of the crown-containing ditopic 

receptors with organic acids and metal cation 

O.A. Fedorova, E.Yu. Chernikova, Yu.V. Fedorov, E.N. Gulakova, M.M. 

Mashura, N.E. Shepel' and M.V. Alfimov 

PSB 60 New Series of 18-Membered Aza-oxa-thia and Coumarin Pendent Armed 

Macrocyclic Systems, Synthesis and Applications 

Abbas Shockravi, Hasan Valizadeh, Hamideh Hoseini and Zahra Taheri 

PSB 61 Molecular Recognition Of Electron-Deficient Guests Molecules By Podand 

Diazacoronands 

Adam Sobczuk, Marcin Pawlak, Jaroslaw Kalisiak, Janusz Jurczak 

PSB 62 An electrochemical sensor for anions based on a tris-imidazolium cage 

and on the Co III /Co II redox change 

Cristina Spadini, Valeria Amendola, Massimo Boiocchi, Benoît Colasson, 

Luigi Fabbrizzi, Maria-Jesús Rodriguez Douton 

PSB 63 pH-Responsive Molecular Shuttles Containing Palladium 

James D. Crowley, David A. Leigh, Paul J. Lusby, Roy T. McBurney, 

Laure-Emmanuelle Perret-Aebi, Christiane Petzold and Mark D. Symes 

PSB 64 Contraction of Supramolecular Double-Threaded Dimer Formed by a- 

Cyclodextrin with Long Alkyl Chain 

Yoshinori Takashima, Shouichi Tsukagoshi, Atsuhisa Miyawaki, Hiroyasu 

Yamaguchi, and Akira Harada 

PSB 65 Switching of Self to non-Self Supramolecular Structures by Isomerization 

Yoshinori Takashima, Naoki Tomimasu, Hiroyasu Yamaguchi and Akira 

Harada 

PSB 66 Sulfides peroxide oxidation in the presence of crown ethers 

A.V.Anisimov, A.V.Tarakanova, Pham Vinh Thai, A.A.Seleznev, 

N.S.Kulikov 

PSB 67 Cooperative Complexation of alpha-Cyclodextrin with Micelle-like 

Aggregates Formed from Amphiphilic Polyanions 

Daisuke Taura, Akihito Hashidzume, and Akira Harada 

PSB 68 Dissociation Kinetics of Tl + , Pb 2+ , Cd 2+ and Bi 3+ Cryptates 

Gary. L. N. Smith, Olajumoke O. Oluwu, Baige Bian, Richard W. Taylor 

PSB 69 Investigation of -cyclodextrin binding ability to xanthine and its 

derivatives. 

Irina Terekhova 

PSB 70 Ditopic dithiophosphoramides and acylthiourea ligands as metal salt 

extractants 

Jy Chartres, Shalima Shawuti, Peter A. Tasker, Christine C. Tong 

PSB 71 Synthesis and preliminary molecular recognition studies of novel protonionizable 

crown ethers containing a diarylphosphinic acid moiety 

Péter Huszthy, Tünde Tóth, György Székely, Viktor Farkas, Miklós Hollósi 

PSB 72 Cyclen based dimers as tridimentional receptors for polyphosphate 

recognition. 

Raphaël Tripier, Stephanie Develay, Michel Le Baccon, Guy Serratrice 

and Henri Handel 

PSB 73 Novel ditopic probes for different metal cation recognition 

Elena Tulyakova, Olga Fedorova, Yuri Fedorov, Gediminas Jonusauskas, 

Alexander Anisimov 

PSB 74 Preparation of new octa(alkoxy) pyrazinoporphyrazines 

Rabia Zeynep Uslu Kobak, Ahmet Gül 

PSB 75 Design, synthesis and study of the first “excimer helicates” 

Miguel Vázquez, M. Eugenio Vázquez, Clara Gómez-Reino, Maurizio 

Licchelli, Manuel R. Bermejo 

PSB 76 Synthesis and characterisation of a liquid-crystalline {2}catenane and its 

copper(I) complex 

Etienne D. Baranoff, Julie Voignier, Takuma Yasuda, Valérie Heitz, Jean- 

Pierre Sauvage, Takashi Kato 

PSB 77 Synthesis, supramolecular architecture and redox properties of cobalt and 

iron(II) macrocyclic and macrobicyclic bis- and tris-dioximates with 2,6-ditert-butylphenol 

pendants 

Yan Z. Voloshin, Dmitrii B. Shpakovsky, Elena R. Milaeva, Tatyana V. 

Magdesieva, Alexander S. Belov 

PSB 78 First synthesis of clathrochelate iron(II) oximhydrazonate with a differ 

orientation of the functionalizing substitutes relative to the capping 1,3,5triazacyclohexane 

ring 

Yan Z. Voloshin, Sergei Y. Erdyakov, Mikhail E. Gurskii, Irina G. 

Makarenko, Ekaterina G. Lebed, Yurii N. Bubnov

PSB 79 Azomacrocyclic derivatives of pyrrole as chromoiononophores and 

fluoroionophores 

Ewa Wagner-Wysiecka, Elzbieta Luboch, and Tomasz Rzymowski 

PSB 80 Cation and anion binding studies of a large N,O-donor macrocycle: Single 

ion extraction and synergistic enhancement 

Marco Wenzel, Kerstin Gloe, Karsten Gloe, Gert Bernhard, Jack K. Clegg, 

Xue-K. Ji, Leonard F. Lindoy 

PSB 81 Tripodal polyamines as anion receptors: Extraction and structural studies 

Marco Wenzel, Bianca Antonioli, Kerstin Gloe, Karsten Gloe, Maria G. 

Sanchez, Gert Bernhard, David J. Bray, Jack K. Clegg, Leonard F. Lindoy 

PSB 82 Carbohydrate Dynamic Combinatorial Libraries for Quadruplex DNA 

Recognition 

Jean-Luc Wietor, Anthony Bugaut, Katja Jantos, Shankar 

Balasubramanian, Jeremy K. M. Sanders 

PSB 83 Synthesis of Functional Aromatic Oligoamides 

Fred Campbell, Jeff Plante, Barbora Malkova and Andrew Wilson 

PSB 84 Hexafunctionalized Borromeates 

Claire R Yates, Diego Benítez and J Fraser Stoddart 

PSB 85 Templated Synthesis of Large Macrocyles by Ring-Closing Metathesis 

Yeni, Markus Albrecht 

PSB 86 Application of benzopyrroles in the construction of anion receptors 

Tomasz Zielinski, Pawel Dydio and Janusz Jurczak 

PSB 87 N,N'-Bis(2-aminoethyl)-2,2'bipyridine-3,3'-dicarboxmide: A Novel 

Fluorescent Chemosensor for Divalent Nickel and Copper 

Rati Kanta Bera, B. K. Kanungo and Minati Baral 

PSB 88 New Maltolic Ligand For Sequestering Lanthanides In Water 

Gianluca Ambrosi, Mauro Formica, Vieri Fusi, Luca Giorgi, Eleonora 

Macedi, Mauro Micheloni, Paola Paoli, and Patrizia Rossi 

PSB 89 Direct C-C coupling of 1,2,4-Triazin-5(2H)-ones with Benzoannelated 

Crown Ethers in the Synthesis of Amino Acid's Receptors. 

Nadezhda A. Itsikson, Mikhail I. Kodess, Anatoly I. Matern, Yuri Yu. 

Morzherin, Oleg N. Chupakhin 

PSB 90 Synthetic, Spectroscopic, Potentiometric Studies and Molecular Modeling 

of a New Biomemitic Siderophore Analogue 

Suban K. Sahoo, Minati Baral and B. K. Kanungo 

PSB 91 Synthesis of new calixarenic dendron 

Mouna Mahouachi, Rym Abidi, Jacques Vicens and Yang Kim 

PSB 92 Cation Binding Properties by Ligands Deriving from Calix[4]crown-5azacrown-5 

Mouna Mahouachi, Rym Abidi, Jong Seung Kim and Jacques Vicens 

PSB 93 The study of cytotoxicity effect and status of oxidative stress of two novel 

synthesized tri-aza macrocyclic diamides as studied in the WI38 cell lines 

Massod Mashhadi Akbar Boojar, Abbas Shockravi 

PSB 94 Synthesis of photochromic crown containing benzo- and naphtopyranes 

Sergey V. Paramonov, Olga A. Fedorova, Valerii P. Perevalov, Vladimir 

Lokshine, André Samat 

PSB 95 Photoresponsive Malachite Green Derivative and Photoinduced Vesicle 

Fusion 

Ryoko M. Uda, Keiichi Kimura 

PSB 96 Stable terbium probes highly luminescent in aqueous solutions: 

macrocyclic ligands derived from N,C-pyrazolylpyridine 

Isabelle Nasso, C. Galaup, B. Mestre, C. Picard 

PSB 97 Development of innovative sol-gel coatings for solid phase microextraction 

based on quinoxaline-bridged cavitands 

Paolo Betti, Federica Bianchi, Franco Bisceglie, Enrico Dalcanale, Monica 

Mattarozzi

40 years of polyazamacrocycles. A personal historical view. 

Thomas A. Kaden 

Department of Chemistry, University of Basel, Spitalstrasse 52, CH 4056 Basel, Switzerland. 

PL 1 

A review of the chemistry of polyazamacrocycles [1] will show how the syntheses of such 

compounds have been improved, how the size of the macrocyclic ring plays an important role in 

the complexation process (macrocyclic effect), how the geometry of the metal ion complexes 

can be controlled, how spectral and magnetic properties as well as the electrochemistry and 

kinetics of complex formation and dissociation are dependent on the properties of these ligands. 

Further developments in this field of chemistry have been the functionalisation of the 

macrocycles with groups, which can be used to modify their solubility and thus their extraction 

properties, or their coordination properties, or can form covalent bonds so that macrocyclic 

complexes can be attached to other molecules, or can carry reactive groups so that one can 

study metal promoted reactions. 

The synthesis of homo- and heteroditopic bis-macrocycles allows to prepare new compounds, 

which depending on the distance between the two metal centres show interesting chemical and 

physical properties. In addition homo- and heteropolytopic systems based on more than two 

macrocycles and open chain ligands have also been prepared and their metal complexes 

studied in detail. 

Finally a review of applications will be given: on one side molecular machines based on 

polyazamacrocycles and on the other side the use of such macrocycles and their metal 

complexes in medicine. 

[1] For reviews on polyazamacrocycles see: 

- N.F. Curtis, Coord. Chem. Rev., 1968, 3, 3; 

- Th. A. Kaden, Topics Curr. Chem., 1984, 121, 157; 

- P. Bernhardt, P. Lawrance, Coord. Chem. Rev., 1990, 104, 297; 

- Th. A. Kaden, Advances Supramol. Chem., 1993, 3, 65; 

- M. Meyer, V. Dahaoni-Gindrey, C. Lecomte, R. Guilard, Coord. Chem. Rev., 1998, 178-180, 

1313. 

Shape-controlled functional materials created by modification of 

preorganized assemblies 

Seiji Shinkai 

Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu 

University, 744 Motooka, Nishi-ku, Fukuoka, 819-0391, Japan 

PL 2 

Combination of supramolecular chemistry with molecular recognition has been successfully 

applied to creating large superstructures with a wide variety of morphologies. Control of shapes 

and patterns of ordered molecular assemblies in nano and micro scales has attracted 

considerable interest as promising bottom-up technology. It is known, however, that these 

molecular assembling superstructures are fragile, reflecting the characteristic of the noncovalent 

interaction, a driving force operating in these molecular systems. In fact, they easily 

collapse or change by small perturbation in the environmental conditions. Thus, over the last 

decade, researchers have been seeking possible methods for the immobilization of these 

superstructures. This lecture focuses on recent advances in molecular orientation facilitated by 

guest inclusion, in situ post-modification under the influence of the molecular assemblies as 

templates, and post-polymerization of ordered molecular assemblies such as organogel fibers 

and crystals to preserve their original superstructures and intensify their mechanical 

strength.[1,2] 

[1] For a recent review, see K. Sada, M. Takeuchi, N. Fujita, M. Numata and S. Shinkai, Chem. 

Soc. Rev., 2007, 36, 415-435 

[2] I. Hwang et al., Angew. Chem. Int. Ed., 2007, 46, 210-213; P. Mukhopadhyay et al., ibid., 

2006, 45, 1592-1595; T. Kishida et al., Org. Biomol. Chem., 2006, 4, 1902-1909

Macrocyclic hosts for supramolecular and traditional coordination 

chemistry 

Kristin Bowman-James 

Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 

66045 USA 

Interactions linking hosts with their guests in chemistry and biology range from simple to 

complex. They include supramolecular “coordination chemistry” involving hydrogen bonding 

networks as well as traditional coordination chemistry involving coordinate covalent bonds with 

transition metal ions. In order to understand the basic topological concepts regulating anion 

recognition (anion coordination chemistry), we designed a series of macrocycles based on 

simple amide/amine frameworks and used a systematic approach to examine the influence of 

increasing complexity or dimensionality. Since anions and transition metal ions often bind 

similar types of functional groups, i.e., protonated amines and amides for the former and neutral 

amines and deprotonated amides in the latter, we have also begun exploring our anion hosts as 

ligands for transition metals ions. Structural and chemical findings for monoatomic (F – , H + , M 2+ , 

M 3+ ), linear (FHF – , N3 – ), and other multiatomic (HSO4 – , ReO4 – , P2O7 2– , Cr2O7 2– ) complexes, 

among others, will be described. 

N N 

N N N 

Bicycles 

N N 

= , 

N 

, O 

N = amine linker 

N 

N 

N N N N 

Tricycles 

N 

N 

PL 3 

Covalent and Coordinative Dynamic Chemistry 

J Fraser Stoddart 

California NanoSystems Institute and Department of Chemistry & Biochemistry, University of 

California, Los Angeles, 607 Charles E Young Drive East, Los Angeles, CA, USA 90095-1569 

The chemical synthesis of (functional) materials is in a state of rapid development and 

considerable flux these days. The profound influence that supramolecular chemistry has had 

on the development of chemical science during the past few decades has led, in the first 

instance, to supramolecular assistance to covalent synthesis, and then subsequently to 

dynamic coordinative and covalent synthesis. Templation is central to success whichever 

variant of the synthetic protocols is being employed. 

For the synthesis of a particular molecular compound or specific extended structure to proceed 

with efficiency, reactions under thermodynamic control have to be associated with the 

overwhelming preference for one compound or structure over all the other possibilities, i.e., lock 

and key chemistry. When kinetic control is operating, reactions which proceed apace and go to 

completion, are very attractive candidates for synthesis, i.e., click chemistry. Phase changes 

can also be used in an extremely effective manner to capture a product in a kinetic fashion from 

an equilibrium mixture of products, e.g., crystallization of one of the less stable compounds from 

a dynamic combinatorial library. 

A Collage of Form and Function 

PL 4 

The lecture will focus, by way of examples, on the reversible nature of imine bond formation, 

imine exchange, olefin metathesis in the presence of (Grubbs) catalysts, and the Menschutkin 

reaction, as well as the irreversible copper-catalyzed Huisgen dipolar 1,3-cycloaddition between 

an alkyne and an azide, all happening in some context or other where templation through metal 

coordination, donor-acceptor interactions and/or hydrogen bonding is operative. The products 

will all be mechanically interlocked compounds, including (bistable) catenanes and (bistable) 

rotaxanes, Borromean rings, Solomon links, and molecular bundles and switches. Functions, 

that will be addressed, will include nanovalves and molecular memory. 

[1] “Molecular Borromean rings,” Science 2004, 304, 1308–1312. 

[2] “A molecular Solomon link,” Angew. Chem., Int. Ed. 2006, 46, 218–222. 

[3] “Efficient templated synthesis of donor-acceptor rotaxanes using click chemistry,” J. Am. 

Chem. Soc. 2006, 128, 10388–10390. 

[4] “A 160-kilobit molecular electronic memory patterned at 10 11 bits per square centimetre,” 

Nature 2007, 445, 414–417.

PL 5 

Anion-Templated Assembly of Interpenetrated and Interlocked Structures 

Paul D. Beer 

Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks 

Road, Oxford, OX1 3QR, UK 

Although mechanically bonded molecules have enormous potential for use in applications 

based on nanometre-scale switching and motion [1], their unique topological cavities intrinsic to 

these interlocked structures also make them of great interest in the molecular sensing arena. In 

the majority of cases cationic and neutral species have been employed as efficient templates in 

mechanical bond construction, whereas the manipulation of anions to direct supramolecular 

assembly remains largely under-developed [2]. 

With the ultimate objective of constructing novel anion sensory receptor systems with 

unprecedented selective anion recognition behaviour we have recently undertaken the 

challenge of exploiting anions to template the formation of interpenetrated and interlocked 

supramolecular assemblies [3]. The lecture will discuss our latest results in the rational designoriented 

development of a general anion templation methodology for the formation of a range of 

pseudorotaxanes [4], rotaxanes [5] and catenanes [6]. 

The application of this anion templation protocol is exploited further in the fabrication of redoxactive 

rotaxane self-assembled monolayers (SAMs) on to gold electrode surfaces which are 

shown to electrochemically recognise chloride anions selectively. Importantly, the unique 

interlocked binding domain that results from macrocycle and thread interpenetration, 

simultaneously amplifies the rotaxane SAMs electrochemical voltammetric response to chloride 

and switches off a response to basic oxoanions such as phosphate. 

[1] J-P. Sauvage, C. Dietrich-Buchecker (Eds.): Molecular Catenanes, Rotaxanes and Knots, 

1999, Wiley-VCH, Weinheim 

[2] R. Vilar, Angew. Chem. Int. Ed., 2003, 42, 1460 

[3] P. D. Beer, M. R. Sambrook, D. Curiel, Chem. Commun., 2006, 2105 

[4] M. R. Sambrook, P. D. Beer, J. A. Wisner, R. L. Paul, A. R. Cowley, F. Szemes, M. G. B. 

Drew, J. Am. Chem. Soc., 2005, 127, 2292 

[5] J. A. Wisner, P. D. Beer, M. G. B. Drew, M. R. Sambrook, J. Am. Chem. Soc, 2002, 124, 

12469. M. R. Sambrook, P. D. Beer, M. D. Lankshear, R. F. Ludlow, J. A. Wisner, Org. 

Biomol. Chem., 2006, 4, 1529 

[6] M. R. Sambrook, P. D. Beer, J. A. Wisner, R. L. Paul, A. R. Cowley, J. Am. Chem. Soc., 

2004, 126, 15364. K-Y. Ng, A. R. Cowley, P. D. Beer, Chem. Commun., 2006, 3676 

Transition Metal-Complexed Catenanes, Rotaxanes and Molecular 

Machines 

Jean-Pierre Sauvage 

PL 6 

Laboratoire de Chimie Organo-Minérale, Université Louis Pasteur/CNRS, U.M.R. 7177, Institut 

de Chimie, 4, rue Blaise Pascal, F-67070 Strasbourg-Cedex, France 

Catenanes represent attractive synthetic challenges in molecular chemistry. The creation of 

such complex molecules as well as related compounds of the rotaxane family demonstrates 

that synthetic chemistry is now powerful enough to tackle problems whose complexity is 

sometimes reminiscent of biology, although the elaboration of molecular ensembles displaying 

properties as complex as biological assemblies is still a long-term challenge. 

The field of artificial molecular machines and motors has experienced a spectacular 

development in the course of the last fifteen years, in relation to biological motors or information 

storage and processing at the molecular level. A recent example consists of a fast-moving 

rotaxane whose ring undergoes a pirouetting motion on the millisecond time scale by oxidizing 

or reducing the central copper atom (Cu II /Cu I ). 

Recently, our group has also proposed a transition metal-based strategy for making twodimensional 

interlocking and threaded arrays. Large cyclic assemblies containing several 

copper(I) centres could be prepared which open the gate to controlled dynamic two-dimensional 

systems and membrane-like structures consisting of multiple catenanes and rotaxanes. 

In the course of the last three years, we have been much interested in endocyclic but non 

sterically hindering chelates. These compounds are based on carefully designed 3,3'biisoquinoline 

derivatives. Some of them have even been incorporated into macrocyclic 

compounds. A particularly efficient and fast moving molecular "shuttle" based on such a chelate 

has been made and investigated as well as three-component molecular entanglements 

constructed by assembling three such ligands around an octahedral metal centre. These 

biisoquinoline-based compounds are particularly promising in relation to fast-responding 

controlled dynamic systems and novel topologies.

PL 7 

Calixarenes in Action: From Anion Recognition to DNA Condensation and 

RNA Cleavage 

Rocco Ungaro 

Dipartimento di Chimica Organica e Industriale, Università degli Studi di Parma and INSTM, 

Sezione di Parma, Viale G.P. Usberti 17/A, I-43100-Parma (Italy) 

Anion Recognition is an important topic in Supramolecular Chemistry and has been tackled 

using various strategies depending on the particular application which one aims to. For many 

years we have been particularly interested in the synthesis of selective receptors for carboxylate 

anions, which are substrates of biological interest, using calixarenes as scaffolds and hydrogen 

bonding as the main supramolecular interaction. [1] 

More recently, we have adorned the upper rim of calix[n]arenes, having different sizes and 

Figure 

Cl Cl 

Cl 

+ 

H2N H N 

+ 

+ 

2 NH2 H N 

Cl 

2 NH 

+ 

2 

NH 

HN 

NH2 HN 

H N 

HN 

2 

NH2 O O O O 

R 

R R R 

R = C 3 H 7 : 4G4Pr-cone 

R = C 6 H 13 : 4G4Hex-cone 

R = C 8 H 17 : 4G4Oct-cone 

Cl 

H2N + 

H 

N 

NH 2 

+ NH2 Cl 

H N NH 

2 

OMe MeO 

OMe 

HN 

Cl 

+ NH2 shapes, with guanidinium groups and used the resulting water soluble multivalent ligands 

(Figure) in DNA binding and cell transfection. By Atomic Force Microscopy (AFM) it has been 

possible to correlate the topology of the ligands with their DNA condensation and transfection 

ability. [2] 

In collaboration with Mandolini’s and Reinhoudt’s groups we have synthesized a series of 

calix[4]arenes bearing at the upper rim a variable number of metal ion chelating units such as 

aza macrocycles ([12]aneN3) or 2,6-bis[(dimethylamino)methyl]pyridine (DMAP). The Zn(II) or 

Cu(II) complexes of these multivalent ligands are able to catalyze the methanolysis of aryl 

esters and the cleavage of phosphodiester bonds in oligoribonucleotides, showing substrate 

selectivity and cooperativity between the metal centers. [3] 

An overview of the most recent results obtained using anion receptors, multivalent ligands, and 

supramolecular catalysts based on calixarenes will be given in the lecture. 

[1] A. Casnati, F. Sansone, R. Ungaro, Acc. Chem. Res. 2003, 36, 246-254. A.V. 

Yakovenko,.I. Boyko, V. Kalchenko, L. Baldini, A. Casnati, F. Sansone, R. Ungaro, J. Org. 

Chem. 2007, 72(9), 3223-3231. 

[2] F. Sansone, M. Dudi, G. Donofrio, C. Rivetti, L. Baldini, A. Casnati, S. Cellai, R.Ungaro, J. 

Am. Chem. Soc. 2006, 128, 14528 – 14536. L. Baldini, A. Casnati, F. Sansone, R. Ungaro, 

Chem. Soc. Rev. 2007, 34, 254-266. 

[3] R. Cacciapaglia, A. Casnati, L. Mandolini, D.N. Reinhoudt, R. Salvio, A. Sartori, R. Ungaro, 

J. Am. Chem. Soc. 2006, 128, 12322-12330 and references therein. 

OMe 

NH 2 

N 

H 2 

n-3 

N 

H 

n = 4: 4G4Me-mobile 



Cl 

+ 

NH2 + 

+ 

Cl 

H 

Cl 

2N NH2 N 

H 2 

NH 

O 

O O 

HN 

O 

NH 2 

NH 

HN 

Cl 

H2N + 

NH2 H2N 4G4Pr-alt 

Cl 

NH2 + 

PL 8 

From Supramolecular Chemistry to Constitutional Dynamic Chemistry 

Jean-Marie Lehn 

ISIS, Université Louis Pasteur, Strasbourg and Collège de France, Paris 

Supramolecular chemistry is actively exploring the design of systems undergoing selforganization, 

i.e. systems capable of spontaneously generating well-defined functional 

supramolecular architectures by self-assembly from their components, on the basis of the 

molecular information stored in the covalent framework of the components and read out at the 

supramolecular level through specific interactional algorithms, thus behaving as programmed 

chemical systems. 

The implementation of such molecular information-controlled self-organizing processes for 

the generation of functional nanostructures provides a powerful approach to nanoscience and 

nanotechnology . 

Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the 

interactions connecting the molecular components of a supramolecular entity and the resulting 

ability of supramolecular species to exchange their constituents. The same holds for molecular 

chemistry when the molecular entity contains covalent bonds that may form and break 

reversibility, so as to allow a continuous change in constitution by reorganization and exchange 

of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the 

molecular and supramolecular levels. 

CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter 

relies on design for the generation of a target entity, while CDC takes advantage of dynamic 

diversity to allow variation and selection. The implementation of selection in chemistry 

introduces a fundamental change in outlook. Thus, self-organization by design strives to 

achieve full control over the output molecular or supramolecular entity by explicit programming, 

whereas self-organization with selection operates on dynamic constitutional diversity in 

response to either internal or external factors to achieve adaptation. 

Applications of this approach in biological systems as well as in materials science will be 

described. 

The merging of the features: - information and programmability, - dynamics and reversibility, 

-constitution and structural diversity, points towards the emergence of adaptive chemistry. 

Lehn, J.-M., Supramolecular Chemistry: Concepts and Perspectives, VCH Weinheim, 1995. 

Lehn, J.-M., Dynamic combinatorial chemistry and virtual combinatorial libraries, Chem. Eur. 

J., 1999, 5, 2455. 

Lehn, J.-M., Programmed chemical systems : Multiple subprograms and multiple 

processing/expression of molecular information, Chem. Eur. J., 2000, 6, 2097. 

Lehn, J.-M., Toward complex matter: Supramolecular chemistry and self-organization, Proc. 

Natl. Acad. Sci. USA, 2002, 99, 4763. 

Lehn, J.-M., Toward self-organization and complex matter, Science, 2002, 295, 2400. 

Lehn, J.-M., Dynamers : Dynamic molecular and supramolecular polymers, 

Prog. Polym. Sci., 2005, 30, 814. 

Lehn, J.-M., From supramolecular chemistry towards constitutional dynamic chemistry and 

adaptive chemistry, Chem. Soc. Rev., 2007, 36, 151.

Exercising Demons: Synthetic Molecular Motors and Machines 

Dave Leigh 

School of Chemistry, University of Edinburgh, The King’s Buildings, West Mains Road, 

Edinburgh EH9 3JJ, UK 

David.Leigh@ed.ac.uk; http//www.catenane.net or www.rotaxane.net 

An exciting contemporary area of chemistry is making molecules with moving parts, with the 

goal that they can function as nanoscopic machines capable of performing physical tasks. To do 

so for any molecular machine more sophisticated than a simple switch requires the introduction 

of ratchet principles into synthetic molecular structures. We will discuss some of the latest 

developments from our group in this area, including the experimental realisation of both energy 

ratchets and information ratchets. [1] 

[1] For some recent papers from the Leigh group see: Nature, 424, 174-179 (2003); Science, 

299, 531 (2003); Science, 306, 1532-1537 (2004); Proc Natl Acad Sci USA, 102, 13378-13382 

(2005); Nature Mater, 4, 704-710 (2005); Angew Chem Int Ed, 44, 3062-3067 (2005); Angew 

Chem Int Ed, 44, 4557-4564 (2005); J Am Chem Soc, 127, 12612-12619 (2005); Proc Natl 

Acad Sci USA, 103, 17650-17654 (2006); Nature, 440, 286-287 (2006); J Am Chem Soc, 128, 

526-532 (2006); J Am Chem Soc, 128, 1784-1785 (2006); J Am Chem Soc, 128, 2186-2187 

(2006); J Am Chem Soc, 128, 4058-4073 (2006); Angew Chem Int Ed, 45, 77-83 (2006); Angew 

Chem Int Ed, 45, 1385-1390 (2006); J Am Chem Soc, 129, 476-477 (2007); Angew Chem Int 

Ed, 46, 72-191 (2007); Nature, 445, 523-527 (2007). 

ICA

Carbon Dioxide and Supramolecular Chemistry 

Dmitry M. Rudkevich 

Department of Chemistry & Biochemistry, The University of Texas at Arlington, Arlington, TX 

76019-0065, USA 

Carbon dioxide (CO2) is the major greenhouse gas. It constantly circulates in the environment 

through a variety of processes known as the carbon cycle. Extensive CO2 circulation in the 

atmosphere, industry and agriculture requires not only its systematic monitoring under a variety 

of conditions, but more importantly, necessitates the development of improved methods of the 

CO2 fixation and chemical utilization. We employ methods and techniques of supramolecular 

chemistry for these purposes. In particular, we explore the dynamic covalent chemistry between 

CO2 and primary amines. [1] 

Our progress will be highlighted in the following directions: 

1. Switchable supramolecular polymers and peptide-based nanoscale architectures from 

CO2 and their further functionalization. [2,3] 

2. Reversibly formed carbamate materials for selective entrapment, separation and storage 

of guest ions and molecules of biological and industrial interest. [4,5] 

3. Supramolecular sensors for CO2 and its toxic derivatives. [6,7] 

[1] D. M. Rudkevich and H. Xu, Chem. Commun., 2005, 2651-2659 (review). 

[2] V. Stastny, A. Anderson and D. M. Rudkevich, J. Org. Chem., 2006, 71, 8696-8705. 

[3] H. Xu and D. M. Rudkevich, Chem. Eur. J., 2004, 10, 5432-5442. 

[4] V. Stastny and D. M. Rudkevich, J. Am. Chem. Soc., 2007, 129, 1018-1019. 

[5] H. Xu and D. M. Rudkevich, Org. Lett., 2005, 7, 3223-3226. 

[6] E. M. Hampe and D. M. Rudkevich, Tetrahedron, 2003, 59, 9619-9625. 

[7] H. Zhang and D. M. Rudkevich, Chem. Commun., 2007, 1238-1239. 

IL 1 

Mechanistic Aspects of Threading of Polymers in Processive Rotaxane 

Catalysts 

Ruud G.E. Coumans, Pilar Hidalgo Ramos, Alexander B.C. Deutman, 

Johannes A.A.W. Elemans, Roeland J.M. Nolte, Alan E. Rowan 

Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED 

Nijmegen, The Netherlands. Email: A.Rowan@science.ru.nl 

IL 2 

Natural processive enzymes, such as -exonuclease or DNA polymerase III, operate by 

threading a DNA strand in a pseudo-rotaxane topology and subsequently slide along the chain 

performing several rounds of catalysis before they dissociate. 1 These highly efficient 

biocatalysts have inspired us to develop the first example of a synthetic processive rotaxane 

catalyst: 2 manganese porphyrin-containing macrocycle was threaded onto a polybutadiene 

strand and mimicked the catalytic action of a natural processive enzyme by catalyzing the 

epoxidation of the double bonds of the polymer while sliding along its chain. 

In order to investigate this threading in more detail a series mono functionalized polymers 

was synthesized which contain a blocking N,N’-dialkyl-4,4’-bipyridinium trap at one side of the 

polymer chain and an open end at the other side. 3 The macrocycles are unable to slip over the 

blocking group and therefore they have to traverse the whole polymer chain before they reach 

the bipyridine trap which quenches the fluorescence of the macrocycle. Fluorescence emission 

studies revealed that the kinetics of threading followed a second order process and that the rate 

of threading was found to dependent on the polymer length with a length-dependent barrier of 

61 J/nm which increase to 93 J/nm when a larger more flexible macrocycle was used. 

The thermodynamics of threading revealed that for all polymers H ‡ on was positive and 

S ‡ on strongly negative with the absolute value of S ‡ on increasing with polymer length. These 

results are supportive of the nucleation mechanism proposed by Muthukumar, 4 resembling the 

transportation of DNA through the opening in a virus particle. 

These studies have provided direct evidence that macrocyclic compounds can readily thread 

onto polymeric chains and slide along. The time needed to reach the blocked end of the 

polymer is related to polymer length, and the rate-limiting step involves a barrier of entropic 

origin in which a certain part of the open end of the polymer has to stretch and unfold. Recent 

studies describing how this threading rate can be controlled using a metallated porphyrincontaining 

macrocycle, will also be discussed. 5 

[1]. Wang, J.; Sattar, A.; Wang, C. C.; Karam, J. D.; Konigsberg, W. H.; Steitz, T. A. Cell 1997, 

89, 1087. 

[2]. Thordarson, P.; Bijsterveld, E. J. A.; Rowan, A. E.; Nolte, R. J. M. Nature 2003, 424, 915. 

[3]. Coumans, R. G. E.; Elemans, J. A. A. W.; Nolte, R. J. M.; Rowan, A. E. Proc. Natl. Acad. 

Sci. U.S.A. 2006, 103, 19647. 

[4]. Muthukumar, M. Phys. Rev. Lett. 2001, 82, 3188. 

[5]. Hidalgo Ramos, P.; Coumans, R. G. E.; Deutman, A. B. C.; Smits, J. M. M.; de Gelder, R.; 

Elemans, J. A. A. W.; Nolte, R. J. M.; Rowan, A. E. J. Am. Chem. Soc. 2007, 129(17) 5699.

Synthetic Strategies and Structural Aspects of Metal-Mediated Multi- 

Porphyrin Assemblies 

Elisabetta Iengo, † Ennio Zangrando, Enzo Alessio 

Department of Chemistry, University of Trieste, 34127 Trieste, Italy. 

† 

Current address: University of Cambridge, Chemical Laboratories, Lensfield Road, Cambridge 

CB2 1EW, UK. 

Porphyrins play a major role as active chromophores in artificial systems mimicking the natural 

photoinduced processes. The formation of coordination bonds between peripheral donor sites 

on the porphyrins and external metal fragments has proved to be an efficient alternative to 

covalent synthesis for the construction of multi-porphyrin assemblies, whose complexity and 

beauty gradually approach those of the multichromophore systems found in Nature. 

In a modular approach, relatively simple metal-mediated porphyrin adducts, owing to their 

thermodynamic and kinetic stability, can be exploited as building blocks in the construction of 

higher order architectures. Thus multichromophore systems become accessible on demand, 

with a limited synthetic effort. 

The collection of solid state 

structures that will be 

reported demonstrates that 

the flexibility of the 

porphyrins and of the metal 

junctions, combined with 

the conformational freedom 

of the coordination bonds, 

may lead to assemblies 

with hardly predictable 

architectures. Examples in 

which X-ray structural determination was essential for establishing the real composition and 

geometry of the multiporphyrin assemblies, such as the slipped-cofacial porphyrin macrocycle 

shown in the figure, will be highlighted. 

Some recent references of our contributions to this field are given below [1-4]. 

[1] F. Scandola, C. Chiorboli, A. Prodi, E. Iengo, E. Alessio, Coord. Chem. Rev., 2006, 250, 

1471-1496. 

[2] E. Iengo, F. Scandola, E. Alessio, Struct. Bond., 2006, 121, 105-144. 

[3] E. Iengo, E. Zangrando, E. Alessio, Acc. Chem. Res., 2006, 39, 841-851. 

[4] A. Prodi, C. Chiorboli, F. Scandola, E. Iengo, E. Alessio, ChemPhysChem, 2006, 7, 1514- 

1519. 

IL 3 

Cyclodextrin-based Supramolecular Architectures and Dynamics 

Akira Harada, Hiroyasu Yamaguchi, Yoshinori Takashima, Yasushi Okumura 

Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. 

E-mail: harada@chem.sci.osaka-u.ac.jp 

Cyclodextrins (CDs) have been extensively used as 

host molecules for small molecules. We found that 

CDs form inclusion complexes with some polymers 

selectively to give pseudo-polyrotaxanes.[1] 

Recently, we found that CD rings pass through 

some groups unidirectionally (Figure1) [2]. In 

addition, we found that the threading process could 

be monitored by using a CD with a PEG chain by 

way of a cinnamoyl group in the presence of a 

competitive guest. (Figure 2) [3] 

When each end of the polymer chain of the 

pseudo-polyrotaxane is blocked by large 

stopper groups, polyrotaxanes were obtained. 

[4] One or two CD rings could be moved by 

using an STM tip along a polymer chain. [5] 

When neighbouring CD units were linked by 

short binding agents, followed by removing 

bulky stopper groups at both ends of the 

polymer chain, tubular polymers were obtained. 

[6] The molecular tube includes long molecules 

like 1,6-diphenylhexatriene to give highly 

fluorescent inclusion complexes. 

When a guest part was attached to a 

cyclodextrin host, they formed intramolecular or 

intermolecular complexes to give 

supramolecular assemblies. When a cinnamoyl 

group was attached to one of 6-OH groups by 

an ester linkage, they formed a cyclic trimer 

(cyclic daisy chain). When a cinnamoyl group 

was attached by an amide bond, they formed a 

Figure 1. Unidirectional threading 

Figure 2. Conformational switching 

Figure 3. α-,β-CD alternating copolymer 

IL 4 

cyclic dimer. When a cinnamoyl group was attached to one of the secondary hydroxyl groups, 

they formed linear oligomers, when the t-Boc group was attached to the cinnamoyl group, they 

formed longer helical supramolecular polymers. In addition we have prepared α−,β-CDalternating 

supramolecular polymers and [2]rotaxane polymers.[7] Supramolecular catalytic 

system [8], stimuli-resposive systems[9], and supramolecular sensors have been developed. 

[1] Chem. Commun., 1990, 1332. Macromolecules, 23, 2823 (1990). 

[2] J. Am. Chem. Soc., 2005,127, 12186: J. Phys. Condens. Matter 2006, 18, S1809; Chem.Euro. J., in 

press.; J. Am. Chem. Soc., 2000, 122, 3797. 

[3] J. Am. Chem. Soc., 2006, 128, 8994; Macromolecules, in press. 

[4] Nature, 356, 325 (1992). J. Am. Chem. Soc., 1994, 116, 3192. 

[5] J. Am. Chem. Soc. ,2000, 122, 5411; 2003, 125, 5080 

[6] Nature, 364, 516 (1993), 370, 126 (1994). 

[7] J. Am. Chem. Soc., 2000, 122, 9876; 2004, 126, 11418; 2005, 127, 2034; 2005, 127, 2984. 

[8] J. Am. Chem. Soc., 2004, 126, 13588; Macromolecules, in press. 

[9] J. Am. Chem. Soc., 2006, 128, 2226; Angew. Chem., Intl. Ed., 2006, 4605.

Complexity from Simple Parts via Subcomponent Self-Assembly 

Jonathan R. Nitschke * , Marie Hutin, David Schultz, Rupam Sarma and Victoria E. Campbell 

Organic Chemistry Department, University of Geneva, 30 quai Ernest-Ansermet, CH-1211 

Genève 4 

Highlights of some of our work in progress, as well as a few of the topics of the first four years of 

our research program, will be presented. 1 Starting with the use of the template effect to create 

stable structures linked together by both covalent (C=N) and coordinative (NM) bonds 2, 3 from 

mixtures of amines, aldehydes, and copper(I) ions, we have generated a variety of structures, 

including a tetrametallic grid held together by the hydrophobic effect, 4 helicates, 5, 6 macrocycles 

and catenates. 7 Four of these constructions are shown below. 

R 

N 

N Cu 

N 

N 

N 

N Cu N 

N 

N 

CuN 

N 

N 

R 

R 

N 

NCu 

N 

N 

R 

O 

O 

N N 

N Cu N 

N Cu N 

N N 

O O 

O 

O 

H 

N 

N 

H 

N N 

N Cu N 

N Cu N 

N N 

H 

N 

H 

N 

O 

O 

N N 

Cu 

N N 

N N 

Cu 

N N 

N N 

Cu 

N N 

The covalent imine (C=N) bonds that knit these structures together are thermodynamically 

stable, but capable of exchange with free 

amines. Differentials between the pKa’s 

of aliphatic and aromatic amines may be 

used as a driving force to effect selective 

imine exchange. As shown at right, 

protonated sulfanilic acid can displace 

the more basic aliphatic diamine a, 

which allows the deprotonated 

sulfanilate to incorporate itself in place of 

the diamine. If the pH of the reaction 

solution is raised, however, the reaction 

reverses: Deprotonated diamine a is 

2 O 

4 H 2N SO 3 - 

N N 

N Cu N 

N Cu 

N N 

N 

H3N NH3 a 

N N 

N Cu N 

N Cu N 

N N 

- O3S SO 3 - 

more nucleophilic than sulfanilate. Changes in pH may thus be used to switch between a closed 

macrocycle and open helicate. 

Current directions of our research program include the selection of specific structures from 

dynamic libraries, 3, 6, 8, 9 the preparation of conducting, metal-containing polymers, and the 

linking together of foldamers (in collaboration with Ivan Huc and Sijbren Otto) into assemblies 

having molecular weights and levels of structural definition comparable to those of proteins. 

1. J.R. Nitschke Acc. Chem. Res. 2007, 40, 103 

2. J.R. Nitschke Angew. Chem. Int. Ed. 2004, 43, 3073 

3. D. Schultz, J.R. Nitschke Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 11191 

4. J.R. Nitschke, M. Hutin, G. Bernardinelli Angew. Chem. Int. Ed. 2004, 43, 6724 

5. J.R. Nitschke, D. Schultz, G. Bernardinelli, D. Gérard J. Am. Chem. Soc. 2004, 126, 16538 

6. M. Hutin, R. Franz, J.R. Nitschke Chem. Eur. J. 2006, 12, 4077 

7. M. Hutin, C.A. Schalley, G. Bernardinelli, J.R. Nitschke Chem. Eur. J. 2006, 12, 4069 

8. D. Schultz, J.R. Nitschke Angew. Chem. Int. Ed. 2006, 45, 2453 

9. M. Hutin, G. Bernardenelli, J.R. Nitschke Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 17655 

O 

H2N NH2 a 

O 

N 

Cu 

N 

I 

O 

O O 

O 

O 

H + 

2 O 

+ 

+ 

O 

- O3S 

OH - 

IL 5 

SO 3 - 

IL 6

Anion binding as a conformational and self-assembly trigger 

Jonathan W. Steed 

Chemistry Department, Durham University, Durham DH1 3LE, UK. Jon.steed@durham.ac.uk 

We have designed a number of anion-binding containers exhibiting dynamic conformational 

behaviour. These systems range from macrobicyclic cryptands (1) exhibiting conformational 

twisting to tripodal (2) and tetrapodal hosts (3) exhibiting significant flexibility of the pendant 

arms. The containers’ dynamic properties are modulated by anion binding. Anion binding may 

also be used to modulate self-assembly and hence rheological properties in supramolecular gel 

phase systems. This lecture explores the scope and uses of this kind of fundamental process in 

preparing new supramolecular sensors and materials. 

1 2 3 

HN 

N + 

N + 

NH 

N + 

HN 

R 

NH 

N + 

R 

O 

O 

N + 

O 

N + 

O 

O 

O HN 

NH O 

O 

R 

HN 

N + 

R 

IL 7 

IL 8 

Oligopyrrole-based chemosensors for potentially hazardous materials 

Jonathan L. Sessler † , Marcin Stpie † , Patricia Melfi † , Kent Nielsen †,‡ , Jan Jeppesen, ‡ Evgeny 

Katayev †,§ , Bertrand Donnio , Jackie Veauthier ° , and Andrew M. Shaw 

† Department of Chemistry & Biochemistry, The University of Texas at Austin, 1 University 

Station A5300, Austin, TX 78712-0165 USA 

‡ Dept. of Physics and Chemistry, University of Southern Denmark, Campusvej 55, DK-5230, 

Odense M, Denmark 

§ Institute for Organoelement Chemistry, Russian Academy of Sciences, Vavilova st. 28, 

Moscow, 119991, Russia 

Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 (CNRS-Université 

Louis Pasteur), 23 rue du Loess BP 43, 67034 Strasbourg Cedex 2, France 

° C-IIAC (Inorganic, Isotope, & Actinide Chemistry), Los Alamos National Laboratory, MS J514, 

Los Alamos, NM 87545, USA 

EvanesCo Ltd, 4 &5 Forde Court, Forde Road, Newton Abbot, TQ12 4AD, United Kingdom 

The design and synthesis of novel receptors with the ability to recognize selectively and signal 

selected analytes through easy-to-visualize changes in color constitutes a critical goal in 

macrocyclic and supramolecular chemistry. We have approached this broad objective via the 

construction of both cyclic and acyclic pyrrole-based receptors that are able to interact with 

cationic, anionic, and neutral substrates through various combinations of metal coordination, 

hydrogen bonding, electrostatic, and donor-acceptor interactions. In this presentation the focus 

will be on systems, such as those shown in Figure 1, that allow for the specific colorimetric 

detection of potentially hazardous analytes, including such canonical risks as high-valent 

radioactive actinide cations, the pertechnetate anion, and electron deficient nitroarene 

explosives. Several lead references are given below. 

The work in the presenter’s laboratory was supported by the National Institutes of Health, the 

National Science Foundation, and the U.S. Department of Energy. 

NH 

NH HN 

N 

H 

N 

N 

isoamethyrin 

Ph Ph 

O N N O 

H H 

NH HN 

N 

NH HN 

BP-DPM 

R 

N 

NH HN 

NH HN 

NH 

N 

HN 

R R R 

R 

R 

R 

R 

R 

R 

R 

R 

R 

R R 

R 

cyclo[8]pyrrole 

Figure 1: Novel receptors and sensors relevant to this presentation. 

N 

S S 

Me Me 

Me 

Me 

N 

S H S S 

NH HN 

S H S S 

N 

Me Me 

Me Me 

S S 

[1] Nielsen, K. A.; Cho, W.-S.; Jeppesen, J. O.; Lynch, V. M.; Becher, J.; Sessler, J. L. J. Am. 

Chem.Soc. 2004, 126, 16296-16297. 

[2] Sessler, J. L.; Katayev, E. A.; Pantos, G. D.; Reshetova, M. D.; Khrustalev, V. N.; Lynch, V. 

M.; Ustynyuk, Y. A. Angew. Chem. Int. Ed. 2005, 44, 7386-7390. 

[3] Stpie, M.; Donnio, B.; Sessler, J. L. Angew. Chem. Int. Ed. 2007, 46, 1431–1435. 

[4] Sessler, J. L.; Melfi, P. J.; Seidel, D.; Gorden, A. V.; Ford, D. K.; Palmer, P. D.; Tait, C. D. 

Tetrahedron, 2004, 60, 11089-11097. 

PrS 

PrS 

S 

S 

PrS SPr 

S 

PrS 

S 

S S 

SPr 

TTF calix[4]pyrrole 

SPr 

SPr

Pyridine-Containing Macrocycles for Oxygen Activation and Anion 

Recognition 

Elena V. Rybak-Akimova, Sonia Taktak, Wanhua Ye, Aida M. Herrera, Voltaire Organo, 

Ivan V. Korendovych, Mimi Cho 

Department of Chemistry, Tufts University, Medford, MA 02155, USA 

Pyridine-containing macrocycles serve as versatile platforms that support biomimetic, redoxactive 

transition metal complexes. Cyclic structure of the ligands allows for systematic variations 

in coordination geometry of the central metal ions, so that structure-reactivity correlations can 

be established. Additionally, amidopyridine structural fragments are capable of forming 

hydrogen bonds with organic guests. Several examples of functional pyridine-containing 

macrocycles will be considered. 

Tetraaza macrocycles bearing an aminopropyl pendant arm (I) forms stable five-coordinate 

complexes with iron(II). Reversible transformations between four-coordinate, square-planar and 

five-coordinate, tetragonal pyramidal complexes allowed us to probe the role of iron 

coordination geometry in redox reactivity of these species. These complexes are efficient 

catalysts in olefin epoxidation with hydrogen peroxide in slightly acidic media, However, in the 

absence of acids, no epoxidation occurs. Protonation of the pendant arm causes the conversion 

of high-spin, five-coordinate complexes into low-spin, pseudo-octahedral species with two labile 

axial sites, thus greatly facilitating olefin epoxidation. These findings differ from commonly 

observed enhancement of redox reactivity due to axial ligand coordination to iron porphyrins.[1] 

Incorporating strong electron-donating amide groups in the macrocycles greatly improves the 

reactivity of their iron(II) complexes (II) with dioxygen. Amide groups can be protonated, serving 

an an intramolecular proton source. The availability of accessible protons alters oxygenation 

pathways: diiron(III)-peroxo intermediates were generated in the absence of protons, while rapid 

conversion to iron(III) oxidation products occurs in the presence of protons.[2] 

Large amidopyridine rings (products of [2+2] condensations, III) provide hydrogen-binding sites 

for molecular recognition of inorganic and organic guests. Selectivity in carboxylate recognition 

was accomplished. These systems can be utilized in designing hetero-ditopic hosts that can 

encapsulate a redox-active metal ion in one compartment, and an organic substrate in another 

compartment.[3] 

R 

R 

N 

H 2N 

NH 

Fe N 

NH 

2+ 

O 

N 

N 

Fe 

NH NH 

N 

O 

NH 

NH 

I II III 

[1] Taktak, S.; Ye, W. ; Herrera, A.M.; Rybak-Akimova, E.V. Inorg. Chem. 2007, 46, 2929-2942. 

[2] Korendovych, I.V. ; Kryatova, O.P. ; Reiff, W.M. ; Rybak-Akimova, E.V. Inorg. Chem. 2007, 

46, ASAP article. 

[3] Korendovych, I.V. ; Cho, M. ; Butler, P.L. ; Staples, R.J. ; Rybak-Akimova, E.V. Org. Lett. 

2006, 8, 3171-3174. 

O 

O 

N 

N 

H 

H 

N 

N 

H 

H 

N 

HN 

HN 

N 

O 

O 

IL 9 

A comparison of mobile phase and stationary phase 

Macrocycle based ion chromatography 

John D. Lamb, Quinn P. Peterson, and Brandon J. Tibbitts 

Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, USA 

Macrocyclic ligands such as crown ethers, cryptands, and resorcinarenes have been 

incorporated into the mobile and stationary phases of ion chromatographic systems. The degree 

to which chromatographic retention of cations and anions is affected depends on the interplay of 

a number of chemical equilibria. Adjustments among these equilibria give the chromatographer 

considerable flexibility in the design of separations. For example, in the separation of anions, 

varying the identity or concentration of mobile phase cation or varying column temperature can 

be used to accomplish a unique brand of gradient separation dubbed capacity gradient 

chromatography, illustrated in Figure 1. Such gradients are typically carried out with the 

macrocycle adsorbed onto or bound to the stationary phase. On the other hand, when 

macrocycles are included as mobile-phase components, they can be used to adjust the elution 

times and orders of cations when using traditional ion exchange columns, or as the primary 

components of chromatographic retention of ions on reversed phase columns. For example, 

this latter approach makes it possible to selectively retain and separate target analyte anions 

such as ClO4 - ion, as illustrated in Figure 2. By optimizing eluent conditions, we are able to 

achieve trace-level quantification of ClO4 - ion to levels below 1 ppb. And in the case of cations, 

we are able to separate and quantify ammonium ion in the presence of high sodium ion even 

when the ratio of sodium to ammonium ions is 60,000:1. 

Figure 1. Separation of anions on 

decyl-2.2.2 column by gradient 

capacity. 1) fluoride 2) acetate 3) 

chloride 4) nitrite 5) bromide 6) 

nitrate 7) sulfate 8) oxalate 9) 

chromate 10) iodide 11) 

phosphate 12) phthalate 13) 

citrate 14) thiocyanate 

Figure 2. Separation of 

anions in water samples with 

perchlorate at three 

concentrations. 

Conductivity (S) 

7 

6 

5 

4 

3 

2 

1 

Cl - - 

, NO3 2- 

SO4 - 

ClO4 0 

0 5 10 15 20 

Time (min) 

100 ppb 

10 ppb 

1 ppb 

IL 10

Supramolecular control of a metal center embedded in a biomimetic 

hydrophobic cavity: the Funnel Complexes. 

Olivia Reinaud 

Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, 

Université René Descartes, 45 rue des Saints-Pères, F-75270 Paris Cedex 06, France 

E-mail: Olivia.Reinaud@univ-paris5.fr 

Modeling the active site of an enzyme is an important tool for a better understanding of its 

catalytic cycle. Classically however, biomimetic inorganic chemistry is mainly focused on 

reproducing the first coordination sphere of the metal ion and little information is available 

concerning the influence, or even the control, that the microenvironment provided by a protein 

can have on the reactivity of the metal. 

The aim of our work is to design supramolecular systems that will mimic both the coordination 

core and the hydrophobic pocket of a metallo-enzyme active site. Our strategy is to synthesize 

calix[6]arene-based ligands that allow the control of the coordination sphere of the metal ion 

together with the approach and the binding of an external molecule. 

Three generations have been yet developed: the first 1 offers three nitrogenous arms, the 

second 2 has a fourth hemi-labile binding site X, the third 3 presents a capped calixarene 

exemplified by the calix-tren ligand that allows a better control of the geometry of the 

supramolecular edifices. Characterization and comparative behavior of the corresponding zinc 

and copper complexes will be presented. 

His His His 

M 

L 

S 

N 

N 

M 

L 

N 

n+ 

X n+ 

N N 

N M 

L 

I II III 

Enzyme active site Calix-models 

X n+ 

N 

N M 

N 

[1]. S. Blanchard, L. Le Clainche, M.-N. Rager, B. Chansou, J. P. Tuchagues, A. Duprat, Y. Le Mest, O. 

Reinaud, Angew. Chem., Int. Ed., 1998, 37, 2732; O. Sénèque, M.-N. Rager, M. Giorgi, O. Reinaud, J. 

Am. Chem. Soc., 2000, 122, 6183; O. Sénèque, M. Giorgi, O. Reinaud Supramol. Chem. 2003, 15, 573; 

U. Darbost, O. Sénèque, Y. Li, G. Bertho, J. Marrot, M.-N. Rager, O. Reinaud, Ivan Jabin, Chem. Eur. J. 

2007, 13, 2078. D. Coquière, J. Marrot and O. Reinaud, Chem. Commun. 2006, 3924. 

[2]. O. Sénèque, M. Campion, B. Douziech, M. Giorgi, Y. Le Mest, O. Reinaud, Dalton Trans. 2003, 

4216; O. Sénèque, M.-N. Rager, M. Giorgi, T. Prangé, A. Tomas, O. Reinaud. J. Am. Chem. Soc. 2005, 

127, 14833. 

[3]. U. Darbost, M.-N. Rager, S. Petit, I. Jabin, O. Reinaud, J. Am. Chem. Soc. 2005, 127, 8517; G. 

Izzet, B. Douziech, T. Prangé, A. Tomas, I. Jabin, Y. Le Mest, O. Reinaud, Proc. Natl. Acad. Sci. USA, 

2005, 102, 6831; X. Zeng, D. Coquière, A. Alenda, E. Garrier, T. Prangé, Y. Li, O. Reinaud, I. Jabin, 

Chem. Eur. J. 2006, 12, 6393. G. Izzet, X. Zeng, H. Akdas, J. Marrot and O. Reinaud, Chem Commun. 

2007, 810. G. Izzet, X. Zeng, D. Over, B. Douziech, J. Zeitouny, M. Giorgi, I. Jabin, Y. Le Mest, O. 

Reinaud, Inorg. Chem. 2007, 46, 375. G. Izzet, M.-N. Rager, O. Reinaud, Dalton Trans. 2007, 771. 

L 

IL 11 

Why are Certain Cyclopeptides so Efficient Anion Hosts? 

Stefan Kubik 

Fachbereich Chemie - Organische Chemie, Technische Universität Kaiserslautern, 

Erwin-Schrödinger-Strasse, D-67663 Kaiserslautern, Germany 

We recently demonstrated that cyclic hexapeptide 1 containing L-proline and 6-aminopicolinic 

acid subunits strongly binds to sulfate or halides even in competitive protic solvents such as 

80% water/methanol.[1] The main reason for this, for a neutral host, unusual property turned out 

to be the sandwich-type structure of the complexes formed in which the anion is included into a 

cavity between two interdigitating cyclopeptide moieties. 

O 

HN 

N 

N 

O 

O 

N 

N 

NH 

NH 

O 

O 

N 

N 

O 

O 

N 

O 

N 

HN 

HN 

O 

N 

N 

O 

N 

O 

N 

O 

NH 

H 

N 

X 

O O 

1 2 

H 

N 

O 

HN 

N 

N 

O 

O 

N 

N 

NH 

NH 

O 

O 

N 

IL 12 

The 2:1 anion complexes of 1 were subsequently converted into 1:1 complexes by covalently 

linking two cyclopeptide rings together. Biscyclopeptides of the general structure 2 have thus 

been obtained that are highly efficient neutral hosts for inorganic anions in aqueous media.[2] 

Anion affinity as well as selectivity of these biscyclopeptides depend on the structure of the 

linker X which was optimized using molecular modeling in collaboration with Benjamin P. Hay 

(Pacific Northwest National Laboratory, Richland, USA) and dynamic combinatorial chemistry in 

collaboration with Sijbren Otto (University of Cambridge, UK).[3] 

Although the anion affinity of such biscyclopeptides is partly a result of the almost perfect 

preorganisation of the two cyclopeptide rings for anion binding as well as the fact that the anion 

is shielded in the complex from the surrounding solvent molecules, it seemed unlikely that 

stability constants of the sulfate complexes of some of these biscyclopeptide of 10 6 - 10 7 M -1 in 

33% water/acetonitrile or 50% water/methanol can be rationalized on the basis of these effects 

alone. Indeed, a detailed structural analysis of the biscyclopeptide/anion complexes as well as 

of the solvent dependence of complex stability revealed that intra-receptor interactions between 

biscyclopeptide regions that are not directly involved in anion binding is an important factor 

contributing to complex stability.[4] Engineering such intra-receptor interactions into synthetic 

hosts therefore seems to be an attractive and powerful strategy to boost host-guest affinities. 

[1] S. Kubik, R. Goddard, R. Kirchner, D. Nolting and J. Seidel, Angew. Chem. Int. Ed. 2001, 40, 

2648-2651. 

[2] S. Kubik, R. Kirchner, D. Nolting and J. Seidel, J. Am. Chem. Soc. 2002, 124, 12752-12760. 

[3] S. Otto and S. Kubik, J. Am. Chem. Soc. 2003, 125, 7804-7805. 

[4] Z. Rodriguez-Docampo, S. I. Pascu, S. Kubik and S. Otto, J. Am. Chem. Soc. 2006, 128, 

11206-11210. 

N 

O

OP 1 

Host Molecules with Switchable Portals: Reversibly Controllable Guest 

Encapsulation 

Thomas Gottschalk, Bernhard Jaun, and François Diederich 

ETH Zürich, Laboratorium für Organische Chemie, 8093 Switzerland 

Reversible switching between a closed conformation and an open form is the key property of 

two novel container molecules, a molecular basket and a molecular tube. In the closed form, 

they encapsulate cycloalkanes such as cyclohexane whereas upon acid-triggered switching to 

the open form, their binding capabilities are completely turned off. Upon neutralization, the 

containers return to their closed conformations and guest binding is restored at full strength. 

Here we describe the design, synthesis, and switchable guest-hosting properties of these novel 

compounds, which are based on the resorcin[4]arene platform. Furthermore we report on 

thermodynamic and kinetic investigations into their host-guest complexation-decomplexation 

equilibria. 

[1] T. Gottschalk, B. Jaun, F. Diederich, Angew. Chem. Int. Ed. 2007, 46, 260-264 

[2] J. R. Moran, S. Karbach, D. J. Cram, J. Am. Chem. Soc. 1982, 104, 5826-5828 

OP 2 

Constitutional sol-gel transcription of nucleobases self-assembly codes 

Carole Arnal-Herault, Mihail Barboiu 

Adaptative Supramolecular Nanosystems Group, Institut Européen des Membranes, IEM/UMII, 

Place Eugène Bataillon, CC047, F-34095 Montpellier, France. 

E-mail: mihai.barboiu@iemm.univ-montp2.fr 

Many research groups have demonstrated that the functional self-organization can be readily 

transcribed into hybrid nanostructures by using the sol-gel process. [1] Accordingly, we have 

reported synthetic routes for preparing self-organized ion-channels systems which have been 

“frozen” in a polymeric matrix, as a straightforward approach for the design of a novel class of 

solid hybrid nanomembranes. [2] 

Nucleobases oligomerization [3] can be an advantageous choice to reinforce the controlled 

communication between interconnected “dynamic supramolecular” and “fixing siloxane” systems. 

Moreover, the different interconverting outputs that nucleobases may form by oligomerization 

define a dynamic polyfunctional diversity which may be “extracted selectively” by sol-gel 

polymerization in solid state, under the intrinsic stability of the system. 

In this context, alkoxysilane nucleobases form in solution different types of hydrogen bonded 

aggregates which can be expressed in the solid state as discrete higher oligomers. After the 

sol-gel process, the constitutional preference for compact geometries in hybrid materials is most 

likely dictated by hydrophobic interactions and 

Hoogsteen H-bonding self-assembly. 

The G-quadruplex with a chiral twisted 

supramolecular architecture represents a nice 

example of a dynamic supramolecular 

system, when guanine and guanosine 

molecules are used. [6] We have recently 

reported a new way to transcribe the 

supramolecular chirality of G-quadruplex at 

the nanometric and micrometric scale. Figure 

1 represents the first picture of the dynamic 

G-quadruplex transcribed at the nanometric 

level; it unlocks the door to the new materials 

world paralleling that of biology. 

Figure 1: SEM image of the twisted hexagonal 

nanorods resulted by sol-gel transcription of 

the chiral G-quadruplex in the hybrid material. 

[1] For reviews see: K. Sada, M. Takeuchi, N. Fujita, M. Numata, S. Shinkai, Chem Soc. Rev. 

2007, 36, 415-435; b) K.J.C. van Bommel, A. Frigerri, S. Shinkai, Angew. Chem. Int. Ed. Engl. 

2003, 42, 980-999. 

[2] a) M. Barboiu, G. Vaughan, A. van der Lee, Org. Lett. 2003, 5, 3073-3076; b) M. Barboiu, J. 

Incl. Phenom. Mol. Rec. 2004, 49, 133-137; c) M. Barboiu, S. Cerneaux, A. van der Lee, G. 

Vaughan, J. Am. Chem. Soc. 2004, 126, 3545-3550 d) A. Cazacu, C. Tong, A. van der Lee, T. 

M. Fyles, M. Barboiu, J. Am. Chem. Soc. 2006, 128 (29) 9541-9548. 

[3] J. L. Sessler, C.M. Lawrence, J. Jayawickramarajah, Chem Soc. Rev.. 2007, 314-325. 

[5] C. Arnal-Hérault, M. Barboiu, A. Pasc, M. Michau, P. Perriat, A. van der Lee, Chem Eur. J. 

2007, in press 

[6] J. T. Davis, Angew. Chem. Int. Ed. 2004, 43, 668-698. 

[7] C. Arnal-Hérault, M. Barboiu, A. Pasc, M. Michau, A. van der Lee, Angew. Chem. Int. Ed. 

Engl. 2007, in press.

OP 3 

Control of molecular architecture by steric and electronic factors: dinuclear 

side-by-side vs tetranuclear [2x2] grid-type silver(I) complexes 

Jason R. Price a , Yanhua Lan a , Geoffrey B. Jameson b , Alejandro Perez-Velasco c , Christopher A. 

Hunter c and Sally Brooker a* 

a 

Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand 

b 

Institute of Fundamental Sciences, Chemistry, Massey University , PO Box 11222, Palmerston 

North, New Zealand 

c 

Krebs Institute for Biomedical Science, Department of Chemistry, University of Sheffield, 

Sheffield, United Kingdom 

The well known plasticity of the coordination geometry of silver(I) offers the opportunity to 

explore the effects that secondary bonding interactions have on supramolecular architectures. 

While the co-ordination of relatively rigid poly-bidentate ligands to Ag(I) has been shown to form 

[2x3], [3x3] and [4x5] grids with the Ag(I) ion adopting a distorted tetrahedral geometry,[1] 

recent investigations by Constable et al [2-4] and Dunbar et al [5] with the bis-bidentate ligands 

1 – 4 resulted in complexes where the Ag(I) did not form [2x2] grid complexes but instead 

formed (a) a side-by-side arrangement of the ligands with Ag(I) ions in pseudo-square planar 

geometries (dppz or 1, 2 & 4 with CF3SO3 - ),[2, 3] (b) a molecular propellor with Ag(I) ions in 

trigonal prismatic geometries (4 with AsF6 - )[5] and (c) a more complex pentanuclear assembly in 

which four silver(I) ions are three coordinated and one has a distorted tetrahedral geometry 

(3).[4] 

N 

R 

N N N 

1 R = H (dppz) 

2 R = Ph 

3 R = SiMe 3 

N 

N 

N 

N N 

4 

N 

R 

N 

N N N R 

Recently, we reported some first row transition metal complexes with 5 (R=PhOMe) 6 where on 

complexation with a metal ion which prefers a tetrahedral geometry [Cu(I)] resulted in a [2x2] 

architecture, whereas with a metal ion that prefers an octahedral geometry generally a side-byside 

arrangement resulted (ligand 5 placed equatorially and solvent molecules in axial sites). 

The surprisingly diverse range of supramolecular architectures observed by Constable et al and 

Dunbar et al inspired us to investigate the Ag(I) co-ordination chemistry of our existing bisbidentate 

ligand. In addition, a family of ligands of general type 5, with varying phenyl ring 

substituents, can be readily prepared and was expected to allow an examination of the effect of 

weak, non-covalent interactions on the molecular architecture of the resulting complexes.[7] The 

results of this study will be presented and discussed. 

[1] M. Ruben, J. Rojo, F. J. Romero-Salguero, L. H. Uppadine, and J.-M. Lehn, Angew. Chem. Int. 

Ed., 2004, 43, 3644. 

[2] E. C. Constable, C. E. Housecroft, B. M. Kariuki, N. Kelly and C. B. Smith, C.R. Chimie, 2002, 5, 

425. 

[3] E. C. Constable, C. E. Housecroft, B. M. Kariuki, M. Neuburger and C. B. Smith, Aust. J. Chem., 

2003, 56, 653. 

[4] E. C. Constable, C. E. Housecroft, M. Neuburger, S. Reymann and S. Schaffner, Chem. 

Commun., 2004, 1056. 

[5] B. L. Schottel, J. Bacsa and K. R. Dunbar, Chem. Commun., 2005, 46. 

[6] Y. Lan, D. K. Kennepohl, B. Moubaraki, K. S. Murray, J. D. Cashion, G. B. Jameson, and S. 

Brooker, Chem. Eur. J., 2003, 9, 3772. 

[7] J. R. Price, Y. Lan, G. B. Jameson, and S. Brooker, Chem. Commun., 2006, 1491. 

5 

Supra-Biomolecular Tandem Assays 

Andreas Hennig, Huseyin Bakirci, and Werner M. Nau 

School of Engineering and Science, Jacobs University Bremen, Campus Ring 1, 28759 

Bremen; e-mail: w.nau@iu-bremen.de 

OP 4 

Building on the work by others in the areas of supramolecular indicator displacement 

assemblies [1-4] and enzyme assays [5-7], as well as our own recent contributions to these 

research areas [8-14], we have devised a new approach to enzyme assays based on the simple 

addition of water-soluble macrocycles and fluorescent dyes [15], which will be described for the 

first time in a symposium. 

[1] Ueno, A.; Kuwabara, T.; Nakamura, A.; Toda, F., Nature 1992, 356, 136-137. 

[2] Koh, K. N.; Araki, K.; Ikeda, A.; Otsuka, H.; Shinkai, S., J. Am. Chem. Soc. 1996, 118, 755- 

758. 

[3] Sindelar, V.; Cejas, M. A.; Raymo, F. M.; Chen, W.; Parker, S. E.; Kaifer, A. E., Chem. Eur. 

J. 2005, 11, 7054-7059. 

[4] Nguyen, B. T.; Anslyn, E. V., Coord. Chem. Rev. 2006, 250, 3118-3127. 

[5] Tawfik, D. S.; Green, B. S.; Chap, R.; Sela, M.; Eshhar, Z., Proc. Natl. Acad. Sci. USA 1993, 

90, 373-377. 

[6] Geymayer, P.; Bahr, N.; Reymond, J.-L., Chem. Eur. J. 1999, 5, 1006-1012. 

[7] Das, G.; Talukdar, P.; Matile, S., Science 2002, 298, 1600-1602. 

[8] Bakirci, H.; Koner, A. L.; Nau, W. M., Chem. Comm. 2005, 5411-5413. 

[9] Bakirci, H.; Nau, W. M., Adv. Funct. Mat. 2006, 16, 237-242. 

[10] Bakirci, H.; Koner, A. L.; Dickman, M. H.; Kortz, U.; Nau, W. M., Angew. Chem. Int. Ed. 

2006, 45, 7400-7404. 

[11] Koner, A. L.; Nau, W. M., Supramol. Chem. 2007, 19, 53-65. 

[12] Hennig, A.; Roth, D.; Enderle, T.; Nau, W. M., ChemBioChem 2006, 7, 733-737. 

[13] Hennig, A.; Florea, M.; Roth, D.; Enderle, T.; Nau, W. M., Anal. Biochem. 2007, 360, 255- 

265. 

[14] Hennig, A.; Ghale, G.; Nau, W. M., Chem. Comm. 2007, doi:10.1039/B618703J. 

[15] Patent pending.

Self-organized fluorescent nanosensors for ratiometric Pb 2+ OP 5 

detection 

Maria Arduini, a Fabrizio Mancin, a Paolo Tecilla, b and Umberto Tonellato a 

a Dipartimento di Scienze Chimiche and CNR-ITM, Università di Padova, via Marzolo 1, 35131 

Padova, Italy 

b Dipartimento di Scienze Chimiche, Università di Trieste, via Giorgieri 1, 34127 Trieste, Italy 

Self-organization of dyes and receptors on proper templates is a new and attractive strategy for 

the easy preparation, modification and optimization of fluorescence chemosensors.[1] In fact, 

the synthetic work, which is often the most demanding task in the development of new 

chemosensors, is reduced to the minimum, since the spatial proximity, the communication 

between the sensor components and, in some cases, even the formation of the substrate 

binding sites are granted by the grafting of simple components to a template. Up to date, 

different templates have been proposed to direct the assembly of the sensors components, 

ranging from surfactant aggregates to quartz surfaces and nanoparticles. Among these, silica 

nanoparticles are particularly attractive for their peculiar features: they are easy to prepare, 

transparent to light and biocompatible. 

Moreover, they can be doped or 

chemically modified with organic 

molecules and engineered into 

compartments performing different 

functions.[2] 

In this communication, we report a silica 

nanoparticles-based chemosensor 

capable to report the presence of Pb 2+ 

ions. In our system, several sensor 

features - working scheme, binding sites, 

sensitivity and ratiometric behaviour - 

take full advantage from the selforganization 

and structural arrangement 

of the particles, giving a clear example of 

the flexibility and broad applicability of 

the template-based self-organized 

approach. 

60-nm diameter silica nanoparticles 

doped with fluorescent dyes and 

N 

O 

H 

S N 

O 

functionalized on the surface with thiol groups (np1) were prepared and studued as fluorescent 

chemosensors for Pb 2+ ions. The particles can detect micromolar metal ion concentrations with 

a good selectivity. Analyte binding sites are provided by the simple grafting of the thiol groups 

on the nanoparticle surface. Once bound to the particles surface, the Pb 2+ ions quench the 

emission of the reporting dyes embedded in the particles. 

Sensor performances can be improved by taking advantage from the easiness of production of 

multishell silica particles. On one hand, signaling units can be concentrated in the external 

shells of the particles allowing a closer interaction with the surface bound analyte (np2). On the 

other, a second dye can be buried in the particles core, far enough from the surface to be 

unaffected by the surface bound Pb 2+ ions, thus producing a reference signal (np3). In this way, 

a ratiometric system is easily prepared by simple self-organization of the particle components. 

[1] F. Mancin, E. Rampazzo, P. Tecilla and U. Tonellato, Chem. Eur. J., 2006, 12, 1844-1854. 

[2] S. Santra, J. Xu, K. Wang, and W. Tan, J. Nanosci. Nanotech., 2004, 4, 590-599. 

O 

1 Si(OEt) 2 

3 

dye 1 "pure" silica 

MPS coating 

O 

NH 

Si(OEt) 3 

np1 np2 np3 

SH 

Si(OEt) 3 

MPS 

dye 1 

dye 2 

Figure 1. Triethoxysilane derivatives used for 

particles preparation and schematic 

representation of the nanoparticles structures 

Nucleotides as Building Blocks for Lanthanide Based Nanoparticles 

Ryuhei Nishiyabu, Nozomi Hashimoto and Nobuo Kimizuka* 

Department of Chemistry and Biochemistry, Graduate School of Engineering, 

Kyushu University, Fukuoka 819-0395, Japan. E-mail: ryuheitcm@mbox.nc.kyushu-u.ac.jp 

Nanomaterials composed of lanthanide ions have been receiving great attention due to their 

unique optical and magnetic properties. Here, we demonstrate self-assembly of nucleotides and 

lanthanide ions gives nanoparticles (NPs) in water, which show sensitized luminescence and 

MRI-active properties. 

We recently reported that molecular pairing of 5'-ATP and cationic cyanine dyes gave 

excitonic supramolecular nanofibers.[1] This finding prompted us to utilize nucleotides as 

building blocks for coordination polymers, especially with lanthanide ions which are expected to 

interact strongly with phosphates and nucleobase moieties. Nucleotide/lanthanide complexes 

were prepared by mixing aqueous solutions of nucleotides and lanthanide ions. Consequently, 

nanoparticles are formed from a wide variety of nucleotides such as second messengers and 

coenzymes. The size of particles is controlled dependent on the molecular structure of 

nucleotides (Figure B and C). Interestingly, nucleotide/lanthanide NPs which formed from Tb(III) 

ions and guanosine phosphates showed intense green emission in water, due to efficient 

energy transfer from guanine moiety to Tb(III) ion (Figure D). The Gd(III) based NPs displayed 

MRI active properties, as a result of shortening T1 of water protons included in NPs (Figure E). 

Furthermore, the nucleotide/lanthanide NPs formation can incorporate various functional 

molecules such as fluorescent dyes, metal nanocrystals and biomacromolecules. Confocal laser 

scanning microscopy (CLSM) showed uniformly distribution of doped fluorescent dyes in NPs 

(Figure F). Incorporation of gold nanoparticles (AuNPs) into nucleotide/lanthanide NPs was also 

confirmed by transmission electron microscopy (Figure G). These adaptive properties promise a 

wide range of applications which have not been accessible from conventional inorganic NPs. 

Lanthanide Ion 

Nucleotide 

Nanoparticle 

Formation 

Self-Assembly 

OP 6 

Figure. Schematic representation of nucleotide/lanthanide based nanoparticle formation (A), 

SEM images of 5’-GMP/Gd (B) and cAMP/Gd NPs (C), Aqueous dispersions of i) 5’-dAMP/Tb, 

ii) 5’-dTMP/Tb, iii) 5’-dGMP/Tb, and iv) 5’-dCMP/Tb NPs under the UV light (254 nm) (D), MRI 

images of 5’-AMP/Gd NPs, 5’-GMP/Gd NPs, and Magnevist (E), CLSM micrograph of carboxy 

fluorescein doped NADH/La NPs (F), and TEM image of AuNPs doped 5’-GMP/Gd NPs (G). 

[1] M. Morikawa, M. Yoshihara, T. Endo and N. Kimizuka, J. Am. Chem. Soc., 2005, 127, 1358.

Catalyst discovery using dynamic combinatorial chemistry 

Leonard J. Prins, Giulio Gasparini, Paolo Scrimin 

Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy 

Dynamic combinatorial chemistry (DCC) relies on the generation of dynamic libraries of 

molecular structures held together either by non-covalent interactions or reversible covalent 

bonds.[1] Consequently, the libraries are at thermodynamic equilibrium and the addition of a 

target to the library results in a spontaneous shift in the library composition favouring the library 

member with the highest affinity for the target. In the last years, dynamic combinatorial 

chemistry has been successfully applied for the identification of receptors for metal ions, small 

organic molecules and biomolecules. Catalyst discovery using DCC remains a largely 

unexplored area; the few catalysts which have been isolated, generally gave very modest rate 

accelerations.[2] Here, we show that an approach called ‘tethering’ is a powerful strategy for 

catalyst discovery using DCC. 

The tethering strategy is based on the covalent coupling of the target to a molecular scaffold. 

Library components that interact with the target are captured via the ‘pseudo’-intramolecular 

formation of a reversible covalent bond. This approach has been very successfully applied for 

the discovery of substrates for a series of proteins.[3] We have applied this approach for the 

selection of molecules able to bind to a phosphonate (as a model of the transition state of a 

carboxylate ester hydrolysis). An initial analysis of a simple model system has revealed that the 

success of applying the tethering strategy strongly depends on the experimental conditions.[4] 

The boundary conditions and the ‘best’ method to perform the library screening will be 

discussed. Next, the correlation between the observed amplification in the dynamic library and 

the catalytic activity will be presented. 

N 

N 

H 

O O 

P 

O 

TBA 

1A 

N 

N 

H 

O O 

P 

O 

TBA 

1B 

O 

O 

N 

Cl 

+ 

+ 

H 2N 

N 

H 

O 

H 2N 

N 

H 

B 

O 

A 

N 

Cl 

amplification 

80 

70 

60 

amplification 

50 

0 10 20 30 40 50 

concentration 

NO amplification 

OP 7 

[1] P.T. Corbett, J. Leclaire, L. Vial, K.R. West, J.-L. Wietor, J.K.M. Sanders, S. Otto, Chem. 

Rev., 2006, 106, 3652-3711. 

[2] B. Brisig, J.K.M. Sanders, S. Otto, Angew.Chem.Int.Ed. 2003, 42, 1270-1273. 

[3] D.A. Erlanson, A.C. Braisted, D.R. Raphael, M. Randal, R.M. Stroud, E.M. Gordon, J.A. 

Wells, Proc. Natl. Acad. Sc. (USA) 2000, 97, 9367-9372. 

[4] G. Gasparini, M. Martin, L.J. Prins, P. Scrimin, Chem. Comm. 2007, DOI: 10.1039/ 

b617450g. 

Structure-Activity Studies on Oligoester Ion Channels 

Thomas M. Fyles, Horace Luong 

Department of Chemistry, University of Victoria, Victoria, BC V8W 3V6, Canada 

One of the many motivations for synthesizing ion channels is that it is difficult to study 

structure-function relationships in the large and complex proteins that make up natural ion 

channels. In a synthetic channel that can mimic the functions of a natural ion channel such 

structure-function studies can (in principle) be simplified. Structure-function optimization of ionic 

conductance also holds the potential use for applications in nanodevices such as sensors, 

separations and signal propagation. 1 

We have recently reported that active oligoester ion channels can be synthesized by a 

relatively concise and efficient solid-phase method. 2 This method provides simple access to an 

array of oligoester compounds from a set of -hydroxyacids (general structure below). 

Recently we have incorporated -aminoacids to produce oligoester-amide channels. As with 

other reported channel-forming systems, we can produce series of compounds that vary in total 

length and/or lipophilicity. Our method also allows us to prepare constitutional isomers in which 

length and lipophilicity are held constant, but the distribution of sites for interaction with lipids, 

ions, and water can be varied systematically. Some examples are shown below: 

An = 

HO2C A1 X1 A2 X2 A3 X3 A4 Y 

O 

OR 

R 

The transport activities of the synthesized compounds incorporated into vesicles were 

monitored using a pH-triggered fluorescent dye assay. Our results clarify the roles of the 

various lipophilic groups, the overall length of the main strand, and the number and locations of 

the central ester carbonyls. Overall amphiphilic characteristics are also significant as indicated 

by the substantial activity differences between the constitutional isomers 1 and 2. 

[1] Fyles, T.M. Chem. Soc. Rev. 2007, 36, 335-347. 

[2] Fyles, T.M.; Hu, C.W.; Luong, H. J. Org. Chem. 2006, 71, 8545-8551. 

CH 2 

n 

R 

X n = 

O 

N 

H 

C 12H 25O 

O 

O Y = 

HO2C CH2 7 O 

O 

CH2 11 O 

O 

O 

O 

CH2 O 

7 

OH 

OC12H25 O 

HO2C O 

CH2 7 O 

O 

CH2 11 O 

1 

O 

CH2 7 

OH 

2 

O 

OH 

O 

H 

OP 8

Efficient tools for the synthesis of cyclen and cyclam derivatives 

Franck Denat, Frédéric Boschetti, Fanny Chaux, Yoann Rousselin, Roger Guilard 

Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB - UMR CNRS 5260) 

9, avenue Alain Savary, BP 47870, 21078 DIJON - FRANCE 

OP 9 

Cyclen, cyclam and related macrocycles have known growing interest owing to their versatile 

coordination properties which allow their use in many fields, including purification of liquids, 

detection of metal traces, catalysis and of course medicine. Indeed, biscyclam AMD3100 is 

known for its anti HIV activity and has been used recently for the mobilization of stem cells. 

Gadolinium complexes of cyclen derivatives are widely used as contrast agents for MRI. 

Bifunctional chelating agents based on tetraazacycloalkanes are of particular interest since they 

are used for labelling biomolecules with radiometals for both diagnosis and therapy, or they can 

be grafted onto a solid support for removing metal from various media. 

There is obviously a strong need for finely tailored ligands with very specific properties and the 

search for powerful synthetic routes towards cyclen, cyclam and their N and/or C-functionalized 

derivatives became a real economical challenge. We wish to present our contribution to the 

synthesis of unsubstituted macrocycles [1] and their functionalization. [2] For instance, the use of 

bisaminal compounds obtained by condensation of linear tetraamines with -dicarbonylated 

derivatives allows the highly selective preparation of N-functionalized [3] and C-functionalized [4] 

macrocycles. This approach presents numerous advantages: the cyclization reactions take 

place in good yield without using high dilution conditions and there is no need for atom 

consuming protection/deprotection sequences neither tedious chromatographic workup. Various 

1,7-difunctionalized cyclens and new cryptands or macrotricycles have also been prepared 

using cyclen for reductive amination of aldehydes and dialdehydes respectively. [5] 

[1] F. Boschetti, F. Chaux, F. Denat, R. Guilard and H. Ledon, WO 2005/000823. 

[2] F. Denat, S. Brandès and R. Guilard, Synlett, 2000, 561-574 and references therein. 

[3] F. Boschetti, F. Denat, E. Espinosa, A. Tabard, Y. Dory and R. Guilard, J. Org. Chem., 2005, 

7042-7053. 

[4] F. Boschetti, F. Denat, E. Espinosa, J.-M. Lagrange and R. Guilard, Chem. Commun., 2004, 

588-589. 

[5] F. Chaux, F. Denat, E. Espinosa and R. Guilard, Chem. Commun., 2006, 5054-5056. 

OP 10 

New discrete and framework metallo-structure: rings chain, helicates and 

tetrahedra. 

J. K. Clegg, a L. F. Lindoy, a D. Schilter a , C. R. K. Glasson, b and G. V. Meehan b 

a) School of Chemistry, The University of Sydney, NSW 2006, Australia b) School of 

Pharmacy & Molecular Sciences, James Cook University, Townsville Qld 4811, Australia 

Metal directed procedures have been employed to produce a range of metallo-supramolecular 

species that incorporate metal complexes as structural elements. Dinuclear metal complex 

'platforms' incorporating aryl-linked bis(-diketonato) ligands have been synthesised. These 

species incorporate coordinatively unsaturated metal centres. The manner by which this latter 

property has been exploited to construct both new discrete and framework structures will be 

discussed. 

A range of metallosupramolecular entities have also been investigated. These include new 

examples of metallo-rings, chains, helicates and tetrahedra. The design principles involved in the 

construction of each structural type will be discussed in terms of the choice of metal ion and 

organic component(s) employed. For example, in one such study involving self-assembly 

techniques, the interaction of 5’’’-dimethylquaterpyridine (L) with iron(II) chloride was 

investigated. 1 This resulted in the assembly of a tetrahedral structure of type [Fe4L6] 8+ (see 

above) that encapsulates an anionic [FeCl4] unit in its central cavity; the inclusion behaviour of 

this host with a range of other anionic guests will be presented.

Cucurbit[n]uril Molecular Containers 

Simin Liu, Wei-Hao Huang, Pritam Mukhopadhyay, Lyle Isaacs* 

Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland, 

20742, USA. 

OP 11 

Interest in the cucurbit[n]uril family[1] of molecular containers has accelerated dramatically in 

recent years due to the availability of a homologous series of hosts (CB[n], n = 5, 6, 7, 8). In 

this contribution we discuss our recent progress in the synthesis of new CB[n] compounds and 

the elucidation of some of the unique aspects of their recognition behavior. We highlight 

several key results from these projects including: 

• CB[7] forms remarkably tight host guest complexes with adamantane ammonium ions with 

binding constants exceeding 10 12 M -1 in water.[2] 

• The CB[6]•cyclohexanediammonium ion complex has a dissociation rate constant of 10-9 s-1 

which is 100-fold slower than Avidin-Biotin.[3] 

• Cucurbit[10]uril can be isolated as a stable compound with a cavity volume of 870 Å 3 . CB[10] 

displays much interesting host-guest chemistry including act as a host for a cationic calixarene 

1 and controlling the folding of triazene-arylene oligomers.[4] 

• Inverted CB[n] (n = 6, 7) form as kinetic intermediates during the synthesis of CB[n].[5] 

• Nor-seco-CB[10] with its two intimately connected cavities forms ternary complexes with 

allosteric control based on guest size.[6] 

[1] J. Lagona, P. Mukhopadhyay, S. Chakrabarti, L. Isaacs, Angew. Chem. Int. Ed. 2005, 44, 

4844-4870. 

[2] S. Liu, C. Ruspic, P. Mukhopadhyay, S. Chakrabarti, P. Y. Zavalij, J. Am. Chem. Soc. 2005, 

127, 15959-15967. 

[3] P. Mukhopadhyay, P. Y. Zavalij, L. Isaacs, J. Am. Chem. Soc. 2006, 128, 14093-14102. 

[4] S. Liu, P. Y. Zavalij, L. Isaacs, J. Am. Chem. Soc. 2005, 127, 16798-16799. 

[5] L. Isaacs, S.-K. Park, S. Liu, Y.-H. Ko, N. Selvapalam, Y. Kim, H. Kim, P. Y. Zavalij, G.-H. 

Kim, H.-S. Lee, K. Kim, J. Am. Chem. Soc. 2005, 127, 18000-18001. 

[6] W.-H. Huang, S. Liu, P. Y. Zavalij, J. Am. Chem. Soc. 2006, 128, 14744-14745. 

Biphenylthioureas as organocatalysts for electrochemical reductions 

Ana M. Costero, Gemma M. Rodríguez-Muñiz, Salvador Gil, Pablo Gaviña 

Departamento de Química Orgánica. Universidad de Valencia. Dr. Moliner, 50. 46100- 

Burjassot. Valencia. Spain 

Over the past years an increasing interest toward the so called organocatalysts has arised [1]. 

Organocatalysts are organic molecules that can be used as efficient catalysts for different type 

of reactions. These catalysts do not contain any metals and for this reason they are very 

convenient from the environmental point of view. Among the different interactions that can be 

established between the catalyst and the substrate, hydrogen-bonding has demonstrated to be 

very useful [2]. Thus, the potential of N,N-disubstituted (thio)ureas to serve as active metal-free 

organocatalysts for a wide range of synthetically useful reactions susceptible to the influence of 

general acid catalysis has been recognized [3]. Although, urea and thiourea derivatives have 

been successfully used for a variety of 

diatereo- and enantioseltive reactions, to the 

A1 

A1 

best of our knowledge no examples of 

catalysis in electrochemical reactions of 

C 1 

C1 

C3 

O 2N N 

organic compounds have been described 

being the described examples related to 

cation oxidation have been reported [4]. 

We now report the catalytic activity exhibed by the biphenyl thiourea derivatives 1-3 [5] (Chart 1) 

in the electroreduction of some carboxylates. 

The effect on the CV of addition of p-methoxybenzoate anions to DMSO solutions of the ligands 

is illustrated in Figures 2 for the case of 1. Here, an additional cathodic peak (C3) near to -600 

mV precedes the peaks C1 corresponding to the reduction of the nitrobiphenyl moiety of the 

ligand previously described. On increasing the concentration of the anion, the peaks C3 

monotonically increase as the anion concentration increases, whereas the peak C1 remains 

essentially unchanged. The voltammetry of the ligand plus anion could be interpreted on 

assuming that the anion coordinates to the ligand via hydrogen bond formation between the 

amide groups of the ligand and the carboxylate group of the anion. However the increment in 

the current as the concentration of anion increases only can be rationalized on considering the 

electrochemistry of the anion that experiment an electroreduction giving rise to 4.4’dimethoxybenzyl. 

[1] For reviews on organocatalysts, see; (a) P. I. Dalko and L. Moisan, Angew. Chem., Int. Ed., 

2001, 40, 3726–3748; (b) P. I. Dalko and L. Moisan, Angew. Chem., Int. Ed., 2004, 43, 5138– 

5175; (c) Acc. Chem. Res. 2004, 37, 487–631; (d) 

[2] P. R. Schreiner, Chem. Soc. Rev. 2003, 32, 289-296. 

[3] (a) T. R. Kelly and M. K. Kim, J. Am. Chem. Soc., 1994, 116, 7072–7080; (b) F. P. 

Schmidtchen and M. Berger, Chem. Rev., 1997, 97, 1609–1646; (c) B. R. Linton, M. S. 

Goodman and A. D. Hamilton, Chem.–Eur. J., 2000, 6, 2449–2455. S. J. Connon, Chem.- Eur. 

J. 2006, 12, 5419-5427. 

[4] A. Nosal-Wiercinska, G. Dalmata, Electroanalysis 2002, 14, 1275-1280. 

[5] A.M. Costero, P. Gaviña, G. Rodríguez-Muñiz and S. Gil Tetrahedron 2006, 62, 8571-8577. 

S 

H 

Chart 1 

N 

R 

H 

1 R=C 6H 5 

2 R=Et 

3 R= 4-NO 2-C 6H 4 

OP 12

OP 13 

Anion sensing in consumer products: from multi-electrolytes to toothpaste 

Pavel Anzenbacher, Jr. and Manuel A. Palacios 

Center for Photochemical Sciences and Department of Chemistry, Bowling Green State 

University, Bowling Green, Ohio 43403, USA. E-mail: pavel@bgsu.edu 

The important role anions play in biological and industrial processes demands reliable sensing 

of anions in multi-analyte environments. The performance of sensor arrays utilizing pattern 

recognition operating in multi-analyte environments may be dramatically improved by utilizing a 

printable polymer host doped with sensors selective to key components of the mixture. This 

way, one can perform fast screening of receptor and sensor moieties, for example by InkJet 

printing of the sensor-polymer mixtures (Sens-Ink) on various surfaces that include glass and 

plastic. The use of a polymer interface layer between the solid support and bulk aqueous 

analyte makes it possible to utilize anion sensors that are otherwise insoluble in water. This 

approach is shown on examples of optical sensors utilizing an analyte-specific change in color 

or luminescence in the presence of an analyte. The rapid pre-screening allows for assembling 

small sensor arrays that are biased toward key components of a particular multianalyte. To 

demonstrate this aspect, we will show examples of arrays utilizing less than ten elements 

capable of sensing inorganic anions, biological phosphates such as AMP and ATP, 

distinguishing between various non-steroidal anti-inflammatory drugs, or identifying different 

toothpaste brands based on their anion content. 

[1] M. A. Palacios, R. Nishiyabu, M. Marquez and P. Anzenbacher, Jr.: Supramolecular 

Chemistry Approach to the Design of High-Resolution Sensor Array for Multi-Anion Detection in 

Water. J. Am. Chem. Soc. 2007, 129, in press (ja0704784). 

A molecular gate based on a porphyrin and a silver lock 

Aurélie Guenet a , Ernest Graf a , Mir Wais Hosseini a , Nathalie Kyritsakas a , Lionel Allouche b 

a LCCO UMR CNRS 7140, Université Louis Pasteur, Institut Le Bel, 4 rue Blaise Pascal 67000 

Strasbourg, France 

b Service Commun de RMN FR CNRS 2351 Université Louis Pasteur, Institut de Chimie, 1 rue 

Blaise Pascal 67000 Strasbourg, France 

Design of molecular switches, rotors and motors is a challenging task that has attracted 

considerable attention over the past fifteen years. [1] Our approach is based on a molecular 

gate which consists of a hinge (purple) and a handle (grey) each bearing a single coordinating 

site (scheme 1). 

Open Closed 

Scheme 1: Schematic representation of the molecular gate 

The hinge is composed of a tin(IV) porphyrin bearing a 4-pyridyl group at one of the four meso 

positions. The handle is formed from a central pyridine moiety bearing two terminal phenoxo 

ligands spaced by two oligoethylene glycol units permitting the connection of the handle to the 

hinge through coordination to the Sn atom (scheme 2). 

N 

O 

N 

N Sn N 

N 

O 

O O 

O O 

O 

O 

O 

N Sn N 

AgOTf 

+ - NEt4 Br 

N 

N N 

O 

O 

O 

O 

O 

O O 

Scheme 2 

In solution, the handle rotates freely around the hinge. The gate is in its open position. However, 

in the presence of a silver cation, both pyridine units of the hinge and the handle simultaneously 

bind to the cation leading to the closing of the gate. Thus, the system behaves as a molecular 

gate controlled by the locking action of Ag(I). The functioning of the gate is based on 

complexation / decomplexation processes induced by external chemical stimuli (addition of 

silver cation and bromide anion). These processes as well as their reversibility were studied by 

multidimensional 1 H NMR experiments. 

The molecular gate presented here is the first step towards the synthesis of a rotor based on a 

hinge equipped with several coordinating sites and a handle bearing a single coordinating unit. 

The introduction of two or more coordination sites (regarded as stations) on the hinge should 

allow the handle to travel from station to station. 

[1] V. Balzani, A. Credi, F.M. Raymo, J.F. Stoddart, Angew. Chem. Int. Ed., 2000, 39, 3348- 

3391, Special Issue, Acc. Chem. Res., 2001, 34, 409-522, W.R. Browne, B.L. Feringa, Nature 

nanotechnology, 2006, 1, 25-35, E.R. Kay, D. A. Leigh, F. Zerbetto, Angew. Chem. Int. Ed., 

2007, 46, 72-191. 

O 

N 

O 

Ag 

O 

O 

N 

OP 14

OP 15 

From non-mesomorphic nature to liquid crystallinity via halogen bonding 

Rossana Intenza, a Pierangelo Metrangolo, a Franck Meyer, a Tullio Pilati, b Giuseppe Resnati, a 

Giancarlo Terraneo a 

a 

NFM Lab-DCMIC “G. Natta”, via Mancinelli, 7 I-20131 Milan, Politecnico di Milano, Italy. 

b 

CNR-Institute of Molecular Science and Technology, University of Milan, via Golgi 19, 20133 

Milan, Italy. 

Halogen bonding, namely any attractive interactions involving halogens as electrophilic species 

[1], can be considered as a first choice intermolecular interaction both reliable and effective to 

understand and rationally design self-assembly processes in supramolecular chemistry, crystal 

engineering, and materials science [2]. A rather new intermolecular interaction being therefore 

accessible, new aggregation processes can be realised with the novelty coming from either the 

molecular identity of single modules that are assembled or from the way the modules are 

arranged in the supramolecular architecture. 

In particular, in the last decade new families of liquid-crystalline materials have been developed 

by the identification of non-covalent interactions such as hydrogen bonding, quadrupolar and 

charge-transfer interactions that can lead to new mesomorphic supramolecular species by selfassembly 

[3]. 

Recently, Bruce [4] and Metrangolo [5] reported that also halogen bonding is effective in 

inducing liquid crystal phase behaviour by combination of nonmesomorphic alkoxystilbazoles 

with either iodopentafluorobenzene or diiodoperfluoroalkanes. 

Here we report a new class of liquid crystal materials formed thanks to the halogen bonding 

occurring between alkoxystilbazoles and 4-iodo-tetrafluoro alkoxystilbenes (Figure 1). A “square 

matrix” n x m made of 25 halogen-bonded supramolecular complexes was obtained and 

characterized by NMR, X-ray diffraction, hot stage polarising optical microscopy and differential 

scanning calorimetry (DSC). Despite both the starting materials are not mesomorphic in nature, 

all the 25 supramolecular adducts develop liquid crystal properties. 

H 2n+1C nO 

n = 4, 6, 8, 10, 12 

N 

I 

Figure 1 

F 

F 

F F 

OC mH 2m+1 

m = 4, 6, 8, 10, 12 

Preliminary results suggest that the mesomorphism of the halogen-bonded 

alkoxystibazole/iodotetrafluoroalkoxystilbene complexes is that of a simple, dipolar mesogen, 

showing a nematic phase at short chain and a smectic A phase with longer chains. 

The generality of this approach will be demonstrated by some other examples of 

supramolecular ionic liquid crystals made by halogen bonding-driven self-assembly. 

[1]. P. Metrangolo, T. Pilati and G. Resnati, CrystEngComm, 2006, 8, 946 (Front Cover). 

[2]. P. Metrangolo, H. Neukirch, T. Pilati and G. Resnati, Acc. Chem. Res., 2005, 38, 386. 

[3]. T. Kato, in Handbook of Liquid Crystals, ed. D. Demus, G.WGray, J. Goodby, H.-W. Spiess 

and V. Vill, Wiley-VCH, Weinheim, 1998. 

[4]. H. L. Nguyen, P. N. Horton, M. B. Hursthouse, A. C. Legon and D. W. Bruce, J. Am. Chem. 

Soc., 2004, 126, 16. 

[5]. P. Metrangolo, C. Prasang, G. Resnati, R. Liantonio, A. C. Whitwood and D. W. Bruce 

Chem. Commun., 2006, 3290 (Hot Paper and Front Cover); Chemical Science, 2006, 7. 

Buttressing Effects in Pseudomacrocyclic Metal Extractants 

Peter A. Tasker, Ross S. Forgan, David K. Henderson, Fiona McAllister, Simon Parsons and 

Peter A. Wood 

School of Chemistry, The University of Edinburgh, Edinburgh, EH9 3JJ, UK 

E-mail: p.a.tasker@ed.ac.uk 

Nearly a third of the world’s copper is now recovered by solvent extraction using salicylaldoxime 

derivatives.[1] The strength and selectivity of Cu extraction depends on formation of 

pseudomacrocyclic structures. [2] 

R 

R' 

X 

N 

O 

O H 

H 

H 

H 

O 

O 

N 

X 

R' 

R 

+Cu 2+ 

R 

R' 

N 

O 

O H 

We have found that the nature of the 3-substituent (X above) has a major influence on 

extractant strength, with NO2 > Cl > MeO > H Me > t Bu for the extractants with R = t Bu or t Oct. 

A favourable buttressing from H-bond acceptor groups such as MeO which favour formation of 

bifurcated H-bonds from the oximic OH and an unfavourable destabilising of interligand Hbonding 

by large groups such as t Bu account for this order. Solid state structures confirm the 

importance of this buttressing effect in stabilizing the pseudomacrocycle structure; cavity sizes 

in the dimers (R = H) decrease in the order X = MeO < Cl < H < Me < t Bu. The integrity of these 

14-membered pseudomacrocycles is maintained at pressure up to 6 MPa and the compression 

of cavity size by up to 6 % should lead to changes in selectivity of metal uptake. 

The effect of pressure on the cavity sizes in the metal-free ligand dimers 

[1] G. A. Kordosky, ISEC, 2002, p853 

[2] P. A. Tasker et al, Comprehensive Coordination Chemistry II, 2004, 9, p759 

X 

H 

Cu 

O 

O 

N 

X 

R' 

OP 16 

R 

+2H +

OP 17 

Biochemical and medicinal applications of the polytopic super- and 

supramolecular systems based on the cage transition metal complexes 

Yan Z. Voloshin, Oleg A. Varzatskii, b Yurii N.Bubnov 

 

A. N. Nesmeyanov Institute of Organoelement Compounds, RAS, 119991 Moscow, Russia 

E-mail: voloshin@ineos.ac.ru 

b 

V.I. Vernadskil Institute of General and Inorganic Chemistry, NASU, 03680 Kiev, Ukraine 

The following main trends and the perspectives of biochemical and medicinal applications of the 

polytopic super- and supramolecular systems based on the transition metal clathrochelates as a 

“molecular scaffold” will be discussed: 

− encapsulation of the radioactive metal ions for diagnostics and therapy 

− prolonged pharmaceuticals and pharmaceuticals for boron-neutron capture therapy (1) 

− antioxidants (2) 

− 

− membrane transport of the radioactive and biological metal ions (3) 

− interaction of the cage complexes with nucleic acids and their self-assembling reactions in 

immunology and molecular biology (recognition of antibodies, antigens and DNA sites) 

− design of HIV inhibitors for the drug therapy 

This work was supported by RFBR ( 05-03-33184, 06-03-32626 and 06-03-90903). 

[1] Y.Z. Voloshin, N. A. Kostromina and R. Krämer, Clathrochelates: synthesis, structure and 

properties, Elsevier, Amsterdam, 2002. 

[2] Y.Z. Voloshin, O.A. Varzatskii et al., Inorg. Chem., 2005, 44, 822-824. 

[3] Y.Z. Voloshin, O.A. Varzatskii et al. , Inorg.Chim.Acta, 2007, 360, 1543-. 

[4] Y.Z. Voloshin, O.A. Varzatskii et al., Russ.Chem.Bull., Int.Ed., 2006, 55, 22-. 

[5] Y.Z. Voloshin, O.A. Varzatskii et al. , Angew.Chem.Int. Ed., 2005, 44, 3400 

[6] A.Mokhir, R.Krämer, Y.Z.Voloshin, O.A.Varzatskii, Bioorg.Med.Chem.Lett., 2004, 14, 2927- 

2929. 

Catalysis in Chiral Supramolecular Flasks 

Kenneth N. Raymond, Michael D. Pluth, Robert G. Bergman 

Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA 

OP 18 

We have described the synthesis of supramolecular clusters based on labile metal-ligand 

interactions.[1,2] The cluster shown is highly negatively charged and water-soluble.[1] However 

it has a hydrophobic interior that strongly and selectively encapsulates hydrophobic 

monocationic guests. Because of the trigonal propeller chirality at the metal vertices and 

mechanical linkage between the metal vertices, these clusters are homochiral and resolvable. 

A supramolecular metal-ligand assembly catalyzes the [3,3]-sigmatropic rearrangement 

of enammonium guests in 

aqueous solution by nearly 

1000 fold. The space 

restrictive host cavity forces 

the substrates to bind in a 

reactive chair-like 

conformation and thus 

accelerates the rates of 

rearrangement. Release and 

hydrolysis of the rearranged 

product enable catalytic 

turnover.[3] The extrusion of a 

side chain of a guest through 

the wall of the host shows the feasibility of polymer chain extrusion and supports the guest 

exchange mechanism that has been proposed.[4] 

The assembly K12Ga4L6 is able to catalyze acid-catalyzed hydrolysis reactions in basic 

solution.[5] A variety of substrate classes have been investigated including orthoformates, 

acetals, and ketals. The hydrolysis of these substrates under basic conditions is greatly 

accelerated by the K12Ga4L6 assembly. Control experiments utilizing tetraethylammonium as a 

strongly binding guest to block the interior of the assembly show competitive inhibition of the 

catalysis. The restrictive interior of the K12Ga4L6 assembly exhibits size selectivity as small 

substrates are hydrolyzed, whereas larger substrates unable to fit inside of the assembly remain 

unreacted. 

[1] D.L. Caulder and K.N. Raymond. 

J. Chem. Soc., Dalton Trans. 1999, 8, 

1185-1200. 

[2] M. Ziegler, A.V. Davis, D.W. 

Johnson and K.N. Raymond. Angew. 

Chem. Int. Ed. 2003, 

[35] D. Fiedler, H. van Halbeek, R.G. 

Bergman and K.N. Raymond, J. Am. 

Chem. Soc. 2006 128, 10240-10252. 

[4] B.E.F. Tiedemann and K.N. 

Raymond, Angew. Chem. Int. Ed., 

2006, 45, 83 –86. 

[5] M.D. Pluth, R.G. Bergman, K.N. 

Raymond, Science, 2007, 316, 85- 

88.

OP 19 

Pyrrolic Tripodal Receptors for Molecular Recognition of Monosaccharides: 

Tuning Selectivity 

Martina Cacciarini, a Oscar Francesconi, a Cristina Nativi, a Stefano Roelens b 

a Dipartimento di Chimica Organica, Università di Firenze, and b CNR – IMC, Polo Scientifico e 

Tecnologico, Via della Lastruccia, 13 – 50019 Sesto Fiorentino, Firenze, Italy 

There has been a considerable interest in recent years for synthetic receptors for molecular 

recognition of carbohydrates. [1] The research in this field was fuelled by the discovery of the 

ubiquitary presence of carbohydrates on cell surfaces, exerting a number of roles relying on 

molecular recognition processes that are crucial for cell’s life, such as, among others, adhesion, 

infection and immune response. [2] Although encouraging results have been obtained, mostly in 

organic solvents, with receptors possessing significant affinities for mono or oligosaccharides, 

selectivity, the most relevant and ambitious target, is still a challenging goal far to be reached. 

Benzene based tripodal architectures have been frequently employed in the last decade to 

develop synthetic receptors for monosaccharides, leading to interesting results. [1] In this 

context, we recently reported a new generation of cyclic (1) and acyclic (2) receptors featuring 

pyrrolic binding sites, which were shown to effectively bind to monosaccharides. [3] 

NH HN HN 

NH 

HN 

HN 

HN 

NH HN 

1 

In an effort to explore the potentials of this new family of receptors, we found that selectivity can 

be directed toward specific monosaccharides by strategically introduce appropriate substituents 

into the architecture of the receptor, preserving the flexibility of the tripodal scaffold. In the 

present communication, the results obtained with this versatile family of hosts, endowed with 

recognition properties among the best reported in the recent literature, will be discussed, 

showing how affinity and selectivity are modulated by an appropriate combination of functional 

groups and substituents. 

[1] For a recent comprehensive review on the subject, see: A. P. Davis, T. D. James, in 

Functional Synthetic Receptors; T. Schrader, A. D. Hamilton, Eds.; WileyVCH: Weinheim, 

2005; pp.45-109. 

[2] B. Ernst, W. Hart, P. Sinaÿ, Carbohydrates in Chemistry and Biology; WileyVCH: 

Weinheim, 2000; Part I, Vol. 2 and Part II, Vol. 4. 

[3] (a) O. Francesconi, A. Ienco, G. Moneti, C. Nativi, S. Roelens, Angew. Chem. Int. Ed. 2006, 

45, 6693-6696. (b) C. Nativi, M. Cacciarini, O. Francesconi, A. Vacca, G. Moneti, A. Ienco, S. 

Roelens, J. Am. Chem. Soc., 2007, ASAP 16/3/2007. 

NH 

H 

N 

HN 

2 

HN 

H 

N 

HN 

Threading of molecular handcuffs to obtain new interlocked twodimensional 

species 

O 

O 

O 

O 

O 

O 

O 

N N 

Cu 

N N N 

Cu 

N N N N N 

O 

O 

O 

O 

O 

O 

O 

O 

O 

a [2]-catenane 

N 

N 

O 

O 

N 

N 

molecular handcuffs 

O 

O 

O 

O 

2+ 

N 

N 

O 

O 

O 

O 

MeO 

MeO 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

N N 

Cu 

N N 

N N 

N N 

Cu 

N N 

N N 

N N 

N N 

Cu 

Cu 

N N N N 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

a non-stoppered [4]rotaxane 

OP 20 

Valérie Heitz a , Jean-Paul Collin a , Julien Frey a , Tomàs Kraus b , Jean-Pierre Sauvage a , Christian 

Tock a 

a. Institut de Chimie de Strasbourg, Laboratoire de Chimie Organo-Minérale, Université Louis 

Pasteur, 4, rue Blaise Pascal, 67000 Strasbourg, France. 

b. Dr. Tomàs Kraus, Institute of Organic Chemistry and Biochemistry, Flemingovo nam. 2, 

16610 Prague, Czech Republic. 

Elaboration of multirotaxanes or multicatenanes incorporating several rings and several threadlike 

fragments is very challenging, as synthetic targets or as prototypes of molecular machines. 

The copper(I) templated strategy used in the group long ago has been extended to more and 

more complex molecules, incorporating several metal centres. We have described recently the 

synthesis of a handcuffs-like bis-macrocycle consisting of two back-to back rigidly connected 

1,10-phenanthroline units as the central core, each phenanthroline being part of a 30membered 

macrocycle. [1] Threading this bis-macrocycle with a large ring gave a [2]catenane 

with an unusual topology as represented below. The bis-macrocycle can also be utilised for 

constructing more complex systems such as, in particular, a rotaxane tetramer or its nonstoppered 

analogue, as depicted in the scheme. [2] 

[1]. "A catenane consisting of a large ring threaded through both cyclic units of a handcuff-like 

compound". J. Frey, T. Kraus, V. Heitz, J.-P. Sauvage, Chem. Commun., 2005, 5310-5312. 

[2]. "Copper(I)-induced threading of two bis-macrocycles on two rods: a cyclic [4]rotaxane". 

J.-P. Collin, J. Frey, V. Heitz, E. Sakellariou, J.-P. Sauvage, C. Tock, New J. Chem. 2006, 

30, 1386-1389. 

4+ 

OMe 

OMe

Selective Transmembrane Anion Conductances of Polycationic 

Calix[4]arenes 

Irene Izzo, a Sabina Licen, b Nakia Maulucci, a Francesco De Riccardis a , and Paolo Tecilla b 

(a) Department of Chemistry, University of Salerno, Via Ponte Don Melillo, I-84084 Fisciano, 

Salerno (Italy); (b) Department of Chemical Sciences, University of Trieste, Via L. Giorgieri, I- 

34127 Trieste (Italy); 

The recent advances in the ion-channel field have revolutioned the perception of the plasma 

membrane dynamic properties. Ion-coupled processes occurring in the phospholipid bilayer play 

a crucial role in energy transduction, movement, antibiosis, and sensing processes. The 

selective disturbance of ion gradients can, therefore, constitute a privileged entry portal for the 

development of new pharmaceuticals, a valuable tool for the design of nanoscale transducers, 

and a favoured starting point to better understand the chemistry and physiology of fundamental 

cell processes. Despite these potentials and in contrast with the inspiring specificity of natural 

ion channels, few synthetic ionophores discriminate cations, and fewer have proven to be 

+ H2N 

HN 

O 

NH 3 + 

O 

O 

H 3N + 

O 

O 

O O 

NH 2 + 

O 

NH 

O NH 

O 

HN 

O 

O 

+ NH2 + H2N 

+ H2N 

HN 

H3N + 

+ 

(x 8 CF3COO NH3 - H3N ) 1 2 

+ 

(x 8 CF + 

3COO NH3 - ) 

O 

NH 3 + 

O O 

O 

O 

O NH 

HN 

+ NH2 + H2N 

H 3N + 

O 

NH 2 + 

O 

NH 

OP 21 

selective anion transporters. [1] 

We hare interested in the developing of synthetic 

ionophores based on steroid [2] and calix[4]arene [3] 

platforms and previous studies provided useful insights 

on cations transport and selectivities. The structural 

information we gained, were rationally embodied in the 

design of plausible anion receptors, with the aim to probe 

their ability to selectively promote anion transport and 

evaluate possible biological implications. 

In this contribution we report design, synthesis, ion 

transport properties, and cytotoxic activities of the 

polycationic transporter 1 and of its simplified cognate 2. 

Exemplars 1 and 2, in their extended conformation, are 

long enough (about 32 Å) to span completely the 

phospholipid bilayer of a liposome, used as membrane 

model. The conjugates act as powerful unimolecular 

proton ionophores, with 1 more active than 2 probably 

due to the more pronounced hydrophobic moieties, which 

maximize partition in the membrane. The ionophores 

display remarkable selectivity for protons over the group 1 

alkali metals, and also discriminate among anions (I - Br - 

Cl - >> NO3 - > Glutamate ClO4 - >SO4 2- ). Most notably, 

the transport efficiency is sensitive to the presence of the non-transported anions which, 

therefore, act as inhibitors of the transport process. Mechanistic hypothesis on the transport 

process will be presented and discussed. 

[1] For a recent review on artificial ionophores see: A. Sisson, M. Raza Shah, S. Bhosale, S. 

Matile, S. Chem. Soc. Rev. 2006, 35, 1269 – 1286. 

[2] F. De Riccardis, M. Di Filippo, D. Garrisi, I. Izzo, F. Mancin, L. Pasquato, P. Scrimin, P. 

Tecilla, Chem. Commun. 2002, 3066-3067. 

[3] N. Maulucci, F. De Riccardis, C. B. Botta, A. Casapullo, E. Cressina, M. Fregonese, P. 

Tecilla and I. Izzo, Chem. Commun. 2005, 1354-1356.

PSA 1 

Efficient synthesis of pseudopeptidic macrocycles through anion templation 

Ignacio Alfonso, Miriam Bru, M. Isabel Burguete, Santiago V. Luis, Jennifer Rubio 

Departamento de Química Inorgánica y Orgánica, UAMOA, Universidad Jaume I, Campus del 

Riu Sec, Avenida Sos Bainat, s/n, E-12071, Castellón (Spain). 

The development of synthetic methods for macrocyclization reactions allows the preparation of 

new receptors and biologically interesting molecules.[1] Usually, these processes are hampered 

by low yields and tedious purification steps, as mixtures of compounds are often obtained. 

Templated synthesis is an attractive alternative for controlling the selectivity and efficiency of 

those processes.[2] In spite of the increasing interest on anion coordination chemistry, anion 

templation approach to this problem is still in its infancy.[3] Taking advantage of the experience 

gained, we designed an anion templated procedure for the selective preparation of a family of 

pseudopeptidic macrocycles which would be difficult to obtain by more conventional 

methodologies. Besides, the anion templation effect has been thoroughly studied using different 

experimental (NMR, ESI-MS, CD, UV) and theoretical (molecular modeling) approaches.[4] 

O O 

NH HN 

R R 

NH2 H2N 

+ 

CHO 

CHO 

O 

O 

N 

H 

NH 

R 

NH 2 

R 

O 

N 

NH 

NH 

N 

O 

R 

N 

R 

CHO 

O 

R 

O 

N 

HN 

HN 

N 

O 

R 

R 

N 

H 

NH 

N 

O 

N 

R 

R 

NH HN 

O O 

N 

N N 

R R 

O 

N 

H 

HN 

N 

R 

O 

O 

O 

NH 

R 

N 

H 

NH HN 

R 

O O 

N N 

R 

N 

H H 

N 

R 

R 

N 

H H 

N 

R 

N N 

O O 

[1] (a) B. Dietrich, P. Viout, J.-M. Lehn, Macrocyclic Chemistry, VCH, New York, 1993. (b) D. 

Parker, Macrocycle Synthesis: A Practical Approach, Oxford University Press, New York, 1996. 

(c) F. Vögtle, Cyclophane Chemistry, Wiley, Chichester, 1993. 

[2] Z. R. Laughrey, B. C. Giba, Top. Curr. Chem. 2005, 249, 67-125. 

[3] R. Vilar, Angew. Chem. Int. Ed. 2003, 42, 1460-1477. 

[4] M. Bru, I. Alfonso, M. I. Burguete, S. V. Luis, Angew. Chem. Int. Ed. 2006, 45, 6155-6159. 

N 

H 

H 

N 

R 

R 

HN 

HN 

O 

O 

PSA 2 

Synthesis and Solid State Structure of a Double Calix[6]arene Nanotube 

Arturo Arduini a , Giovanni Faimani a , Andrea Pochini a , Andrea Secchi a , Franco Ugozzoli b , Chiara 

Massera b 

a Dipartimento di Chimica Organica e Industriale dell’Università, Viale G. P. Usberti 17/a, I- 

43100, Parma, Italy 

b Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica e Chimica Fisica 

dell’Università, Viale G. P. Usberti 17/a, I-43100, Parma, Italy 

The functioning of new molecular devices, able to perform programmed tasks, derive from the 

chemical properties and the spatial orientation of the fragments or components that constitute 

their skeleton. In the phase of the design of these systems, very convenient guidelines are 

provided by the principles of supramolecular chemistry, especially in those cases where these 

devices originate from self-assembly processes, should respond to external stimuli and function 

as molecular machines. [1] 

With the aim to synthesize new molecular devices, designed to perform specific functions, we 

have showed that the three-phenylureido calix[6]arene (I) can act as three-dimensional 

heteropolytopic receptor. It can be threaded selectively from the upper rim by suitable axles 

derived from the 4,4’bipyridyl and yields oriented pseudorotaxanes endowed with high 

thermodynamic stability. These supramolecular complexes can be reversibly decomposed 

through electrochemical stimuli and can be stoppered to yield oriented rotaxanes that differ for 

the orientation of the two calixarene rims with respect to the different stoppers. [2] 

1.65 nm 

NH 

HN 

O 

NH 

HN 

O 

O MeO 

MeO O OMe O 

O 

O 

O 

I 

HN 

HN 

O 

O N 2 NO2 NO2 

O MeO 

MeO O OMe O 

O 

NH 

HN 

NH 

O 

NH 

HN 

O 

NH 

O MeO 

MeO O OMe O 

O 

O 

O 

II 

These findings prompted us to explore the possibility to exploit the calix[6]arene platform for the 

construction of tubular molecules in view of their use as oriented molecular pores or channels. 

Herewith we describe the synthesis of a double calix[6]arene derivative (II) obtained from the 

head to tail linkage of two calix[6]arene sub-units together with the solid state structure of its 

pseudorotaxene with dioctylbipyridinium tosylate. 

(1) V. Balzani, M. Venturi, A. Credi Molecular Devices and Machines, A Journey into the 

Nanoworld Wiley-VCH, Weinheim (2003). 

(2) a) A. Arduini, F. Ciesa, M. Fragassi, A. Pochini, A. Secchi Angew. Chem. Int. Ed. 2005 44, 

278. b) A. Credi, S. Dumas, S. Silvi, M. Venturi, A. Arduini, A. Pochini, A. Secchi J. Org. 

Chem. 2004, 69, 5881. 

2.30 nm

PSA 3 

Thermodynamics of the selective encapsulation of aqueous cationic guests 

into a supramolecular tetrahedral anionic host 

Giuseppe Arena a , Carmelo Sgarlata b , Valeria Zito b , Kenneth N. Raymond C , Bryan E. F. 

Tiedemann c 

a 

Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, 95125 Catania, Italy 

b 

Istituto di Biostrutture e Bioimmagini, C.N.R. - Sezione di Catania, Viale A. Doria 6, 95125 

Catania, Italy 

c 

Department of Chemistry, University of California, Berkeley, CA, 94720-1460, USA 

Supramolecular chemistry harnesses the simplicity of self-assembly to create large discrete 

structures with complex functionality [1]. In particular, cavity-containing supramolecular 

assemblies enable host-guest chemistry, modulating the properties of a small molecule by 

virtue of encapsulation. The ability of reactants and products to enter and exit the host cavity is 

a key feature in controlling encapsulated reaction chemistry, especially if the host assembly is 

designed to have catalytic activity [2]. 

Raymond et al have described a rational approach to the design of self-assembled metal 

clusters which may be used as nanoscale reaction vessels [3]. The interaction of some 

alkylammonium guests with the tetrahedral host [M4L6] 12- (M = Ga(III) and L = 1,5-bis(2,3dihydroxybenzamido)naphthalene) 

has been described [3]. The encapsulation of Et4N + by 

[M4L6] 12- is depicted below. 

1 

H NMR spectroscopy shows that the host has a marked preference for the inclusion of Et4N + 

over the larger Pr4N + and But4N + . However, the binding energy of this interaction has never 

been quantified by direct calorimetry. Here we present a nanocalorimetric study of the 

encapsulation of Et4N + , Pr4N + and But4N + . This study has made it possible to determine 

simultaneously the binding constant and the H for the encapsulation of these guests by the 

host [4]. The data for the encapsulation of these alkylammonium salts are critically compared. 

[1] J. W. Steed and J. L. Atwood, Supramolecular Chemistry; John Wiley & Sons, Chichester, 

2000; R. M. Yeh, A. V. Davis and K. N. Raymond, In Comprehensive Coordination Chemistry II, 

M. Fujita Ed., Elsevier, New York, 2003, Vol. 7, pp 327-355. 

[2] A. V. Davis, R. M. Yeh and K. N. Raymond, Proc. Natl. Acad. Sci. U.S.A., 2002, 99, 4793- 

4796. 

[3] T. N. Parac, D. L. Caulder and K. N. Raymond, J. Am. Chem. Soc., 1998, 120, 8003-8004; 

D. L. Caulder, R. E. Powers, D. L. Parac and K. N. Raymond, Angew. Chem. Int. Ed., 1998, 37, 

1840-1843. 

[4] P. Gans, A. Sabatini and A. Vacca, http://www.hyperquad.co.uk/hypdeltah.htm. 

PSA 4 

Synthesis and Characterization of Novel Unsymmetrical Phthalocyanines 

with Crown Ether Unit 

Yasin Arslanoglu, Esin Hamuryudan* 

Technical University of Istanbul, Department of Chemistry, 34469, Istanbul, Turkey, 

Fax:(+90) 212 285 63 86, e-mail: arslanoglu@itu.edu.tr 

Phthalocyanines (Pc’s) and their metal complexes (PcM’s), as well as their analogues attract 

much attention because of their electronic structure features, giving rise to many of applications 

in materials science. Unsymmetrical phthalocyanines, despite the comparatively complicated 

preparation methods, are gaining more consideration recently because of their high potential for 

modern applications, e.g. in molecular electronics, mostly as self-assembled, highly-ordered 

thin films.Since their first appearance in the literature about four decades ago, crown ethers 

have taken a key role to understand supramolecular interactions and novel applications for 

heteromacrocycles emerged from there in many areas of chemistry and biology. These might 

include their use in the fields of phase transfer catalysis, ion selectivity, iono electronics, etc. A 

combination of these two potentially promising units (i.e. phthalocyanines and crown ethers) has 

yielded products showing interesting properties. 

In this work, we described the synthesize and characterization of novel unsymmetrically 

substituted metallophthalocyanine which has been synthesized by statistical condensation of a 

mixture of 4,5-bis (hexylthio)-1,2-dicyanobenzene and benzo (15-crown-5) substituted 

phthalonitrile. 

O 

O 

O 

O 

O 

O 

N 

N 

N 

S S 

S 

N 

M 

N 

[1] E. Hamuryudan, Dyes and Pigments, 2006, 68,151-157. 

[2] S.J. Lange, J.W. Sibert, A.G.M.Barrett and B.M. Hoffman, Tetrahedron, 2000,56, 7371-7377. 

[3] Y. Arslanoglu, A. Koca and E. Hamuryudan Polyhedron, 2007, 26, 891-896. 

S 

N 

N 

N 

S 

S

Tetra-Cationic phthalocyanines 

Yasin Arslanolu, Esin Hamuryudan* 


Fax:(+90) 212 285 63 86, e-mail: arslanoglu@itu.edu.tr 

PSA 5 

Metallophthalocyanines (PcMs) have been widely studied for many years, mainly for their 

properties as dyes and catalysts. The recent advances in materials science have identified 

many new applications for PcMs as active materials in various fields, for example in nonlinear 

optical (NLO) devices as semiconducting materials, as liquid crystals, photosensitizers and 

electrochromic devices, amongst others. PcMs possess an extended network of -electrons, 

have planar or nearly planar structures in many cases, and show high thermal and 

photochemical stabilities. Since most PcMs are insoluble, and therefore difficult to process, the 

introduction of substituents at the Pc ring is a necessary approach to increase their solubility. 

The synthesis and characterization of metalophthalocyanines tetra-substituted with 

dimethylaminoethylsulfanyl groups on peripheral positions were achieved by cocyclotetramerization 

of 4-(2-dimethylaminoethylsulfanyl)-1,2-dicyanobenzene with paramagnetic 

metal salts (CoCl2,CuCl2 etc...). Compounds were characterized by their elemental analysis, 

UV-Vis, FT-IR, and mass spectroscopic methods. The study of their ESR and chemical 

properties is now in progress and the results will be published elsewhere . 

[1] Dabak S, Gumus G, Gul A, and Bekaroglu O. J. Coord. Chem. 1996, 38, 287-293. 

[2] Y. Arslanolu and E. Hamuryudan Dyes and Pigments, 2007, 75, 150-155. 

[3] Law, W.F.; Liu, R.C.W.; Jiang, J.; Ng, D.K.P. Inorganica Chimica Acta, 1997, 256,147-150. 

PSA 6 

Water Soluble, NIR Emitting Boradiazaindacene Dyes as Fluorescent Ion 

Sensors 

Serdar Atilgan, Tugba Ozdemir and Engin U. Akkaya* 

Middle East Technical University, Department of Chemistry, 06531 Ankara, Turkey. 

Boradiazaindacenes (a.k.a. BODIPY) found applications in diverse array of fields. 

Distyryl-boradiazaindacenes are especially promising considering their long wavelength 

absorption (650-685 nm, typically) and emission characteristics. We have recently 

demonstrated that a water soluble distyryl-boradiazaindacene derivative (1) showed a 

remarkable photodynamic activity.[1] Water solubility is an important issue in designing 

practically useful fluorescent chemosensors, as well. In this study, well-known aryldipicolylamine 

group has been incorporated into a distyrl-boradiazaindacene structure. In 

addition, the chemosensor 2 carries six TEG (triethyleneglycol) units to improve solubility. 

Metal ion binding is signalled by a hypsochromic shift and increase in emission intensity. The 

design, synthesis and characterization of the chemosensor will be presented. 

[1] Atilgan, S.; Ekmekci, Z.; Dogan, A. L.; Guc, D.; Akkaya, E. U. Chem. Commun. 2006, 4398- 

4400.

Self-assembly of N,C-linked peptidocalix[4]arenes 

L. Baldini, G. Faimani, A. Casnati, F. Sansone, R. Ungaro 

Dipartimento di Chimica Organica e Industriale, Università di Parma, via Usberti 17/a, 43100 

Parma, Italy (laura.baldini@unipr.it) 

In living organisms, peptides and amino acids play a fundamental role in many processes 

controlled by molecular recognition, such as cell recognition or enzymatic catalysis. Thanks to 

their ability to form weak interactions that are highly selective and efficient they are involved in 

the formation of several self-assembled structures such as -helices, -sheets and nanotubes. 

With the aim of developing artificial receptors able to mimic the molecular recognition 

mechanisms of biological systems, we synthesized the first example of a calixarene amino acid 

(1)[1] and optimized the reactions for its insertion in a pseudopeptide sequence. 

The resulting peptidocalixarenes (e.g. 2) are self-complementary (the N-linked arm is 

complementary to the C-linked arm and viceversa) in terms of hydrogen bonding donor and 

acceptor groups. As a consequence, in apolar solutions they self-assemble in dimeric capsulelike 

structures held together by hydrogen bonds between the CO and NH groups (e.g. 3).[1] 

In order to evaluate the scope of these self-assembling systems and to further characterize the 

structure of the self-assembled capsules, we synthesized new members of this N,C-linked 

peptidocalixarene family. The correlation of the self-assembling properties of the new 

compounds with their structure, together with 1D and 2D NMR studies allowed us to shed more 

light on the geometry of the hydrogen bonding motif and on the factors that control the selfassembly 

process. 

N 

H 2 

HO 

O OH 

O 

1 

HO 

O 

CbzHN 

O 

HN 

NH 

O 

HO 

O OH 

O 

2 

O 

O 

HN 

NH 

O 

O 

self-assembly 

O 

O 

O 

N 

H 

O 

N 

H 

O 

O 

H 

N 

H 

N 

O 

H 

N 

O 

HO 

O 

O OH 

HO O OH O 

[1] F. Sansone, L. Baldini, A. Casnati, E. Chierici, G. Faimani, F. Ugozzoli and R. Ungaro, J. 

Am. Chem. Soc. 126, 6204-6205 (2004). 

3 

O 

N 

H 

O 

H 

N 

H 

N 

O 

O 

H 

N 

O 

H 

N 

PSA 7 

O 

O 

O 

Acyclic pyrrole-based anion receptors: Design, synthesis, and anion 

binding properties 

Jonathan L. Sessler † , Natalie M. Barkey † , G. Dan Pantos ‡ , Vince M. Lynch † 

† Univeristy of Texas at Austin, 1 University Station A5300, Austin, TX 78712 

‡ Univeristy of Cambridge, Cambridge CB2 1EW, UK 

Anions have a wide range of importance both in chemical, as well as biological, systems; 

thus, the design and synthesis of novel receptors with the ability to selectively recognize or bind 

a specific class of anions is a rapidly developing field of supramolecular chemistry. 1,2 

A series of novel, acyclic pyrrole-based anion receptors have recently been designed and 

synthesized in the Sessler group (Figure 1). These systems, which are based on pyridine 2,6dicarboxamides, 

bind nitrite and carboxylate anions with good selectivity in dichloroethane 

solution and are also capable of binding cyanide anions weakly. Control systems, incorporating 

a benzene-1,3-dicarboxamide spacer, or those wherein the connectivity of the amide linkage is 

“reversed,” either failed to act as effective anion receptors or displayed very different 

selectivities. Such observations provide support for the notion that small perturbations in the 

structure of these receptors can lead to drastic changes in their anion-binding properties. 3 

Efforts to attach these systems, as well as other oligopyrrolic anion receptors, to 

cellulose-mediated solid support structures are underway and will be presented as appropriate. 

O 

O 

O 

N 

H 

HN 

N NH HN 

O 

O 

O 

O 

O O O 

O 

O 

H 

N HN 

N NH HN 

O 

O 

O O 

O 

O O O 

O 

O 

H 

N 

NH 

O 

O 

O 

HN 

O HN 

O 

O O O 

O 

H 

N N 

H 

O 

O 

O O 

DPPic DPPic II DPIPh RA DPPic 

Figure 1: Novel anion receptors relevant to this presentation. 3 

N N H 

O HN 

O 

O 

O O 

PSA 8 

[1] Camiolo, S; Gale, P; Hursthouse, M.B.; Light, M.E. Org. Biomol. Chem. 2003, 741 

[2] Sessler, J.L.; Camiolo, S.; Gale, P.A. Coord. Chem. Rev. 2003, 17 

[3] Sessler, J.L.; Barkey, N.M.; Pantos, G.D.; Lynch, V.M. N. J. Chem. 2007. Published on web.

PSA 9 

Cell penetrating borosilica nanoparticles: potential delivery agents for BNCT 

Maria Arduini 1 , Giuliana Battanolli 1 , Luca Baù 1 , Fabrizio Mancin 1 , Umberto Tonellato 1 , Chiara 

Compagnin 2 , Lucia Celotti 2 , Maddalena Mognato 2 , Elena Reddi 2 

1 University of Padova, Department of Chemical Sciences, via Marzolo 1, 35131, Padova, Italy 

2 University of Padova, Department of Biology, via Bassi 58/B, 35121, Padova, Italy 

Boron neutron capture therapy (BNCT) exploits the nuclear reaction which occurs upon 

irradiation of a 10 B nucleus located in a tumor cell with low energy neutrons. Fission of the boron 

nucleus gives rise to an α particle and a recoiling 7 Li nucleus, the actual radiotherapic agents. 

The short penetration length of these highly ionizing particles (5-9 µm, less than a typical cell 

diameter) ensures that the damage is confined to the cells where fission events take place, thus 

endowing BNCT with the potential to become a very selective form of radiotherapy. [1] 

Delivering high doses of boron to tumor tissues in a selective fashion is key to the success of 

BNCT. Boron-containing drugs investigated so far include boronated analogues of aminoacids 

and nucleosides, functionalized boron clusters, antibody conjugates and T-cells loaded with 

boron carbide nanoparticles. [2] 

In this communication we discuss the development of novel boron delivery agents based on 

organically modified silica nanoparticles. Silica nanoparticles provide an ideal scaffold for the 

realization of biological and medical nanodevices: they are non-toxic and water soluble, they 

accumulate preferentially in tumor tissues and are easily functionalized, for instance, with 

imaging, targeting or shielding agents. These remarkable qualities make silica nanoparticles 

excellent candidates for a prominent place in the next generation of boron carriers. 

Mixed silicon and boron oxide nanoparticles containing a fluorescent dye were synthesized via 

a modified Stöber method (ammonia catalyzed co-condensation of oxide precursors in alcohol) 

and their toxicity, uptake and intracellular localization were studied. 

These initial attempts were plagued by low boron loading and extensive boron leaching due to 

the hydrolytic instability of the Si-O-B linkage. Two different routes were then investigated to 

address these problems: modification of the oxide network in order to exclude water from the 

interior of the nanoparticles, and replacement of the oxygen bridge with a more stable bridging 

moiety. The former strategy involves the introduction of methyl groups into the oxide network 

through the use of a mixture of suitable silicon precursors, while the latter relies on the selfcondensation 

of a single precursor with pre-formed Si-(CH2)2-B bonds. 

The efficacy of these two approaches will be discussed with respect to the boron loading and in 

vitro behavior of the different kinds of nanoparticles. 

[1] R.F. Barth et al., Clin Cancer Res, 2005, 11, 3987-4002 

[2] G. Wu et al., Anti-Cancer Agents in Medicinal Chemistry, 2006, 6, 167-184 

Screening of 1,3,4-oxadiazoles by narrow-bore HPLC with various 

peptidomimetic calixarene-bonded stationary phases . 

G. Bazylak a and A. A. Haidar b 

PSA 10 

a Department of Pharmaco-Bromatology, Faculty of Pharmacy, Collegium Medicum, Nicolaus 

Copernicus University, Jagiellonska 13, 85-067 Bydgoszcz, Poland Tel: +4852 585 3915; Fax: 

+4852 585 3817; E-mail: gbazylak@cm.umk.pl 

b Al Khalil Pharmacy, Beirut 110236, Lebanon 

Concave hydrophobic surface of the calixarene grafted silica can be treated as the valuable 

peptidomimetic system for study of multiple associations between circulating drugs and serum 

proteins. Thus, retention behaviour in series of 1,3,4-oxadiazoles with a potent analgesic activity 

were determined in the narrow-bore isocratic and gradient HPLC systems employing 

calix[6]arene-, calix[8]arene- as well as tert-butyl calix[4]arene-bonded stationary phases. When 

acetonitrile + 2.65 mM phosphoric acid (55 : 45, v/v), pH* 3.25, mobile phase was applied 

retention of these compounds increased with diminishing of their overall hydrophobicity 

according to the general preference of more polar compounds by calixarene cavity in time of its 

non-specific host-guest supramolecular interactions. The size of calixarene cavity and its upperrim 

substitution slightly modified observed retention order, resolution and selectivity of 

separation for oxadiazoles. Compare to retention on the highlyend-capped and polar-embedded 

octadecylsilica HPLC columns an extended separation of some positional isomers of 

halogenated oxadiazoles were observed on the used calixarenetype HPLC supports. In addition 

formation of the 1:1 inclusion host-guest complexes between each calixarene-type stationary 

phase and oxadiazoles were studied with MM+ and AM1 molecular modelling methods. The 

structural and energetic factors leading to the hydrogen bond stabilized inclusion complexes 

between mentioned species were considered and used for explanation of observed retention 

sequence and separation selectivity of oxadiazoles in applied HPLC systems. The effect of 

mobile phase components as acetonitrile and phosphate anion on deprotonation and monolayer 

formation of silica-bonded calixarenes as well as their molecular recognition abilities in 

developed HPLC procedures and previously reported PVC-based membrane electrodes [1] was 

also discussed. 

1] G. Bazylak, L.J. Nagels, H.J. Geise, Comb.Chem. & High Throughput Screen., 2004, 7, 345 . 

359

PSA 11 

Copper(II) Complexes of Aza Pyridinophanes and Terpyridonophanes as 

SOD Mimics 

Salvador Blasco, a Jorge González, a Enrique García-España, a Pablo Gaviña, b Hermas 

Jiménez, a Raquel Belda, a Conxa Soriano, b José M. Llinares, Carmen Terencio. c 

a) Departament de Química Inorgànica, Instituto de Ciencia Molecular, Facultat de 

Química,Universitat de València. 

b) Departament de Química Orgánica, Instituto de Ciencia Molecular, Universitat de València, 

Burjassot. 

b) Departament de Farmacología, Facultad de Farmacia Avda. Andrés Estellés s/n, Universitat 

de València, 46100 Burjassot. 

Aerobic living organisms use atmospheric oxygen as metabolic oxidant for producing the energy 

required in their living processes. The amount of consumed oxygen by higher organisms is so 

large that they require an almost constant supply of dioxygen. In spite of this necessity, oxygen 

has enough oxidizing power to produce the oxidation of organic matter. If this oxidation does not 

readily occur at room temperature is because reaction of O2 with most biomolecules is 

kinetically prevented. However, the reduction of O2 to water yields intermediate species which 

are reactive and toxic. Therefore, living organisms need to develop defense mechanisms in 

order to remove these species or converting them into useful chemicals for metabolic purposes. 

Superoxide dismutase (SOD) is one of the key enzymes in this mechanism and has the role to 

protect cells from the damage caused by superoxide radicals. 

Under normal conditions in healthy organisms free radicals are trapped by SOD present in 

mitochondria, blood or in the extracellular space. However, when there is an overproduction of 

radicals or/and deficient working of the defense mechanisms their control becomes problematic. 

Therefore, the preparation of small molecules able to mimic the active site of Cu2Zn2-SOD or 

Cu2Cu2-SOD has been a research topic of great interest following the pioneering work of 

Lippard’s group.1-4 

Herewith we report on a series of pyridine and terpyridine ligands whose Cu(II) binuclear 

and Zn(II)-Cu(II) mixed complexes display an interesting behavior as SOD mimics. We discuss 

the speciation in solution, the electrochemistry and paramagnetic NMR behavior of the 

dimetallic copper(II)-imidazole systems and we analyze the pH range of existence of the 

imidazolate (Im-) bridge. Additionally, we present the crystal structure of the crystalline complex 

[ Cu2L (Im) (Br) (H2O) ] ( CF3SO3 ) 2·3H2O ( L = 2, 6, 9, 12, 16 – pentaza [17] - ( 5, 5 ’’ ) – 

terpyridinocyclophane ) and we analyze its magnetic properties in relation with related binuclear 

complexes. 

[1] (a) G. Kolks, C. R. Frihart, H. N. Rabiniwitz and S. J. Lippard, J. Am. Chem. Soc.,1976, 98, 

5720. (b) P. K. Coughlin, J. C. Dewan, S. J. Lippard, E. Watanabe and J.-M. Lehn, J. Am. 

Chem. Soc., 1979, 101, 2652 2 (a) M. G. B. Drew, C. Cairns, A. Lavery and S. M. Nelson, J. 

Chem. Soc., Chem. Commun., 1980, 1120.. 

[3] G. Tabbi, W. L. Driessen, J. Reedijk, R. P. Bonomo, N. Veldman, and A. L. Spek, Inorg. 

Chem., 1997, 36, 1168. 

[4] (a) C. A. Salata, M.-T. Youinou and C. J. Burrows, Inorg. Chem., 1991, 30, 3454.(b) U. 

Weser, L. M. Schubotz, E. Lengfelder, J. Mol. Cat., 1981, 13, 249. (c) E. Kimura, Y. Kurogi, M. 

Shionoya and M. Shiro, Inorg. Chem., 1991, 30,4524otes 

PSA 12 

Hydrazone Exchange Dynamic Combinatorial Libraries in Aqueous and 

Organic Solvents 

Ana Belenguer a , Jingyuan Liu a , Christoph Naumann b and Jeremy K. M. Sanders a 

a Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, 

UK. 

b School of Molecular and Microbial Biosciences, University of Sydney, NSW 2006, Australia 

Dynamic Combinatorial Chemistry (DCC) has emerged as a new strategy for the discovery of 

novel host-guest systems.[1] Building blocks containing the functionalities for reversible 

chemistry are reacted under such conditions as to promote supramolecular interactions 

between the template and the best host; it forms a Dynamic Dombinatorial Library (DCL) which 

is under thermodynamic control. In our group we have investigated predominantly two DCL 

chemistries: disulfide exchange [2] and hydrazone exchange.[3] [4] Previous hydrazone 

exchange DCL work [3] [4] has used relatively long and flexible building blocks (tripeptides); 

containing the two complementary functionalities, aldehyde and hydrazide (AB system). In this 

poster we attempt to extend the methodology by investigating the AA-BB hydrazone exchange 

systems with shorter and more rigid building blocks; we use two complementary building blocks, 

one contains the 2 aldehyde (BB) functionalities while the other contains the 2 hydrazide 

functionalities (AA). These form hydrazones which exchange under DCL conditions. In order to 

investigate the DCLs in aqueous and organic solvent we have used dihydrazide with different R 

substituents. The effect of a heteroatom on the aromatic dialdehyde / diketone building block is 

investigated. 

Higher 

Oligomer 

Octamer 

N 

H 2 

H 

N 

R 

H 

N 

NH 2 

O O 

A-A (dihydrazide) 

O 

+ 

X 

R1 

O 

R1 

B-B (dialdehyde/diketone) 

Template 

TFA 

O 

R1 

N 

N 

X 

R 

Dimer 

N 

N 

R1 

O 

R1 

R1 

X 

Hydrazone 

exchange 

N 

H 

N 

N 

N 

H 

O 

O 

R 

R 

H 

N 

O N 

O 

N 

N 

H 

Hexamer 

X 

Tetramer 

[1] P. T. Corbett, J. Leclaire, L.Vial, K. R. West, J-L. Wietor, J. K. M. Sanders and S. Otto, 

Chemical Reviews, 2006, 106(9), 3652-3711 

[2] A. L. Kieran, A. D. Bond, A. M. Belenguer and J. K. M. Sanders, Chemical Communications, 

2003, 21, 2674-2675. 

[3] R. T. S. Lam, A. Belenguer, S. L. Roberts, C. Naumann, T. Jarrosson, S. Otto and J. K. M. 

Sanders, Science, 2005, 308(5722), 667-669 

[4] J. Liu, K. R. West. C. R. Bondy, J. K. M. Sanders, Organic & Biomolecular Chemistry, 2007, 

5(5), 778-786. 

R1 

R1

PSA 13 

Halide anion interactions with dicopper(II) and dicobalt(II) bistren cryptates 

Greta Bergamaschi, Valeria Amendola, Luigi Fabbrizzi, Antonio Poggi 

Dipartimento di Chimica Generale, Università di Pavia, 27100 Pavia, Italy 

Homodimetallic bistren cryptates include polyatomic anions, displaying size and shape 

selectivity. [1] The dicopper(II) complex of cryptand 1, containing 2,5-dimethylfurane spacers, 

forms very stable inclusion complexes with halides, in an aqueous solution buffered at pH 5, the 

event being signalled by the development of an unusually intense charge transfer band, 

responsible for the bright yellow colour. [2] A slight pH increase (to 7) induces halide extrusion, 

which is replaced by an hydroxide ion, with a colour change to seawater green. 

The crystal and molecular structure of the [Cu2 II (1)(Cl)] 3+ inclusion complex is shown in the 

Figure above. In order to avoid OH competition, interaction of halides with [Cu2 II (1)] 4+ has been 

now investigated in an aprotic solvent (e.g. MeCN) through spectrophotometric titration 

experiments. On chloride addition to a cryptate solution, the following species form in sequence: 

(i) {[Cu2 II (1)]Cl[Cu2 II (1)]} 7+ , in which a Cl ion bridges two Cu II centres of two distinct cages; (ii) 

the [Cu2 II (1)(Cl)] 3+ inclusion complex; (iii) [Cu2 II (1)(Cl)2] 2+ , in which each metal centre has its own 

Cl coordinated. Noticeably, the strong absorption band at 410 nm ( = 8000 M 1 cm 1 ) and the 

intense yellow colour are observed only with the {[Cu2 II (1)] Cl[Cu2 II (1)]} 7+ and [Cu2 II (1)(Cl)] 3+ 

species, thus specifically involving the Cu II ClCu II fragment. Similar behaviour was observed 

on titration with Br and I . 

Also cobalt(II) forms a stable dimetallic cryptate complex with 1, whose anion inclusion 

tendencies have been investigated in MeCN solution. On halide addition the two ‘bridged’ 

species form {[Co2 II (1)]X[Co2 II (1)]} 7+ and [Co2 II (1)(X)] 3+ but no intense charge transfer 

band develops. Moreover, on further halide addition, Co II ions are abstracted from the cage. In 

any case, for both Cu II and Co II cryptates, thermodynamic constants of anion inclusion equilibria 

are higher than 10 5 and cannot be determined exactly through spectrophotometric titrations. 

Ligand 1 was then reacted with an excess of C16H33Br, to give the hexa-cetylated derivative 2, 

which afforded the formation of the dimetallic species [Cu2 II (2)] 4+ in apolar media (n-hexane, 

toluene). 

[1] M. Boiocchi, M. Bonizzoni, L. Fabbrizzi, G. Piovani, A. Taglietti, Angew. Chem., Int. Ed., 

2004, 43, 3847-3852. 

[2] V. Amendola, E. Bastianello, L. Fabbrizzi, C. Mangano, P. Pallavicini, A. Perotti, A. Manotti 

Lanfredi, F. Ugozzoli, Angew. Chem., Int. Ed., 2000, 39, 2917-2920. 

Dynamic Combinatorial Chemistry – a Selection Based Approach to 

Catalysis 

Enda Bergin, a David Lewis, b Zoe Pikramenou b and Sijbren Otto. a 

a 

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, 

UK. 

b 

School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK. 

Dynamic Combinatorial Chemistry is proving to be a tremendously rich and fruitful field, 

combining the fast screening of combinatorial chemistry with the variety and ease of synthesis 

associated with a chemically dynamic system.[1] Disulfide exchange has previously been 

successfully used in the search for macrocyclic molecular receptors,[2] and proof-of-principle 

results have been achieved in the search for catalysis, both for the Diels Alder reaction[3] and 

acetal hydrolysis.[4] In this work we attempt to extend this methodology by the use of thiol 

containing compounds capable of binding metal ions, in the expectation that these will produce 

more active catalysts. A number of thiol-containing ligands have been synthesised (1-3), and 

their behaviour under disulfide exchange conditions, in the presence of d- and f- block metal 

ions, has been explored. 

HO 2C CO 2H 

N 

N 

HN O 

CO 

O NH 

2H 

N 

SH SH 

HS 

R 1 

R 2 

N N 

OH HO SH 

NH 

N 

NH HN 

1 2 3 

PSA 14 

[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] For recent examples see (a) Vial, L.; Ludlow, R. F.; Leclaire, J.; Perez-Fernandez, R.; Otto, 

S. J. Am. Chem. Soc. 2006, 128, 10253-10257. (b) Rodriguez-Docampo, Z.; Pascu, S. I.; Kubik, 

S.; Otto, S. J. Am. Chem. Soc. 2006, 128, 11206-11210. 

[3] Brisig, B.; Sanders, J. K. M.; Otto, S. Angew. Chem., Int. Ed. 2003, 42, 1270-1273. 

[4] Vial, L.; Sanders, J. K. M.; Otto, S. New. J. Chem. 2005, 29, 1001-1003 

SH

PSA 15 

Can electron-deficient aromatic rings be utilized to bind anions by design? 

Orion B. Berryman, § Jeffrey S. Meisner, § David P. Stay, § Darren, W. Johnson, § Vyacheslav S. 

Bryantsev, Benjamin, P. Hay † 

§ Department of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403, USA, the 

Oregon Nanoscience and Microtechnologies Institute (ONAMI) and † Chemical Separations 

Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA 

The observation of anions being attracted to electron-deficient aromatic rings has recently 

received considerable attention. Focus has centered on computational studies of anions 

interacting with charge neutral electron-deficient aromatic rings. A number of crystal structures 

support these claims while fewer examples exist demonstrating solution measurements of this 

interaction. It has been theorized that electron-deficient arenes could be used to aid in the 

performance of anion receptors. This presentation addresses the preferred binding geometry for 

this interaction as well as strategies for designing receptors that bring multiple arenes to bear on 

a single anion. Association constants are reported for first generation receptors and single 

crystal x-ray structures and electronic calculations reveal a preferred off center binding 

geometry for anions interacting with electron-deficient arenes. Can electron-deficient aromatic 

rings offer binding selectivity that is atypical to traditional anion binding techniques? Efforts to 

answer this question will be presented. 

Figure 1. A) Section of a [K(18-crown-6)(1,2,4,5-tetracyanobenzene)2] + Br - crystal structure. 

B) CAChe MM3 model of a receptor•I - complex. 

PSA 16 

Dimerization of a hydrogen-bonded 2,6-alkynylpyridyl scaffold is induced by 

both water and anions. 

Orion B. Berryman, § Charles A. Johnson, § Michael M. Haley, § Darren, W. Johnson, § 

§ Department of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403, USA, the 

Oregon Nanoscience and Microtechnologies Institute (ONAMI) 

The water molecule plays a vital role in forming synergistic hydrogen bonds in a number of 

systems ranging from synthetic hexameric nanoscale capsules to crucial hydrogen bonds in 

enzymatic active sites – in many cases these hydrogen bonds dictate both structure and 

function. Anions do not share the same structural diversity as water, although recently they 

have been used as directing elements in self-assembly. Very rarely do anions and water serve 

the same role in self-assembled systems. 

A series of new fluorescent anion receptors based on a 2,6-alkynylpyridine scaffold will be 

described. The synthetic versatility of the receptor core allows for developing a wide range of 

hydrogen bonding receptors. Examples include a sulfonamide-functionalized receptor that forms 

a 2:2 dimer with both water or halides (Cl - , Br - ), depending on the protonation state of the 

pyridine core. This is an unusual example of both halides and water molecules serving the 

same structural role in a synthetic self-assembled system. The solution dynamics of these 

systems will be discussed in the context of anion recognition and a barrage of single crystal xray 

structures will provide structural clues for optimizing these new anion receptors. 

Figure 1. A) Crystal structure of the 2:2 receptor•H2O complex. 

B) Crystal structure of the 2:2 receptor•Cl- complex

Sensing with cavitands: Moving from selectivity to specificity 

Paolo Betti a , Gionata Battistini b , Luca Prodi b , Enrico Dalcanale a 

a Dipartimento di Chimica Organica ed Industriale, Università di Parma, viale G.P. Usberti 17/a, 

43100 Parma, Italy 

b Dipartimento di Chimica “G. Ciamician”, via F. Selmi n.2, 40126 Bologna, Italy 

Quartz-Crystal-Microbalance mass transducers (QCM) are by far the easiest platforms to 

translate the chemical recognition proprieties of a receptor in a treatable signal. We have 

already designed and tested QCM supramolecular sensors using phosphonate cavitands as 

coated molecular receptors. These cavitands present a phosphonate bridging group as 

hydrogen bond acceptor having the P=O group oriented alternatively inward (POin) or outward 

(POout) with respect to a preorganised cavity, capable of CH-π interactions.[1] The simultaneous 

presence of the two interactions which is possible only for the POin isomer, provides an 

exceptional rise in selectivity toward short chain alcohols.[2] However, upon increasing the 

chain length of the alcohol, the purely dispersive unspecific interactions become dominant with 

respect to the specific ones, jeopardizing the selectivity of the sensors. 

To overcome this problem and reach the desired specificity we have designed and tested a new 

class of phosphonate cavitands incorporating a suitable transduction group (a chromophore), 

which can be activated exclusively by the molecular recognition event. 

More specifically, by coupling the H-bond acceptor to the chromophore it has been possible to 

change the emission spectra of the chromophore upon analyte complexation. This behavior has 

been observed both in solution and in a coated solid film. 

O 

O 

O 

R 

R 

O 

NH 

R 

O 

P 

O 

R 

O 

O 

O 

Analytes 

Emission Spectra 

[1] R. Pinalli, M. Suman, E. Dalcanale, Eur. J. Org. Chem., 2004, 451 – 462 

[2] L. Pirondini, E. Dalcanale, Chem. Soc. Rev., 2007, 35, in press 

PSA 17 

The Construction of Coordination Networks Incorporating {M(tpy)2} n+ PSA 18 

(tpy = 

2,2:6,2-terpyridine) Groups 

Jonathon E. Beves, a Edwin C. Constable, a Catherine E. Housecroft, a Cameron J. Kepert b , 

Markus Neuburger, a David J. Price b and Silvia Schaffner a 

a Department of Chemistry, University of Basel, Spitalstrasse 51, CH-4056, Basel, Switzerland 

b School of Chemistry, University of Sydney, NSW 2006, Australia 

Iron(II) and ruthenium(II) complexes of 2,2’:6’,2’’-terpyridine are the focus of extensive interest 

in supramolecular chemistry [1]. The inclusion of these groups into extended structures offers 

the opportunity to build electrochemical or photophysical properties into addressable molecular 

frameworks. 

~7 Å 

N 

N 

~18 Å 

N 

N 

N 

Ru 

N 

N N 

N 

1 2 

N 

2+ 

~22 Å 

N 

N 

NH 

N 

N N 

Ru 

N N 

We are developing [2] coordination polymers containing {M(tpy)2} units. A key building block is 

the ligand 4’-(4-pyridyl)-2,2’:6’,2”-terpyridine, which acts as a terdentate ligand with a pendant 4pyridyl 

ring. In these structures the {M(tpy)2} moieties act as ‘expanded 4,4'-bipyridines’ in which 

the two 4-pyridyl metal-binding domains are separated by metal-containing {M(tpy)2} scaffolds. 

Figure 1 ([Ru(tpypy)2]-Ag-)n coordination polymer 

[1] E. C. Constable, Chem. Soc. Rev., 2007, 36, 246. 

[2] J. E. Beves, E. C. Constable, C. E. Housecroft, C. J. Kepert, D. J. Price, CrystEngComm, 

2007, in press. 

N 

HN N 

3 

N 

2+

PSA 19 

DNA Binding by a New Metallointercalator Containing a Proflavine Group 

Bearing a Hanging Chelating Unit 

Carla Bazzicalupi, a Andrea Bencini, a Antonio Bianchi, a Tarita Biver, b Alessia Boggioni, b Sara 

Bonacchi, a Andrea Danesi, a Claudia Giorgi, a Fernando Secco, b Barbara Valtancoli, a Marcella 

Venturini b 

a Department of Chemistry, University of Florence, Via della Lastruccia 3, 50019, Sesto 

Fiorentino, Italy, antonio.bianchi@unifi.it. b Department of Chemistry and Industrial Chemistry, 

University of Pisa, Via Risorgimento 35, 56126, Pisa, Italy, ferdi@dcci.unipi.it 

Recent developments in biochemistry concern the design of new molecules that are able to bind 

DNA via supramolecular interactions. These new probes can provide a better understanding of 

the activity of many drugs and anticancer agents and be of help in developing new diagnostic 

tools. 

The new proflavine-based ligand D, containing a hanging chelating diethyelentriamine moiety, 

and its Zn(II) complex bind calf thymus DNA according to a biphasic behaviour defined by two 

H2N 

HN 

N NH2 NH2 NH2 NH2 

N 

NH2 NH2 NH2 NH2 

NH2 NH2 NH2 NH2 

of the dye affinity for the polymer. On the other hand, 

at high P/D values the interaction takes place via 

intercalation of the proflavine residue between base 

pairs, without significant effects deriving from the 

presence of Zn(II). 

Molecular modeling calculations performed with 

appropriate base pair sequences show that the 

intercalative binding should be more favourable when 

involving CG base pairs, even if also intercalation 

between AT base pairs leads to stable complexes. 

Most likely, in the case of AT sequence also 

significant groove binding occurs. 

In contrast with the common behaviour of basestacking 

intercalators, modeling calculations indicate 

that the intercalative binding of the present dye 

should mostly involve only one filament of the double 

helix (Figure 1), probably due to NH +… O interactions 

between the protonated acridine nitrogen and the 

oxygen atoms of the polyanion. Most likely this 

peculiar binding feature is favoured by the structure 

of the intercalator which was designed with the 

intention of inserting the chelating hanging group on 

the C9 atom of acridine in order to allow the N10 

atom to project towards the polymer chain. 

D 

different binding modes depending on the polymer to 

dye molar ratio (P/D), forming complexes of 

considerable stability. At relatively low P/D values, 

both the metal-free ligand and its Zn(II) complex 

associate with DNA, externally to the base pairs, with 

principal involvement of the polyamine moiety. The 

presence of the metal ion leads to a fourfold increase 

Figure 1 

Exploration of -Extended Interactions: 

Discopus as a new class of molecular receptor 

Cécile Givelet, Laura M. Scott, Brigitte Bibal 

University of Bordeaux 1 

Institut des Sciences Moléculaires, UMR CNRS 5255 

351 cours de la Libération, 33405 Talence, France. 

b.bibal@ism.u-bordeaux1.fr 

Among molecular interactions, - and CH- interactions play a key role in Nature (protein 

folding, cellular signalisation) and in artificial nano-devices. The understanding and the 

modulation of these interactions is a fundamental problem, crucial to the development of future 

applications in the fields of molecular transport, detection and separation of aromatic and 

aliphatic compounds. 

The main objective of our work is to explore -extended architectures as original receptors and 

controlled assemblies partners. Our new concept of discopus structures is highly relevant for 

selective molecular recognition in different media. Its discotic core is available for interaction 

and the bulky out-core prevents uncontrolled aggregation. 

DISCOPUS 

We present here a new class of -extended receptors: the hexa-discopus 1a-b and 2. 

Structures 1 and 2 were synthesised from veratrole in few steps with excellent yields. Their 

affinity for either biological and toxic aromatics or carbohydrates were evaluated using UV- 

Visible absorption and Fluorescence emission titrations. 

R 

R O 

P 

O 

O 

R 

P 

O R 

R 

O 

P 

R O 

R O 

P 

R 

O 

O 

O R 

P 

R 

O 

P 

O R 

R 

1a : R = Ph 

1b : R = C 6H 4-p-OH 

R 

R R 

Si 

O 

O 

R 

Si 

R R 

R 

R 

Si 

R O 

R 

R O 

Si 

R 

2 : R = i-Pr 

R 

O R 

Si 

R 

R 

Si 

O R 

R 

PSA 20 

For instance, dopamine and D-Glucose were complexed in water-Methanol (96/4, v/v) with a 

10 +4 M association constant. 

Nature of the -extended interaction and its selectivity were also evaluated.

Lead(II) complexation by calix[4]-hydroxamates. 

Synthesis, X-ray structure and potentiometric studies in ion selective 

electrodes 

Maria Bocheska and Urszula Lesiska 

Department of Chemical Technology, Chemical Faculty, Gdask University of Technology, 80- 

952 Gdask, Poland, marboch@chem.pg.gda.pl 

Hydroxamic acid moiety is found in naturally occurring metal complexing compounds, 

known as siderophores, which are especially strong iron(III) chelators. [1]. These natural 

compounds of rather low molecular weight are produced by bacteria and fungi and play crucial 

role in the iron uptake and transport into the cell. But it was also found that compounds with 

hydroxamic units are able to complex other metal cations, such as for example Cu(II), Al(III), 

Pb(II) or uranyl ions. Such ability of siderophores generate many important biological activities 

(antibacterial, antifungal, anticancer or specific enzyme inhibition) which makes them worth to 

be considered as a potential pharmaceutics. Also synthetic ligands are planned based on the 

structure of natural siderophores and on coordination geometry of the metal ion to be complex. 

The determination of heavy metals in variety of samples (drinking or waste waters) is of 

urgent need. Naturally occurring siderophores seem to be very effective chelators, active in 

metal recovery and waste remediation. However, majority of these compounds known in nature 

are water soluble and such property disqualify them from the use as active materials for 

chemical sensors. To use them for such purpose in chemical sensors (ion-selective electrodes 

(ISEs) they should of higher lipophilicity. 

We use t-butylcalix[4]arene as a scaffold for building synthetic siderophores. We present 

here synthesized hydroxamate derivatives of p-tert-butylcalix[4]arene and their ionophoric 

properties when applied in the membrane of ion selective electrodes (ISEs). The electrodes are 

lead (II) selective with nernstian slope in a wide linear range (10 -6 – 10 -1 M). Crystal structures of 

the complex of ligand 1 with Pb(ClO4)2 was obtained and will be presented. The interaction with 

lead(II) cations was also studied by 1 H NMR [2,3]. 

[1] J.B. Neilands, Science, 156, 1967, 1443 

[2] U. Lesiska, PhD Thesis, Gdansk, Poland 2007-04-20 

[3] U. Lesiska, M. Bocheska, publication in preparation 

Acknowledgement 

FINANCIAL SUPPORT FROM GDASK UNIVERSITY OF TECHNOLOGY (DS 014668/003) ARE GRATEFULLY 

ACKNOWLEDGED 

. 

PSA 21 

Anion receptors based on the cooperation of metal coordination and 

hydrogen bonding 

Renato Bonomi, Fabrizio Mancin and Umberto Tonellato 

Università di Padova, Dipartimento di Scienze Chimiche, via Marzolo 1, 35131 Padova, Italy 

Anions are the most important species in the natural world and are critically involved in 

many of known chemical processes. They are at the center of energy transduction (ATP), 

biological information processing (DNA and RNA) or as a cofactors in many chemical 

reactions.[1] The synthesis and study of synthetic receptors for the purpose of anion recognition 

continues, therefore, to attact increasing attention within the supramulecular community. 

Since the beginning of anion coordination chemistry the main strategies in the design 

of synthetic anion complexing reagents have focused on cationic polyammonium, guanidinium 

system and a variety of Lewis acidic containing metals ions receptors.[2] In this systems the 

Coulombic forces largely dominate the long-range noncovalent communication between 

molecules. Neutral organic receptors which bind anions solely via favourable hydrogen bond 

interactions, instead, have also been recently exploited. The spherical anion is then bind by an 

array of hydrogen bonds within a cavity formed in a molecular framework. A better selectivity is 

achievable with this strategy, but low affinity is expected in competitive protic solvents. 

In this 

communication we 

describe a strategy to 

obtain new anion 

receptors with high 

binding constats and 

selectivity in acquoses 

solvents. This strategy is 

based on the 

introduction of groups 

capable to donor 

hydrogen in the 

structure of suitable 

metal ion complexes. In 

H 

N N 

N 

Mn+ A- H 

H 

H H 

H 

N 

N 

1 

N 

this way, the metal ion provides high affinity for the substrate either by coordination and 

electrostatic interactions while hydrogen bond donor groups cooperate to increase the substrate 

affinity and provide a size selective cleft for the anion itself. 

In the case of ligands 1 and 2, reported in Figure 1, three or two amino groups have been 

introduced in the in such position to allows the formations of intracomplex hydrogens bonds with 

the metal bound substrate. Preparation of the ligands and their Cu(II) and Zn(II) complexes and 

anion recognition resuts are reported. 

[1] Schrader, T.; D.Hamilton, A. Functional Synthetic Receptors, Wiley-VCH, 2005. 

[2] Beer, P.D.; Cadman, J. Coord. Chem. Rev. 2000, 205, 131. 

N 

H 

Figure 1 

H 

A 

H 

N N 

- 

N 

N 

M n+ 

N 

N N 

2 

PSA 22 

H

Self-Assembled Rosette Nanotubes with Increased Inner Diameter 

Gabor Borzsonyi, Andrew Myles, and Hicham Fenniri* 

Supramolecular Nanoscale Assembly Group, National Institute for Nanotechnology and 

Department of Chemistry, University of Alberta, Edmonton, AB, Canada 

PSA 23 

Programmed self-assembly is a desirable method to construct nanoscale materials. Bicyclic 

self-complementary DNA hybrid base G^C was previously shown to self-assemble into 

hexameric rosette supermacrocycles, which stack on one another to form rosette nanotubes 

(RNT’s) with an inner diameter 1.1 nm (Figure 1. A) 1 . We sought to increase the inner diameter 

of the RNT’s by synthesizing tricyclic derivative XG^C (Figure 1. B). The synthesis and 

characterization of the resulting expanded RNT’s will be presented. 

[1] Fenniri, H.; Mathivanan, P.; Vidale, K. L.; Sherman, D. M.; Hallenga, K.; Wood, K. V.; 

Stowell, J. G. J. Am. Chem. Soc. 2001, 123, 3854. 

PSA 24 

New fluorescent sulphonamides receptors for selective anion sensing 

Claudia Caltagirone, Philip A. Gale, Mark E. Light 

School of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK 

Selective sensing of anions is one of the most intensively-studied areas in supramolecular 

chemistry due to its potential application in the areas of medicine and environmental sensing. 

[1] Considerable efforts have been made to develop hydrogen-bonding donors/receptors 

containing urea, thiourea, amide, and sulfonamide moieties. Our recent work shows that 

receptors containing both bis-ureas based on an ortho-phenylenediamine scaffold and amides 

as hydrogen donors are particularly good receptors for carboxylates.[2][3] We decided to 

synthesise the new fluorescent receptors 1 and 2 containing the ortho-phenylenediamine 

scaffold appended with one or two dansyl groups respectively as sulfonamide hydrogen donor 

groups and investigate the fluorescent sensing properties of these systems. The results of these 

studies will be presented in this poster. 

N 

H 

O 

N 

H 

O 

HN 

S O 

N 

NH 

1 2 

[1] J.L. Sessler, P.A. Gale and W.-S. Cho, Anion Receptor Chemistry, Ed. J.F. Stoddart, Royal 

Society of Chemistry, Cambridge, 2006. 

[2] S.J. Brooks, P.A. Gale, M.E. Light, Chem. Comm., 2006, 4344.; S. J. Brooks, P.A. Gale and 

M.E. Light, Chem. Commun., 2005, 4696; S,J. Brooks, P,A. Gale and M,E. Light, 

CrystEngComm, 2005, 7, 586. 

[3] S.J. Brooks, S.E. Garcìa-Garrido, M.E. Light, P.A. Cole, P.A. Gale, Chem. Eur. J., 2007, 13, 

3320. 

N 

O 

O 

S 

N 

H 

O 

N 

H 

HN 

S 

O 

O 

N

Functional [2×2] Grids 

Xiao-Yu Cao a , Jack Harrowfield a , Jean-Marie Lehn a , Augustin Madalan a , Jonathan R. 

Nitschke a,b 

a Institut de Science et d'Ingénierie Supramoléculaires, 8, allée Gaspard Monge, 67083 

Strasbourg, France 

b Department of Organic Chemistry, University of Geneva, 30 quai Ernest-Ansermet, 1211 

Genève 4, Switzerland 

PSA 25 

Generation of well-defined supramolecular architectures from metal-directed self-assembly of 

complexes of multidentate ligands has emerged as a highly promising pathway to nanometresized 

functional materials during the last decade. Grid-type metallosupramolecular entities are 

of particular interest as they form well-defined arrays of metal ions that exhibit novel optical, 

electronic and magnetic properties. The extensively studied [2×2] grids possess similar fourfoldsymmetric 

structural features to those of the versatile scaffolds of calix-[4]arenes and 

porphyrins, but are distinguished by the ease of ringing changes such as the nature of their 

substituents, the bound metal ions and size of the ligands. 

Here, we report the modification of two types of bis-hydrazone ligands by the introduction of 

functional residues. Complex formation with metal ions [Fe(II), Co(II), Ni (II), Cu(II), Zn(II) etc.] 

gives [2×2] grids with two distinct modes of decoration. "Axial" decoration provides "bisquartet" 

receptor arrays on each side of the grid. "Lateral" decoration provides multivalent assemblies 

with eight branches surrounding the grids. The ultimate goal of this work is to produce grids with 

appropriate functionality to act as multivalent receptors for biomolecules, that is, to provide what 

may be termed “nanosized biochips”. 

[1] Nitschke, J. R.; Lehn, J.-M. Proc.Natl. Acad. Sci. U. S. A. 2003, 100, 11970-11974. 

[2] Ruben, M.; Rojo, J.; Romero-Salguero, F. J.; Uppadine, L. H.; Lehn, J.-M. Angew. Chem.-Int. 

Ed. 2004, 43, 3644-3662. 

[3] Tielmann, P.; Marchal, A.; Lehn, J.-M. Tetrahedron Lett. 2005, 46, 6349-6353. 

[4] Barboiu, M.; Ruben, M.; Blasen, G.; Kyritsakas, N.; Chacko, E.; Dutta, M.; Radekovich, O.; 

Lenton, K.; Brook, D. J. R.; Lehn, J.-M. Eur. J. Inorg. Chem. 2006, 784-792. 

[5] Cao, X.-Y.; Kyritsakas-Gruber, N.; Harrowfield, J.; Madalan, A.; Nitschke, J.; Ramirez, J.; 

Rissanen, K.; Russo, L.; Stadler, A.-M.; Vaughan, G.; Lehn, J.-M. Eur. J. Inorg. Chem. In press. 

PSA 26 

Binding studies of a protonated dioxatetraazamacrocycle with anionic 

guests 

Sílvia Carvalho a , Rita Delgado a,b , Michael M. G. Drew c , Vânia Calisto d and Vítor Félix d 

a Instituto de Tecnologia Química e Biológica, UNL, Apartado 127, 2781-901 Oeiras, Portugal; 

b Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal; C School of 

Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK d Departamento de 

Química, CICECO, Universidade de Aveiro, 3810-193 Aveiro, Portugal 

Email: silviac@itqb.unl.pt 

The interest in the recognition process of anionic species (guests) and different synthetic hosts 

arises mainly from the importance of anions in the environment, the medicine and in industry. 

The recognition is achieved by formation of non-covalent bonds between a rigid and preorganized 

host architecture and the guest sites [1,2]. 

In the present work, the association ability of H4[26]pbz2N4O2 4+ [3] for 

N 

O 

N 

[26]pbz2N4O2 

N 

O 

N 

phthalate (ph 2- ), isophthalate (iph 2- ), terephthalate (tph 2- ), 

benzenetricarboxylate (btc 3- ), citrate (cit 3- ), cyclohexanetricarboxylate 

(cta 3- ) and malonate (mal 2- ) was evaluated by potentiometric and NMR 

spectroscopic measurements. 

The binding constants of the 

(Hn[26]pbz2N4O2) n+ with the various anions 

were determined in aqueous solution at 

298.2 K and 0.10 M KCl. The strongest 

associations were observed for the iph 2- and 

btc 3- anions. 

1 H NMR titrations in D2O allowed to understand the type of 

interactions involved in the host-guest association process. 

The single crystal structures of H4[26]pbz2N4O2 4+ with ph 2- and 

tph 2- anions showed that both guests are inserted between two 

macrocyclic units forming supramolecular associations as illustrated for tph 2- in the figure above. 

The molecular recognition processes between the receptor and selected carboxylate anions 

(ph 2- , iph 2- and btc 3- ), as well as halides (F - , Cl - , Br - and I - ), were also investigated by molecular 

dynamics simulations carried out in water solution. The obtained structural and theoretical 

energetic data will be presented and compared with the experimental results. 

[1] V. Amendola, M. Bonizzoni, D. Esteban-Gómez, L. Fabbrizzi, M. Licchelli, F. Sancenón, A. 

Taglietti, Coord. Chem. Rev., 250, 1451, 2006. 

[2] S. Carvalho, R. Delgado, N. Fonseca, V. Félix, New J. Chem., 30, 247, 2006. 

[3] S. Carvalho, R. Delgado, M. G. B. Drew, V. Félix, Dalton Trans., in press 

The authors acknowledge the financial support from Fundação para a Ciência e Tecnologia (FCT) and 

POCI, with coparticipation of the European Community fund FEDER (Project n. POCI/QUI/56569/2004). 

Sílvia Carvalho also acknowledges the PhD grant from FCT (SFRH/BD/13793/2003).

PSA 27 

Structural and thermodynamic investigations on the formation of porphyrin 

metallacycles 

Massimo Casanova a , Elisabetta Iengo a , Pablo Ballester b and Enzo Alessio a 

a 

Department of Chemistry, University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy (email: 

mcasanova@.units.it) 

b 

ICIQ, Av. Països Catalans 16, 43007 Tarragona , Spain 

We previously synthesized the rhenium(I) fac-[Re(CO)3Br(Zn-4’MPyP)2] (1) [1] and 

ruthenium(II) trans,cis,cis-RuCl2(CO)2(Zn-4’MPyP)2 (2) [2] complexes in which the two zinc 

mono-pyridylporphyrins (4’MPyP) are coordinated to the metal in cis geometry. Compounds 1 

and 2, which were fully characterized by 1 H-NMR and X-ray diffraction (2), can act as tweezers 

to coordinate a ditopic nitrogen ligand of suitable geometry. 

The reactions of 1 and 2 towards 5,10-dipyridyl-15,20-diphenylporphyrin (4’cisDPyP, scheme) 

and other nitrogen ligands have now been investigated using 1 H-NMR, UV-vis spectroscopy 

and ITC titrations techniques and the binding constants determined. 

M 

N N 

N 

N 

N ZnN N ZnN 

N 

N 

4'-cisDPyP 

N 

N 

N ZnN 

NZnN N N N N 

N 

NH HN 

N 

[1] Massimo Casanova, Ennio Zangrando, Fabio Munini, Elisabetta Iengo, Enzo Alessio, Dalton 

Trans., 2006, (42),5033-5045 

[2] Enzo Alessio, Michela Macchi, Sarah L. Heath and Luigi G. Marzilli, Inorg. Chem. 1997, 36, 

5614-5623 

M 

N N 

The synthesis and characterisation of a porphyrin functionalized with 

2,2’:6’,2”-terpyridine ligands 

Paulina Chwalisz, Edwin C. Constable, Catherine E. Housecroft. 

Department of Chemistry, University of Basel, Spitalstrasse 51, 

CH-4056, Basel, Switzerland. 

PSA 28 

Porphyrins have been extensively studied for the last fifty years and there are many actual and 

potential applications making such systems very attractive synthetic targets. They may be 

applied as electrochemical sensors or in the area of alternative energy sources. More recently, 

they have been studied for applications in photodynamic therapy.[1] 

Herein, we present the synthetic route employed to obtain porphyrin functionalized 2,2’:6’,2”terpyridine 

(tpy) ligands and their metal complexes. Introducing the tpy component offers a 

means to coordinate a range of metals in a pseudo-octahedral geometry in addition to the 

porphyrin N4 donor site. 

The synthetic strategy for the preparation of terpyridine-based porphyrins is based on Lindsey’s 

procedure [2], in which catalytic amounts of a Lewis acid (Et2O:BF3) are used. The 

condensation reaction between pyrrole and 4’-phenylcarbonyl-2,2’:6’,2’’-terpyridine carried out 

in dichloromethane is employed for the synthesis of the target ligand. 

[1] Pandey, R. K.; Zheng, G. Porphyrins as Photosensitizers in Photodynamic Therapy, in The 

Porphyrin Handbook, Kadish, K. M.; Smith, K. M.; Guilard, R., editors; Academic Press: San 

Diego, CA, 2000; Vol. 6, Chapter 43, pp. 157- 230. 

[2] Lindsey, J. S. Synthesis of meso-Substituted Porphyrins, in The Porphyrin Handbook, 

Kadish, K. M.; Smith, K. M.; Guilard, R., editors; Academic Press: San Diego, CA, 2000; Vol. 1, 

Chapter 2, pp. 45-118.

Neutral supramolecular systems incorporating bis--diketonat metallocyclic 

building blocks: a remarkable reversible single crystal-singol crystal bond 

breaking/bond forming transformation under pressure. 

Jack K. Clegg a , Katrina A. Jolliffe b , Leonard F. Lindoy, a Simon Parsons, c David Schilter, b Peter 

Tasker c and Fraser J. White. c 

a 

Centre for Heavy Metals Research, School of Chemistry, F11, University of Sydney, NSW, 

Australia, 2006. 

b 

School of Chemistry, F11, University of Sydney, NSW, Australia, 2006. 

c 

Centre for Science at Extreme Conditions and School of Chemistry, King’s Buildings, 

University of Edinburgh, West Mains Road, Edinburgh, Scotland, EH9 3JJ 

The interaction of a variety of aryl-linked bis--diketones with cobalt(II), nickel(II), copper(II), 

zinc(II), gallium(III), iron(III) and zirconium(IV) has been investigated with the aim of obtaining 

new metallo-supramolecular assemblies. New binuclear, trinuclear and tetranuclear assemblies 

have been shown to form in a variety of geometries including helical, co-bifacial, triangular and 

tetrahedral arrangements that reflect the directional properties of the ligand and the metal 

ion.[1-2] 

In particular, the use of copper(II) leads to the formation of neutral dinuclear and trinuclear 

species containing coordinatively unsaturated metal centres. These can then be reacted with 

nitrogen-containing ligands to form extended ‘linked’ structures including discrete ‘dimers of 

dimers’ and a variety of 1D, 2D and 3D network solids.[3-4] 

When using 1-methylpiperazine as a ‘linking’ ligand a one dimensional chain polymer results (I). 

When a single crystal of this complex is loaded into a diamond anvil cell and the pressure 

increased, a fully reversible chemical reaction occurs. The structure transforms from a polymer 

to a discrete dimeric species (II). This transformation is accompanied by a phase change from 

triclinic to monoclinic. This is the first such example of a reversible pressure induced singlecrystal 

to single-crystal chemical reaction yet reported. 

[1] D. J. Bray, J. K. Clegg, L. F. Lindoy, D. Schilter, Adv. Inorg. Chem., 2006, 59, 1-39 

[2] J. K. Clegg, D.J. Bray, K. Gloe, K. Gloe, M. J. Hayter, K. A. Jolliffe, G. A. Lawrance, G. V. 

Meehan, J. C. McMurtrie, L. F. Lindoy, and M. Wenzel, Dalton Trans., 2007, in press. 

[3] J. K. Clegg, Aust. J. Chem. 2006, 59, 660; 

[4] J. K. Clegg, K. Gloe, M. J. Hayter, O. Kataeva, L. F. Lindoy, B. Moubaraki, J. C. 

McMurtrie, K. S. Murray and D. Schilter, Dalton Trans., 2006, 3977; 

PSA 29 

A ditopic biomimetic receptor : role of the 1 st , 2 nd and 3 rd coordination 

spheres. 

D. Coquière a , T. Prangé b , J. Marrot c , B. Colasson a , O. Reinaud a . 

PSA 30 

a Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, 

Université René Descartes, 45 rue des Saints-Pères, 75270 Paris cedex 06, France 

b Laboratoire de Cristallographie, UMR CNRS 8015, Université René Descartes, 4 avenue de 

l’Observatoire, 75270 Paris cedex 06, France 

c Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles St-Quentin en 

Yvelines, 45 av. des Etats-Unis, 78035 Versailles cedex, France 

Calix[6]arenes are superb molecular platforms offering a -basic hydrophobic cavity that can act 

as a selective receptor for a variety of molecules. For such a case, only the cone conformation 

of the calixarene is able to act as a molecular host. We have extensively described a system 

that presents a biomimetic tris-imidazole core at the small rim [1]. This system allows efficient 

binding of a metal ion such as Zn(II) that acts as a glue, fixing at the same time three aromatic 

units of the calixarene core. As a result, the tetrahedral complex behaves as a remarkable 

receptor for small exogenous neutral ligands. 

Recently, we have discovered efficient methods allowing the selective functionalization of the 

calixarene large rim [2, 3]. This opened the possibility of synthesizing ditopic calixarene ligands. 

Here, the coordination chemistry and the host-guest properties of a calix[6]arene containing a 

nitrogenous binding site at each rim are presented [4]. 

Zn(II)-monometallic complex (left) hosting a dopamine derivative and Zn(II)-bimetallic complex 

(right) encapsulating H302 - . 

[1] O. Sénèque, M.-N. Rager, M. Giorgi and O. Reinaud, J. Am. Chem. Soc., 2001, 123, 8442. 

[2] S. Redon, Y. Li and O. Reinaud, J. Org. Chem., 2003, 68, 7004. 

[3] D. Coquière, H. Cadeau, Y. Rondelez, M. Giorgi and O. Reinaud, J. Org. Chem., 2006, 71, 

4059. 

[4] D. Coquière, J. Marrot and O. Reinaud, Chem. Commun., 2006, 3924.

PSA 31 

Anion-promoted deprotonation processes in urea-metallocyclam conjugates 

Guido Colucci, Luigi Fabbrizzi, Mauro Garolfi, Maurizio Licchelli 

Dipartimento di Chimica Generale, viale T. Taramelli 12, I-27100 Pavia, Italy 

The metal complexes of the azacyclam derivative 1 were prepared by a one-pot synthesis 

involving the condensation of the open-chain tetraamine 1,9-diamino-3,7-diazanonane with 

formaldehyde and 4-nitrophenylurea, in the presence of Cu II or Ni II . Similar template reactions 

have been extensively investigated along the last two decades and allow one to introduce a 

variety of functionalities onto the cyclam framework [1]. 

450 nm 

Complexes [Cu(1)] 2+ and [Ni(1)] 2+ display the expected solution properties of macrocyclic 

complexes, in particular, a high stability toward demetallation, even in strongly acidic media. 

The absorption spectrum of [Cu(1)] 2+ shows a strong band centred at 335 nm (14700 M 1 cm 1 ) 

ascribed to the nitrophenylurea moiety and a much weaker band at 520 nm due to a d-d 

transition. On addition of fluoride, the band at 335 nm decreases, while a new band appears at 

452 nm, whose intensity reaches a limiting value at 2 equiv. of F . This spectral change has to 

be ascribed to the deprotonation of the NH fragment, with formation of HF2 and has been 

previously observed in urea derivatives containing strongly electron-withdrawing substituents 

[2]. Similar results were observed on titration with acetate. 

On titration of the model urea derivative 2, the new band begins to develop only on addition of 

large excess of fluoride (or acetate) and its intensity is in any case much lower than that 

observed in the case of [Cu(1)] 2+ . These results show that the proximate metallocyclam subunit 

strongly enhances the acidity of the urea NH fragment, probably due to the coordination of the 

deprotonated amide group to the metal centre, according to a scorpionate mode. Further 

studies are in progress in order to define the role of the metal in the anion interaction at the 

amide functionality in azacyclam complexes. 

[1] A. De Blas, G. De Santis, L. Fabbrizzi, M. Licchelli, A. M. Manotti Lanfredi, P. Morosini, P. 

Pallavicini, F. Ugozzoli, J. Chem. Soc., Dalton Trans. 1993, 1411-1416 and references therein. 

[2] (a) M. Boiocchi, L. Del Boca, D Gomez, L. Fabbrizzi, M. Licchelli, E. Monzani, J. Am. Chem. 

Soc. 2004, 126, 16507-16514; (b) V. Amendola, D. Esteban-Gomez, L. Fabbrizzi, M Licchelli, 

Acc. Chem. Res. 2006, 39, 343-353. 

Novel jellyfish-shaped amphiphilic cyclic oligosaccharide analogues: 

synthesis and self-aggregation properties 

Cinzia Coppola, Lorenzo De Napoli, Giovanni Di Fabio and Daniela Montesarchio 

Dipartimento di Chimica Organica e Biochimica, Università degli Studi di Napoli “Federico II”, 

Complesso Universitario di Monte S. Angelo, via Cintia, 4, I-80126 Napoli, Italy 

Carbohydrates are attractive scaffolds for the construction of macrocycles since they are 

rigidified building blocks, displaying multiple, selectively manipulable hydroxyl functional groups 

with a well defined stereochemistry. Among the plethora of natural or artificial macrocycles 

known from the literature, a great deal of attention is currently devoted to amphiphilic 

cyclodextrins 1 , obtained by grafting lipophilic appendages on the cyclic oligosaccharide core. 

Sugar-containing amphiphilic molecules are cell membrane mimics and are expected to be 

biocompatible. They may be inserted into lipid systems as natural or artificial membranes 

through their hydrophobic moiety and act as transmembrane ion channels 2 . Fine tuning of the 

properties and complexation abilities of cyclic oligosaccharides can be achieved by selectively 

modifying their oligosaccharide backbone, for example by replacing the O-glycosidic bonds with 

more chemically and enzymatically stable interglycosidic linkages. 

In this frame we focused our attention on a new family of cyclic oligosaccharide analogues 

having the glucoside units connected through phosphodiester linkages. In particular, we have 

synthesized, by exploiting both solid phase and classical solution approaches, cyclic phosphatelinked 

oligosaccharides (CyPLOS) composed of phenyl-β-D-glucopyranosyl monomers 4,6linked 

through phosphodiester bonds (1-3, Figure). Key intermediate in our synthetic strategy 

was a suitable phosphoramidite derivative of phenyl-β-D-glucopyranoside (4). 3 

PhO 

HO 

O 

O 

P 

O 

-O OH 

O O 

P 

O 

O 

- 

O 

HO 

1 (n=1) 

2 (n=2) 

3 (n=3) 

O 

OH 

OPh 

n 

NC 

N 

P 

O 

O 

BzO 

4 

ODMT 

O 

OPh 

OBz 

PSA 32 

Starting from differently derivatised carbohydrate scaffolds, our synthetic efforts are currently 

devoted to cyclic phosphate-linked oligosaccharides with a broader chemical diversity. We here 

present a set of novel jellyfish-shaped amphiphilic CyPLOS, functionalised with long aliphatic, 

flexible chains on the secondary hydroxyls. The self-aggregation properties of these cyclic 

oligosaccharides have been investigated by means of 1 H and 31 P NMR, CD and UV 

spectroscopy. We envisage that these novel artificial carbohydrate analogues can display 

interesting properties, by virtue of their characteristic amphiphilic nature, as well-defined selfassembling 

materials able to selectively transport cations through membranes. 

[1] a) A.R. Hedges, Chem. Rev., 1998, 98, 2035-2044; b) B. Perly, S. Moutard, F. Djedaïni- 

Pilard, PharmaChem, 2005, 4, 4-9. 

[2] L. Jullien, T. Lazrak, J. Canceill, L. Lacombe, J. M. Lehn, J. Chem. Soc., Perkin Trans. 2 

1993, 1011. 

[3] a) G. Di Fabio, A. Randazzo, J. D’Onofrio, C. Ausin, A. Grandas, E. Pedroso, L. De Napoli 

and D. Montesarchio, J. Org. Chem., 2006, 9, 3395-3408. b) J. D’Onofrio, C. Coppola, G. Di 

Fabio, L. De Napoli, and D. Montesarchio, Eur. J. Org. Chem., 2007, in press.

PSA 33 

Ratiometric Ion Sensors by Rational Design: Modulated Resonance Energy 

Transfer in Fluorescence Sensing of Cations 

Ali Coskun, Ruslan Guliyev and Engin U. Akkaya* 

Middle East Technical University, Department of Chemistry, 06531 Ankara, Turkey. 

Fluorescent chemosensor design is an active field of supramolecular chemistry, not only 

because of potential practical benefits in cell physiology, analytical and environmental 

chemistry, but also as a proving ground for manipulation and/or engineering of various 

photophysical processes towards an ultimate goal of selective and sensitive signaling of 

targeted molecular or ionic species. Recently, boradiazaindacenes have become the 

fluorophore of choice in many chemosensor designs, not only because of their exceptional 

properties as fluorophores, but also as a result of their remarkably rich chemistry. Previously, 

we reported[1] a dimeric boradiazaindacene, which can be converted into an energy transfer 

cassette and furthermore, into a ratiometric ICT (internal charge transfer) based cation sensor, 

selective for silver ions, all through simple structural modifications. In that design the two 

fluorophores were kept very close to each other, so that the through-space EET was nearly 

100% efficient, thus creating a large pseudo-Stokes’ shift chemosensor. ICT based 

chemosensors typically, have an advantage of two distinct emissive states, (analyte-free and 

analyte-bound) which makes these chemosensors potentially wavelength-ratiometric i.e., 

internal referencing of the signal is possible, eliminating potential artifacts.[2] 

We now demonstrate that the EET modulation can be either on the energy donor or 

energy acceptor site. 

EET 

D A R 

Larger EET 

D A R 

[1] Coskun, A.; Akkaya, E. U. J. Am. Chem. Soc. 2005, 127, 10464. 

[2] Coskun, A.; Akkaya, E.U. J. Am. Chem. Soc. 2006, 128, 14474. 

D 

EET 

Smaller EET 

A 

D A 

Artificial transmembrane ion channels from commercial surfactants 

Khayzuran S. J. Iqbal, Marcus C. Allen, Flavia Fucassi and Peter J. Cragg 

PSA 34 

School of Pharmacy and Biomolecular Sciences, University of Brighton, Brighton BN2 4GJ, UK 

As part of our ongoing interest in artificial transmembrane ion channels 1 we wished to harness 

the membrane penetrating qualities of these surfactants to the ion specific filtering abilities of 

rigid macrocycles. Thus far the examples in the literature relate predominantly to modified 

calixarenes 2 and derivatives that pair up within a bilayer to effect transport in a manner 

reminiscent of the gramicidin class of antibiotics. 3 Here we report preliminary results for Na + 

transport across a phospholipid bilayer by a new class of transmembrane ion channel mimetic 

compounds where the filtering effect of a calixarene has been coupled to the membrane 

piercing qualities of a commercial surfactant. Compound 1 was prepared through tosylation of 

commercially available Triton X-100 ® . Reaction of 1 with 4-t-butylcalix[4]arene in a 2:1 ratio, 

according to literature procedures for 1,3-dialkylation of calixarenes, 4 yielded compound 2. We 

then prepared a trisubstituted derivative with no free phenolic groups, 3, from the larger 

homologue, 4-t-butylcalix[6]arene trimethylether. Electrophysiology data show that at low 

concentrations 3 forms single channels (Na + flux: 7 x 10 6 ions s -1 ) but at higher concentrations 

multiple insertions occur without compromising membrane integrity. 

Synthesis of Tritonylcalixarenes Bilayer conduction of Na + : a) 4 µM and b) 64 µM 

[1] K. S. J. Iqbal and P. J. Cragg, Dalton Trans., 2007, 26. 

[2] J. de Mendoza, F. Cuevas, P. Prados, E. S. Medows and G. Gokel, Angew. Chem. Int. Ed., 

1998, 37, 1534; V. Siderov, F. W. Kotch, J. L. Keubler, Y.-F. Lam and J. T. Davis, J. Am. Chem. 

Soc., 2003, 125, 2840. 

[3] Y. Tanaka, Y. Kobuke and M. Sokabe, Angew. Chem. Int. Ed. Engl., 1995, 34, 693. 

[4] M. D. Lankshear, A. R. Cowley and P. D. Beer, Chem. Commun., 2006, 612.

PSA 35 

Molecular design of macrocyclic receptors containing two phenanthroline 

units and evaluation of their binding ability 

Carla Cruz a , Rita Delgado b,c , Michael G. B. Drew d , Vítor Félix a 

a Departamento Química, CICECO, Universidade de Aveiro, 3810-193 Aveiro, Portugal 

b Instituto de Tecnologia Química e Biológica, UNL, Apartado 127, 2781-901 Oeiras, Portugal 

c Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal 

d School of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK 

Carboxylate substrates participate in many chemical, biological and environmental processes. 

A wide number of these compounds is used in several industrial (e.g. toys) and agricultural 

applications (e.g pesticides). 1 Searching for suitable synthetic sensors for these substrates, the 

molecular design of macrocyclic receptors incorporating two 

phen moieties was undertaken. 3 The (Hi[26]phen2N4O2) i+ , 

(Hi[26]phen2N6) i+ and (HiMe2[30]phen2N6) i+ receptors, were 

synthesized and their acid-base behaviour evaluated by 

potentiometric and 1 H NMR methods. 3 For [26]phen2N4O2, five 

protonation constants were determined, the fifth proton is 

located in one of the phen nitrogen atoms. This assignment, 

was confirmed by the crystal structures of the receptor as 

bromide and chloride salts. In the solid state, the 

(H5[26]phen2N4O2) 5+ cation adopts a “horseshoe” topology with 

{(H5[26]phen2N4O2)Br4(H2O)} + 

enough room to accommodate three or four halogen anions 

through the N–H···X (Cl - or Br - ) hydrogen bonding interactions 

(left). This structural result prompted us to envisage these 

receptors as good candidates to promote the selective uptake of carboxylate substrates through 

the establishment of multiple and cooperative electrostatic interactions and hydrogen bonds. 

The binding interaction of the three receptors with several carboxylates (bzc - , naphc - , anthc - , 

pyrc - , ph 2- , iph 2- , tph 2- and btc 3- ) and herbicides (PMG, ATCP and 

2,4-D) was investigated in water. The binding data available now 

show that the Hi[26]phen2N4O2 i+ uptakes selectively charged or 

extended aromatic carboxylate anions, such as btc 3- (4.0–8.5 pH 

range) and pyrc - (pH < 4.0) from an aqueous solution containing 

the remaining aliphatic and aromatic anions as pollutants or 

contaminants. A further insight on the molecular recognition 

process was obtained by molecular dynamics simulations in water 

solution. For example, the binding of btc 3- to the 

(H5[26]phen2N4O2) 5+ occurs with insertion of the anion between 

the two phen units showing that the molecular recognition 

involves N–H···O multiple hydrogen bonds complemented by - 

stacking interactions (right). 

[1] V. Amendola, M. Bonizzoni, D. Esteban-Gómez, L. Fabbrizzi, M. Licchelli, F. Sancenón and 

A. Taglietti, Coord. Chem. Rev. 2006, 250, 1451–1470. 

[2] K. E. Krakowiak, J. S. Bradshaw, W. Jiang, N. K. Dalley, G. Wu and R. M. Izatt, 

J. Org. Chem. 1991, 56, 2675–2680. 

[3] C. Cruz, R. Delgado, M. G. B. Drew and V. Félix, J. Org. Chem. 2007, in press. 

The authors acknowledge the financial support from Fundação para a Ciência e Tecnologia 

(FCT) and POCI, with coparticipation of the European Community fund FEDER (Project n. 

POCI/QUI/56569/2004). C. C. acknowledges the PhD grant from FCT (SFRH/BD/19266/2004) 

and ITQB for the access to the potentiometric and NMR facilities. 

Controlled uptake-release of the citrate anion in a system capable of 

pH-driven triple Cu 2+ translocation 

Giacomo Dacarro, Piersandro Pallavicini, Angelo Taglietti 

Dipartimento di Chimica Generale, Università di Pavia, v.le Taramelli, 12 – 27100 Pavia 

The pH-controlled translocation of one or two metal cations plays an important role for the 

change in shape and in the secondary coordinative properties of the molecular system inside 

which the process takes place.[1] As an example, we have recently demonstrated that in a 

macrocyclic system capable of double Cu 2+ translocation, the pH-controlled movement of the 

cations may be exploited for the uptake-release of a bridging imidazolate anion.[2] We have 

now sinthesized non-cyclic ligands capable of simultaneous double and triple pH-controlled 

Cu 2+ translocation. The movement of the cations from sites in which they are coordinatively 

saturated to sites in which they are coordinatively unsaturated candidates these system for the 

controlled uptake-release of multidentate anionic species, thanks also to the particular geometry 

of the multicomponent ligands. In particular, we have found that in a system capable to 

simultaneously move three Cu 2+ cations, the citrate anion is selectively bound at pH 6, when the 

Cu 2+ cations are inside binding sites in which only four donors are coordinating them, giving a 

complex with an overall + 6 charge. A jump to pH values higher than 8 makes the three Cu 2+ 

cations to move inside deprotonated amino-amido binding sites, forming a coordinatively 

saturated and neutral complex. As a consequence, the citrate anion is released. 

N N 

N 

N 

O 

NH 

HN 

O O 

HO N NHO 

NHNH 

N 

N 

HNO NH 

O 

NH 

HN 

O 

O 

O 

HN NH 

O 

O 

O 

- 6H + 

+ 6H + 

N N 

N 

N 

HN NH 

N 

N 

HN NH 

HN 

NH 

N N 

- - N 

N O 

N 

N 

- 

- O 

O - 

- O 

O 

O 

+ 

O 

O 

O 

O 

PSA 36 

[1] a) P. Pallavicini, G. Dacarro, C. Mangano, S. Patroni, A. Taglietti and R. Zanoni, Eur. J. 

Inorg. Chem., 2006, 4649-4657; b) A. Aurora, M. Boiocchi, G. Dacarro, F. Foti, C. Mangano, P. 

Pallavicini, S. Patroni, A. Taglietti and R. Zanoni, Chem. Eur. J., 2006, 12, 5535; c) V. 

Amendola, L.Fabbrizzi, C. Mangano, H. Miller, P. Pallavicini, A. Perotti and A. Taglietti, Angew. 

Chem. Int. Ed., 2002, 41, 2553; d) V. Amendola, L. Fabbrizzi, C. Mangano and P. Pallavicini, 

Acc. Chem. Res., 2001, 34, 488 

[2] L. Fabbrizzi, F. Foti, S. Patroni, P. Pallavicini and A. Taglietti, Angew. Chem. Int. Ed., 2004, 

43, 5073 

O 

O 

O

A photocontrollable receptor for Cu II 

Giacomo Dacarro, Paola Ricci, Angelo Taglietti 

Dipartimento di Chimica Generale Università degli Studi di Pavia, Viale Taramelli 12, 27100 

Pavia, Italy 

Ligand LH2 shows the expected behaviour towards transition metal cations: it is able to bind 

only Ni II and Cu II as a consequence of deprotonation of amido groups, to give neutral 

complexes. Moreover, the different position in the Irving- Williams series accounts for the ability 

of the ligand to discriminate between the two cations: at pH between 4.5 and 6.5 only Cu II is 

bound by this receptor, even in presence of other cations. This behaviour is shared by a big 

number of ligands based on the diamino-diamido donor set, [1] but in this case the receptor 

features are photocontrollable. When linear LH2 is irradiated for a few minutes with a 366 nm 

radiation in a degassed water/methanol (4:1) solution, the disappearance of the tipical 1 La 

anthracene band is observed. 1 H-NMR 

spectra confirms the formation of 

macrocyclic ligand LCH2, which is 

obtained via a [4s+4s 

photocicloaddition. When the ligand is 

in the cyclic form, no binding of Cu II and 

Ni II is observed in the studied pH 

range. Molecular modelling of the cyclic 

ligand show a highly strained structure 

and a cavity which is not preorganized 

to bind cations. Thus, in this case the 

high enthalpic demand for the 

deprotonation of amidic groups is not 

balanced by an appropriate energy gain 

coming from complex formation. 

Moreover, no cyclization is observed 

when CuL is irradiated in the same 

conditions. The macrocyclic compound 

LCH2 reverts to the open form, at room 

temperature and in the dark, following a 

first order kinetic with an half time of 8 

LH2 

LCH2 

NH HN 

NH HN 

O O 

NH HN 

NH HN 

O O 

NH HN 

NH HN 

hours. The rate of the back reaction can be controlled with temperature: for example it becomes 

20 times faster if temperature is raised to 45 °C. This kind of photocicloaddition reaction, which 

is well known in literature and applied to several photoswitchable systems, [2] was applied for 

the first time to a poliamminic ligand and in aqueous solution, to obtain a photocontrollable 

receptor selective for Cu II . In addition, variations of the acid-base properties are observed upon 

irradiation: when the ligand is in the diprotonated form (pH0.5 pH units). 

[1] L. Fabbrizzi, M. Licchelli, P. Pallavicini, A. Perotti, A. Taglietti, D. Sacchi, Chem. Eur. J., 

1996, 2, 1, 167 

[2] a) H. Bouas-Laurent, A. Castellan, J. P. Desvergne, R. Lapouyade, Chem. Soc. Rev., 2000, 

29, 43; b) Y. Molard, D. M. Bassani, J. P. Desvergne, N. Moran, J. H. R. Tucker, J. Org. Chem., 

2006, 71, 8523-8531 

T 

h 

Cu 2+ , OH - 

Cu 2+ , OH - 

N 

N 

Cu +2 

Cu +2 

N 

O O 

h 

N 

O O 

PSA 37 

CuL 

PSA 38 

Synthesis of biomimicking receptors by the molecular imprinted polymers 

(MIP) technique, for application in chemical sensors 

Maria Pesavento, Girolamo D’Agostino, Antonella Profumo, Giancarla Alberti, Raffaela Biesuz, 

Dip. Chimica Generale, Università di Pavia. Via Taramelli 12, I-27100 Pavia, Italy 

The concepts of supramolecular assembling of molecules are applied to the preparation of 

molecular imprinted polymers (MIP). These are solids containing sites exactly suited to 

accommodate a particular molecule, the template. 

Solids of this kind have a number of useful applications as selective receptors, for 

example for the extraction of the template from complex matrices [1] and for sensors [2]. As a 

matter of fact, the central part of a chemical or biochemical sensor is the recognition element, 

which is responsible for specifically binding the target analyte, while the transducer translates 

the chemical signal generated upon binding into a quantifiable output signal. The recognition 

element is usually a biological molecule such as an antibody or enzyme. The biomolecules have 

some drawbacks, so that biomimetic receptor systems capable of binding target molecules with 

affinities and specificities similar to natural receptors have been synthesized. Whereas for small 

target molecules, such as inorganic ions, artificial receptors can often be obtained through 

rational design and chemical synthesis [3] this may prove difficult if the analyte is a large and 

complex molecule. Molecular imprinting in synthetic polymers (MIP) is being increasingly 

adopted in this case and have therefore been called ‘antibody mimics’ [4] 

The scheme of the molecular imprinting procedure is here reported 

The imprinting is obtained by associating the target molecule with polymerizable active 

monomers (methacrylic acid in the case of the MIPs here synthesized) in a solvent, through 

relatively weak bonds as hydrogen bonds, dipole-dipole and lipophilic interaction, and by bulk 

polymerization in the presence of a crosslinker. 

In this investigations the target molecules (templates) are some triazines (atrazine and cyanuric 

acid), and a thioxantene, ITX (isopropyl-9H-thioxanthen-9-one). 

A potentiometric sensor ISE for atrazine based on MIP membranes, was obtained [5] 

The membranes were characterized electrochemically in aqueous solution. 

It has been found that when a potential step of –850 mV vs Ag/AgCl(sat) is applied to a glassy 

carbon electrode in contact with a MIP membrane a current flows, decreasing with time. 

The faradic process is not ascribable to the target molecules, nevertheless the current 

intensity depends on the concentration of the template in the aqueous solution phase. This is 

due to a variation of the conductivity of the membrane resulting from the association of the 

template to the specific site in MIP. The observed effect was very specific for the template. In 

the case of analogous polymers, obtained in the absence of the template (NIP), the current was 

independent of the concentration. 

. 

[1] A.Martin-Esteban, Fresenius J Anal Chem., 2001, 371, 370-795 

[2] K.Haupt, K. Mosbach,) Chem Rev, 2000, 100,2495-2504 

[3] J.-M Lehn, Supramolecular Chemistry; 1995, Wiley-VCH: Weinheim,. 

[4] G. Vlatakis, L. I Andersson, R Muller, and K. Mosbach, Nature 1993, 361, 645-650. 

[5] G D’Agostino, G. Alberti, R. Biesuz and M. Pesavento, Biosensors and Bioelectronics, 2006, 

2, 145-152.

PSA 39 

Cucurbit[n]uril as Supramolecular Structures and Drug Delivery Vehicles 

Yunjie Zhao a , Linta Chalissery a , Beth Campbell a , Damian Buck a , Gant Collins a and Anthony 

Day a 

a Chemistry, School of Physical Environmental and Mathematical Sciences, University of New 

South Wales @ Australian Defence Force Academy, Canberra, ACT 2600, Australia. Email: 

a.day@adfa.edu.au 

Supramolecular structures as drug delivery vehicles are of interest as methods to increasing the 

efficacy and/or decreasing the toxicity of pharmaceutical applications. Increased efficacy can 

potentially be achieved via improved bio-stability, slow release, effective targeting of a drug to 

be delivered, and improved solubility. A reduction in toxicity of pharmaceuticals can potentially 

be achieved by selective delivery, concentration controls via slow release, and by limiting bioside-reactions. 

We have found that cucurbit[n]uril, Q[n], have the potential to achieve some of 

the above goals by direct encapsulation of drugs.[1,2] As an ongoing study into drug delivery 

and Q[n] utility in this area, we have made a foray into the employment of Q[n] as a component 

within micelles to form pockets capable of holding drugs or direct encapsulation of a drug and 

the embedding of the association complex within the micelle. In addition, and as an extension 

to this approach we have examined the use of Q[n] as an aid to drug delivery where the Q[n] 

acts as a spacer to generate cavities within the core of modified dendrimers, as an indirect Q[n] 

application. 

[1] Mark S. Bali, Damian P. Buck, Andrew J. Coe, Anthony I. Day and J. Grant Collins, 

“Cucurbituril binding of trans-[{PtCl(NH3)2(µ-NH2(CH2)8NH2)] 2+ and the effect on the reaction 

with cysteine”, J. . Chem. Soc. Dalton 2006, 45,5337-44. 

[2] Nial J. Wheate, Damian P. Buck, Anthony I. Day and J. Grant Collins “ Cucurbit[n]uril binding 

of platinum anticancer complexes”, J. Chem. Soc. Dalton 2006, (3) 451-455. 

PSA 40 

Gas phase computational and experimental characterization of a 

tetraphosphonate “aquarius” cavitand that carries water and alcohols 

Chris Harmon a , Jason Furlow a , Chadin Dejsupa a , Enrico Dalcanale b , and David V. Dearden a 

a Department of Chemistry and Biochemistry, C100 Benson Science Building, Brigham Young 

University, Provo, Utah 84602-5700 U.S.A. 

b Dipartimento di Chimica Organica ed Industriale and INSTM, Università di Parma, Parco Area 

delle Scienze 17/A, 43100 Parma, Italy 

Whereas supramolecular hosts that bind ammonium or metal ions in the gas phase are 

relatively common, hosts for alcohols are rare. We report computational and experimental 

characterization of a tetraphosphonate resorcarene host 1 (Figure 1) that selectively binds 

water and alcohols in the gas phase, which we believe is the first example of such a system. 

CH3 H3C O O CH3 P 

P 

O 

O 

O 

O 

H 3C 

O 

O 

P 

H3C O 

CH 3 

O 

O 

P 

O CH3 Figure 1. The “aquarius” 

cavitand 1. 

CH 3 

Using extensive conformational searching with the MMFF force 

field, followed by full geometry optimization at the B3LYP/6- 

31G* level of theory, we have computed gas phase structures 

and energies for low energy conformers of 1 and its complexes 

with H3O + , H3O + •H2O, and various protonated primary and 

secondary alcohols. The computed B3LYP/6-31G* binding 

energy for H3O + is 430.8 kJ mol –1 . As the length of the alkyl 

chain increases for n-alcohols, the binding energy decreases 

from about 380 kJ mol –1 for methanol down to about 350 kJ 

mol –1 for n-butanol through n-heptanol. The smaller n-alcohols 

bind preferentially with the alkyl chain inside the resorcarene 

cavity (Figure 2), but as chain length increases this preference 

reverses and for n-propanol and longer alkyl groups the chain 

points out of the cavity. 

These results are consistent with experiments carried out using 

Fourier transform ion cyclotron resonance mass spectrometry, 

which indicate that under collisional activation the alcohol 

complexes dissociate primarily via loss of the hydrocarbon chain 

to produce the very stable hydronium complex. Dissociation 

thresholds from energy-resolved experiments [1] are also 

consistent with the computational results; in particular, the 

threshold for loss of water from the H3O + •H2O complex (with a 

B3LYP/6-31G* water binding energy of 137.5 kJ mol –1 ) is much 

less than that for loss of water from the H3O + complex (computed 

water binding energy of 430.8 kJ mol –1 ). All of the complexes we 

have examined are labile toward exchange of water or alcohol for 

ethanol; we report ethanol exchange rate constants for each of 

the complexes. This work is supported by the U.S. National 

Science Foundation (NSF CHE 0615964). 

Figure 2. B3LYP/6-31G* 

computed structure of 

the “tail in” complex of 

protonated ethanol 

(space filling) with 1 

(tubes). 

[1] Zhang, H.; Ferrell, T. A.; Asplund, M. C.; Dearden, D. V. Int. J. Mass Spectrom. 2007, in 

press.

New emitters for mass spectrometric observation of supramolecular 

complexes: sonic spray and porous polymer monolith electrospray 

Nannan Fang, Joseph S. Gardner, Roger G. Harrison, John D. Lamb, David V. Dearden 

Department of Chemistry and Biochemistry, C100 Benson Science Building, Brigham Young 

University, Provo, Utah 84602-5700 U.S.A. 

Supramolecular complexes present special challenges to mass spectrometry (MS). 

Supramolecular samples are typically available in small amounts, are often impure, and require 

special care to avoid dissociation as they are transferred into the gas phase. Most current 

supramolecular MS work uses electrospray ionization (ESI), but even ESI is too energetic for 

many supramolecular complexes. We discuss two new approaches to introduce 

supramolecular complexes into the gas phase for MS study. 

In sonic spray ionization (SSI) [1], dissolved samples (typically mM concentrations) are pumped 

through a capillary that is nested inside a second, larger capillary. Gas is pumped through the 

larger capillary such that it emerges with sonic velocity. This sheath gas nebulizes the sample 

solution into small droplets that evaporate, gently introducing the analyte into the mass 

spectrometer interface. We have successfully observed metal-assembled resorcinarene and 

triazine complexes using this method, in many cases detecting species we could not observe 

using conventional electrospray ionization (ESI). 

Typical ESI sources tend to discriminate in favour of 

easily ionized species. The result is relative peak 

heights that are not representative of solution 

concentrations. One answer to this problem is to use 

ESI spray emitters with orifices on the order of 1 m ID, 

which produce droplets so small that a typical droplet 

contains less than one analyte complex. However, 

these “nanospray” emitters tend to plug or break, and 

produce low absolute signal strength (because the low 

nL h –1 flow rates result in fewer ions delivered per unit 

time). We have investigated the use of porous polymer 

monolith (PPM) emitters [2] as a means of retaining the 

advantages of nanospray without incurring the 

disadvantages noted above. PPM emitters involve 

formation of a porous polymer in the end of a relatively 

large (75-150 m ID) capillary, resulting in many small 

emission sources (Figure 1). In comparison to 

conventional tapered fused silica microelectrospray 

emitters, the PPM emitters produce generally stronger 

absolute signal with much greater temporal stability, 

Figure 1. Electron micrograph of 

the end of a PPM emitter. 

PSA 41 

which we demonstrate through observations of well-characterized 18-crown-6•alkali cation 

complexes. Further, the PPM emitter produced relative peak heights for the various complexes 

in good agreement with known concentration ratios in solution, in contrast to conventional ESI 

emitters. These emitters therefore appear promising for MS studies of supramolecular systems. 

This work is supported by the U.S. National Science Foundation (NSF CHE 0615964). 

[1] Gardner, J.S.;Harrison,R.G.;Lamb,J.D.;Dearden,D.V. New J. Chem. 2006, 30, 1276- 

1282. 

[2] Koerner, T.; Turck, K.; Brown, L.; Oleschuk, R. D. Anal. Chem. 2004, 76, 6456-6460. 

PSA 42 

Dynamic Covalent Chemistry of Formaldehyde Acetals. A Facile Synthesis 

of Macrocycles. 

Roberta Cacciapaglia, Stefano Di Stefano, Luigi Mandolini 

Dipartimento di Chimica and IMC – CNR Sezione Meccanismi di Reazione and Università di 

Roma La Sapienza, Box 34 - Roma 62, 00185 Roma, stefano.distefano@uniroma1.it 

Dynamic Covalent Chemistry (DCC) is receiving growing interest for its potentialities in the field 

of organic synthesis and in the discovery of new receptors.[1] We have recently reported [2] that 

the metathesis reaction of formaldehyde acetals (formals), carried out in chloroform in the 

presence of catalytic amounts of trifluoromethanesulfonic acid, nicely serves to the purpose of 

generating the whole family of interconverting macrocycles Ci. These cyclophanes are fully 

interchangeable under the adopted mild conditions. The reversibility of the system can be 

exploited in the amplification of the yield of one component of the family by the addition to the 

equilibrating mixture of a selective guest of the targeted component. 

In this communication we report on the impressive amplification of the dimer C2 by the addition 

of silver cation acting as a thermodymanic template. This amplification was carried out using as 

feedstock the polymeric material obtained in the batchwise acid catalysed reaction of trioxane 

with 1,4 benzenedimethanol. 

A significant amplification of the trimer C3 by the template effect of the guanidinium cation, is 

also reported. 

[1] P. T. Corbett, J. Leclaire, L. Vial, K. R. West, J.-L. Wietor, J. K. M. Sanders, S. Otto Chem. 

Rev. 2006, 106, 3652-3711. 

[2] a) R. Cacciapaglia, S. Di Stefano, L. Mandolini J. Am. Chem Soc. 2005, 127, 13666-13671; 

b) R. Cacciapaglia, S. Di Stefano, L. Mandolini Chem. Eur. J. 2006, 12, 8566-8570.

PSA 43 

Self-assembled fluorescent micellar sensors for pH windows: how to easily 

tune the window position along the pH axis 

Piersandro Pallavicini, Yuri Diaz Fernandez, Carlo Mangano, Luca Pasotti and Stefano Patroni 


Micellar fluorescent sensors for pH windows may be self-assembled in water by combining a 

fluorophore, a lipophilic pyridine derivative and a lipophilic tertiary amine inside the same 

micelle. In particular 2-dodecylpyridine and N,N-dimethyl-dodecylamine may be advantageously 

used with pyrene as a fluorophore in TritonX-100 micelles.[1] Being pyridinum and trialkyl 

amines efficient intramicellar quenchers of pyrene fluorescence (by electron transfer 

mechanisms), transition from OFF to ON state, and again from ON to OFF state, takes place at pH 

values corresponding to pyridium and ammonium pKa, as pictorially represented in the scheme. 

Modulation of the position and amplitude of the fluorescent window along the pH axis has been 

obtained by changing the substituents on the tertiary amino and pyridine moieties, in order to 

directly influence their pKa. We now have developed a new and straightforward approach to 

move at will the fluorescent ON window along the entire pH axis. The pKa of acidic species is 

modified by micellization with respect to their intrinsic values found in pure water. In particular, 

changing the overall charge of a micelle results in a change of the observed acidic constants: 

the more the micellar charge is negative, the lower is the observed deprotonation constant. We 

thus used only 2-dodecylpyridine and N,N-dimethyl-dodecylamine as bases but we 

progressively added increasing quantities of sodium dodecyl sulphate (SDS) to TritonX-100 

micelles. We observed a shift of the fluorescent window position towards higher pH values with 

a continuous smooth trend as a function of SDS molar fraction. Potentiometric determination of 

the protonation constants confirmed that the shift is due to the change in the observed 

protonation constant of the micellized species. Starting from all-TritonX-100 and ending will all- 

SDS micelles, the whole “traditional” pH axis (2-12) may be spanned by the ON fluorescent 

window. 

[1] Yuri Diaz-Fernandez, Francesco Foti, Carlo Mangano, Piersandro Pallavicini, Stefano 

Patroni, Aurora Perez-Gramatges and Simon Rodriguez-Calvo, Chem. Eur. J., 2006, 12, 921- 

930 

A Directed Four-Component Self-Sorting System 

Roy D’souza and Werner M. Nau* 

Jacobs University Bremen, Campus Ring 1, D-28759 Bremen, Germany 

Self-sorting phenomena are a cornerstone in the functioning of biological systems. This ability of 

molecules to recognize specific other molecules within complex mixtures is less frequently 

observed in synthetic systems. [1] While thermodynamic versus kinetic control has already been 

reported for sorting behavior, [2] we now introduce a chemical control element, thereby 

establishing a show-case of directed self-sorting. 

SO 3 

SO 3 

N 

N 

O 3S 

O 3 S 

SO 3 

SO 3 

CX4•1 CX4•2 

N 

N 

-CD•1 -CD•2 

O 3S 

N 

O3S N 

N 

N 

Zn 2+ 

O 3 S 

O 3S 

Zn 2+ 

N 

N 

N 

N 

SO 3 

PSA 44 

We propose a four-component system, consisting of two hosts (p-sulfonatocalix[4]arene and cyclodextrin) 

and two guests (1 and 2), as a proof-of-principle. [3, 4] Both hosts have similar 

affinity to bind to either of the guests. However, upon the addition of Zn 2+ , the preferential 

formation of a strongly bound ternary complex between Zn 2+ , p-sulfocalix[4]arene and 1 

simultaneously induces the complexation of -cyclodextrin with 2. This “clean-up” behavior 

successfully illustrates the potential of externally regulating the complexity of a system. It takes 

advantage of the interplay of competitive versus cooperative binding to increase the selectivity 

of supramolecular interactions in apparently complex multicomponent systems. 

[1] A. Wu and L. Isaacs, J. Am. Chem. Soc., 2003, 125, 4831-4835. 

[2] P. Mukhopadhyay, P. Y. Zavalij and L. Isaacs, J. Am. Chem. Soc., 2006, 128, 14093- 

14102. 

[3] H. Bakirci, X. Zhang and W. M. Nau, J. Org. Chem., 2005, 70, 39-46 

[4] H. Bakirci, A. L. Koner, M. H. Dickman, U. Kortz and W. M. Nau, Angew. Chem. Int. Ed., 

2006, 45, 7400-7404 

SO 3

PSA 45 

A fast-moving electrochemically-driven molecular shuttle: the biisoquinoline 

effect. 

Fabien Durola, Jean-Pierre Sauvage 

Laboratoire de Chimie Organo-Minerale, UMR 7177 du CNRS 

Institut de Chimie, Université Louis Pasteur, 4 rue Blaise Pascal, 67000 Strasbourg, France 

Two different copper-complexed [2]rotaxanes have been prepared and their 

electrochemically triggered motions have been investigated. Both compounds contain the same 

thread, which consists of a 2,9-diphenyl-1,10-phenanthroline (dpp) chelate and a 2,2',6',2''terpyridine 

(terpy) unit, whereas the threaded rings are different. In the first case, it is a 30membered 

ring derived from dpp. In the second compound, the ring incorporates a 8,8'diphenyl-3,3'-bi-isoquinoline 

(dpbiiq) chelate, which is at the same time non sterically hindering 

but endocyclic. By playing with the stereoelectronic preferences of copper (I) and copper (II), 

the ring with its complexed copper atom can be translocated from one station to the other 

reversibly. For the dpp-containing ring, the electrochemically-driven motion is extremely slow 

(hours to days). By contrast, the dpbiiq-based system is set in motion very readily, the 

translation process occuring in the milliseconds to seconds timescale, i.e. at least 4 orders of 

magnitude faster than for its dpp-based homologue. [1] 

[1] F. Durola, J.-P. Sauvage, Angew. Chem. Int. Ed., 2007, in press. 

PSA 46 

Efficient synthesis of copper(I)-rotaxane complexes via « click chemistry » 

Stéphanie Durot a , Pierre Mobian a , Jean-Paul Collin a , Jean-Pierre Sauvage a 

a Institut de Chimie de Strasbourg, Laboratoire de Chimie Organo-Minérale, Université Louis 

Pasteur, 4 rue Blaise Pascal, F-67070 Strasbourg cedex, France 

In the course of the last 15 years, the field of rotaxanes has experienced a spectacular 

development, mostly in relation to molecular machines [1, 2] and new materials. Threads and 

rings can be quantitatively assembled using copper(I) as a template. Pseudo-rotaxanes are 

then converted to rotaxanes by a stoppering reaction, that can be the limiting step, since the 

reaction conditions have to be compatible with the other functions present in the precursor. The 

efficient synthesis of new rotaxanes using « click chemistry » is described here. 

« Click chemistry » [3, 4] is a modular approach that relies on near perfect reactions. These 

reactions must be wide in scope, give very high yields, proceed from readily available reagents, 

and be easy to perform (that means ideally, be insensitive to oxygen and water). They should 

also be selective chemical transformations, and the workup as well as the product isolation 

should be simple. The prototype of a « click » reaction is the 1,3-dipolar cycloaddition of azides 

and alkynes, and especially the copper(I)-catalyzed synthesis of 1,2,3-triazoles. 

This reaction has been used for the synthesis of new copper(I)-rotaxane complexes by a double 

stoppering approach. The remarkable efficiency of such a strategy has to be emphasized, with 

yields ranging from 60 to 65 % (scheme 1). [5] The mild reaction conditions of the « click 

chemistry » methodology are clearly very well adapted to the synthesis of copper(I)-rotaxane 

complexes, especially when copper(I)-complex precursors are relatively unstable. It is expected 

that such methodology will also be suitable for more elaborate rotaxanes. 

N 3 

N N 

Cu 

N N 

I 

N3 O 

O O 

O 

O 

O 

N N 

Cu 

N N 

I 

O 

O O 

O 

O 

O 

, PF 6 

N3 

, PF6 N3 i) 

62 % 

i) 

65 % 

O 

O 

N 

N 

N 

N N 

Cu 

N N 

I 

O 

O O 

O 

O 

O 

, PF 6 

N N 

Cu 

N N 

I 

N N 

O 

O O 

N 

N 

N 

N 

O 

O 

O 

i) 3 eq. 4-[tris[(t-butyl)phenyl]methyl]phenyl propargyl ether 

0.5 eq. Cu(CH 3CN) 4.PF 6, 0.4 eq. Na 2CO 3, CH 2Cl 2/CH 3CN (7/3), 20 C, 21 h 

O 

, PF6 N 

N O 

N 

Scheme 1: synthesis of a Cu(I)-rotaxane complexes via « click chemistry ». 

[1] V. Balzani, M. Venturi, A. Credi, Molecular Devices and Machines - A journey into the 

Nanoworld, Wiley-VCH, Weinheim, 2003. 

[2] B. Champin, P. Mobian, J.-P. Sauvage, Chem. Soc. Rev. 2007, 36, 358. 

[3] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004 

[4] H. C. Kolb, K. B. Sharpless, Drug Discov. Today 2003, 8, 1128. 

[5] P. Mobian, J.-P. Collin, J.-P. Sauvage, Tetrahedron Lett. 2006, 47.

Bishydrazide derivatives of isoindoline – the simple anion receptors 

selective for carboxylates 

Pawe Dydio a,b , Tomasz Zieliski a , Janusz Jurczak a,b 

a 

Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 

Warsaw, Poland 

b 

Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland 

Anions are of crucial importance in many essential chemical and biological processes, due to 

this fact the development of strong and selective artificial anion receptors is an area of intensive 

exploration. [1] Recently scientists’ attention has been focused on neutral ligands which bind 

anions by hydrogen bond. Because of directional and distance-dependent character of this 

interaction it is possible to construct binding sites adjusted for specific anion. Thus, in order to 

achieve high selectivity, researchers investigate hosts that use hydrogen bond donors as 

anchoring points (mainly amide, sulphonoamide, urea, hydrazide, hydrazone groups or pyrrole 

moiety). [2] Presence of a chromophore in such systems can lead to optical sensors for anions. 

1,3-diiminoisoindoline moiety combines both of these attractive features – contains acidic proton 

NH and has been used for construction of artificial dyes. Therefore, we decided to examine 

simple hydrazide-based receptors built on isoindoline skeleton. 

. 

N 

N N 

O 

N 

O O 

N 

H 

H H 

C H 5 11 

C H 5 11 

Scheme 1 

N 

N N 

N 

H 

N 

H H 

O 

O 

N 

N 

H 

N 

H 

N 

N 

H 

N 

N 

O 

O 

N 

N N 

N N 

H 

H 

H 

N H N 

H 

1 2 3 4 

PSA 47 

We prepared bishydrazides (1-4) derived from isoindoline (Scheme1) and examined their anion 

binding properties. NMR and UV/Vis titrations revealed that these simple acyclic ligands, 

equipped with just three (five for 4) anchoring points, have strong affinity towards anions even in 

the very demanding solvent – DMSO. We observed high selectivity of our ligands for 

carboxylates over phosphates. Moreover, these compounds signal presence of anions by 

switching-on absorption of visible light. 

[1] J. L. Sessler, P. A. Gale, W. S. Cho, Anion Receptor Chemistry, The Royal Society of 

Chemistry, Cambridge, 2006. 

[2] S. O. Kang, R. A. Begum, K. Bowman-James, Angew. Chem. Int. Ed., 2006, 45, 7882-7894; 

P. A. Gale, R. Quesada, Coord. Chem. Rev., 2006, 250, 3219-3244. 

O 

Protonated Macrobicycle Host Containing Pyridine Head-Units for the 

Recognition of Anions 

David Esteban-Gómez, Carlos Platas-Iglesias, Teresa Rodríguez-Blas and Andrés de Blas. 

Universidade da Coruña; Departamento de Química Fundamental, Facultade de Ciencias, 

Campus da Zapateira s/n (15071) A Coruña, Spain. 

Herein In this work we report two macrobicyclic receptors based on azacrown platforms 

containing pyridine head units useful for anion recognition. UV-Vis and 1 H NMR studies indicate 

that these receptors can be triprotonated in acetonitrile by addition of CF3COOH. The first two 

protonation processes involve the protonation of the nitrogen atoms of the crown moiety, while 

the third protonation occurs on the pyridine nitrogen atom. The interaction of the protonated 

lateral macrobicycles with different anions have been followed by means of spectrophotometric 

titrations in acetonitrile solution. Among the different anions investigated, the highest affinity of 

these receptors is observed with chloride. The association constants for the interaction of halide 

anions with the protonated forms of the macrobicycles vary in the following order: 

F - < Cl - > Br - > I - , with an increase of the binding constants by more than two logarithmic units 

from F - to Cl - being observed for L 1 . The association constants also indicate an important 

degree of selectivity of these macrobicyclic receptors for Cl - over Br - or I - . On the other hand, 

the binding constants data indicate that these receptors present a high sulphate to nitrate 

binding selectivity. 

ε x 10 -3 M -1 cm -1 

25 

20 

15 

10 

5 

0 

N 

NH HN 

N 

N 

O n 

O O 

L 1 : n = 1 

L 2 : n = 2 

ε x 10 -3 M -1 cm -1 

2.7 

2.6 

2.5 

2.4 

2.3 

2.2 

2.1 

2.0 

CF3COOH NH 

N 

H 

HN 

[Bu4N]·A 0 2 4 6 8 10 

250 300 350 400 450 

wavelength, nm 

equiv H + 

NH HN 

O n 

O O 

319 nm 

ε x 10 -3 M -1 cm -1 

25 

20 

15 

10 

5 

0 

3+ 

ε x 10 -3 M -1 cm -1 

5.5 

5.0 

4.5 

4.0 

3.5 

3.0 

wavelength, nm 

NH 

N 

H 

A 

HN 

NH HN 

O n 

O O 

- 

0 1 2 3 4 

equiv Cl - 

300 nm 

PSA 48 

250 300 350 400 

The X-ray crystal structures analysis of the chloride and bromide complexes of L 1 

confirms the formation of the desired supramolecular complexes, with the halide anions being 

hold within the macrobicyclic cavity by five NH···X hydrogen bonds. 

2+

Macrocyclic Porphyrin-Bidentate Chelate Conjugates 

Jonathan A. Faiz, Fabien Durola and Jean-Pierre Sauvage. 

Laboratoire de Chimie Organo-Minérale, Université Louis Pasteur, Institut de Chimie, 4 rue 

Blaise Pascal, 67070 Strasbourg, France. 

The synthesis of macrocycles that contain both porphyrin and chelating units is an interesting 

challenge for in the construction of molecular machines that utilise the coordination properties of 

both the chelate and the metallated porphyrin. We have developed a direct approach using 

commercially available tetrakis(4-hydroxyphenyl) porphyrin as a starting material. Statistical 

cyclisation reactions with either phenanthroline or biisoquinoline [1,2] units have led to the 

macrocycles I and II. It has been shown that careful choice of the chelating unit and the chain 

length can lead to the preferential formation of the cis or trans isomers of the porphyrin 

macrocycle. Alkylation of the remaining phenol groups with a THP-masked alcohol provides a 

site for deprotection and subsequent functionalisation to create double macrocycles capable of 

simultaneously threading two axles. This provides a complementary approach to the synthesis 

of double macrocycles [3] and 4-rotaxanes [4] already investigated by us. 

THPO 

O 

O 

N 

O O 

N 

N 

H 

H 

N 

I 

N 

N 

O 

O 

OTHP 

[1] L. Flamingni, A.M. Talarico, J.-C. Chambron, V. Heitz, M. Linke, N. Fujita and J.-P. Sauvage, 

Chem. Eur. J., 2004, 10, 2689-2699 and references therein. 

[2] F. Durola, D. Hanss, P. Roesel, J-P. Sauvage and O.S. Wenger, Eur. J.Org. Chem., 2007, 

125-135. 

[3] J. Frey, T. Kraus, V. Heitz and J-P. Sauvage, Chem. Commun., 2005, 42, 5310-5312. 

[4] Collin, J. Frey, V. Heitz, E. Sakellariou, J-P. Sauvage and C. Tock, New. J. Chem., 2006, 10, 

1386-1389. 

O 

O 

N 

O 

OTHP 

O 

O 

N 

NH N 

N HN 

THPO 

II 

O 

PSA 49 

O 

O 

PSA 50 

Supramolecular assemblies of heterostylbene molecules: structure and 

properties 

O. A. Fedorova, a Yu. V. Fedorov, a N. E. Shepel, a E. N. Gulakova, a M. M. Mashura, a 

G. Jounauskauskas b . 

a 

A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 

Vavilova str., 28, GSP-1, Moscow, 119991, Russia; fedorova@photonics.ru 

b 

Centre de Physique Moléculaire Optique et Hertzienne – UMR CNRS 5798, University 

Bordeaux, France 

Aggregates of organic dyes have been extensively studied and reported in the literature 

because of their application in many fields of science, such as photographic process, organic 

photoconductors, photo-assisted process in biological systems, a prominent nonlinear optics 

materials. Molecular self-association of dyes is a well-known phenomenon, occurring in 

concentrated solution of dyes or induced by its preferential adsorption onto a wide variety of 

substrates, such as solids and microheterogeneous media. In the report the associate formation 

of the crown-containing hetarylphenylethenes assembled due to combination of coordination 

bonds, hydrogen bonds and stacking interaction was analyzed. The principals of the 

construction of the aggregates of the determined architecture were suggested. 

O O 

O 

O 

O 

O O 

O O 

O 

O O 

O 

O 

O 

N 

N 

N + 

N+ 

O 

O 

O 

O O 

N 

N 

O 

O 

N 

- 

OH 

O 

O 

N 

OH 

OH 

N 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O O 

O 

O 

O 

O O 

O 

O 

O 

O O 

O O 

O 

O O 

O 

O 

O 

O O 

O O 

O 

O O 

O 

O 

N + 

N + 

O 

O 

N N 

N N 

N N 

O O 

O 

The formation of the assemblies is observed by the change in the electronic absorption 

and emission spectra, since they have different photophysical properties when compared with 

the dye monomer. The formation of these aggregates is strongly dependent of several factors, 

like dye molecular structure, nature of metal cations and presence of organic acids. It was found 

that photochemical transformations of the assemblies of dyes substantially differ from those of 

initial dye monomer. 

Acknowledgment. The study was supported by CRDF (Grant RUC2-2656-MO-05), INTAS (Grant 

03-51-4696), RFBR (Projects No. 06-03-32899 and 05-03-32268). 

O O 

O 

O O 

O 

O 

O 

O 

O 

N+ 

N+ 

O 

O O 

O 

O 

O 

O 

O O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O

A novel pyrenyl appended tricalix[4]arene with enhanced fluorescence for 

Al 3+ PSA 51 

sensing. 

Amel Ben Othman, a,b Jeong Won Lee, c Rym Abidi, b,* Jong Seung Kim, c,* and Jacques Vicens a,* 

a 

ULP-ECPM, UMR 7178-LC4-IPHC, Laboratoire de Conception Moléculaire, 25, rue Becquerel, 

F-67087 Strasbourg, Cédex, France 

b 

Université de Bizerte, Facultés des Sciences, 7021 Zarzouna-Bizerte, Tunisie 

c 

Department of Chemistry, Dankook University, Seoul 140-714, Korea 

Aluminium is the most widely distributed metal in the environment and is extensively used in 

modern life. It is neurotoxic and can induce many diseases, such as Alzheimer’s disease, 

Parkinson’s disease and amyotrophic lateral sclerosis, etc. Compared to other metal cations, 

chemosensors aimed to detect and evaluate concentrations of aluminium are not so developed 

and the need to prepare molecular probes for this metal exists. In the present work we 

synthesized novel pyrenyl appended tricalix[4]arene which presents enhanced fluorescence 

during Al 3+ sensing. We have shown the need for the receptor to be tripodal for complexation to 

occur. Of importance seems the fact that the chelating part of the receptor is separated from the 

signalling moieties. In our case the separation is made by the use of calixarenes which are 

selectively 1,3-dialkylated. 

Tren- N-tricalix[4]arene appended with three pyrenyl showed an enhanced fluorescence in the 

presence of Al 3+ and at less extend of In 3+ in acetonitrile. The ligand was shown to form a 1:1 

complex with Al 3+ , the metal cation being located in the tren part. The association constant (Ka) 

of tren- N-tricalix[4]arene for the Al 3+ cation was calculated to be 8.7 × 10 3 M -1 in acetonitrile. 

The present work develop the synthesis of pyrene amide calix[4]arenes as chemosensors for 

the detection of cations and anions. 

We used the 1 H NMR technique to locate Al 3+ in the ligand cavity. The NMR solution was 

submitted to the MALDI TOF technique to show evidence of a 1:1 complex in the solution with 

m/z = 3051.541 (Ligand + Al 3+ -3H + ). 

O 

O 

OH 

OH 

HN 

O 

H 

N 

O 

O NH 

N 

HN O 

O 

HN 

OH 

OH 

O 

O O 

NH 

HO 

HO 

O 

O 

Al 3+ 

N 

N 

Al 

N 

O 

O 

O 

OH 

OH 

O 

HN 

O 

3+ 

N O 

O 

OH 

OH 

H 

N 

O 

O 

O 

HO 

HO 

O 

NH 

O 

Plausible mode of complexation of Al 3+ cation by tren- N-tricalix[4]arene. 

Intramolecular FRET triggered Hg 2+ PSA 52 

ion sensing in tricalix[4]arene system 

Amel Ben Othman, a,b Jeong Won Lee, c Rym Abidi, b,* Jong Seung Kim, c,* and Jacques Vicens a,* 

a 



b 


c 


It is well known that mercury is a very volatile element, and its vapors can be a dangerous 

source of air pollution, thus representing a serious risk for human health. So, the design of 

chemosensors able to selectively recognize and sense mercury has attracted considerable 

interests. The main issue in designing effective sensor is to easily convert molecular recognition 

into photochemical changes with a high selectivity and sensitivity. For the chemosensors, the 

photochemical changes in the sensing modules are mainly based on the photo-induced electron 

transfer (PET), Chelation-Enhanced Fluorescence (CHEF) and fluorescence resonance energy 

transfer (FRET). Taking our interest into account of the fluorescence resonance energy transfer 

a novel sensor for Hg 2+ ion based on switchable FRET has been investigated. 

O O 

O 

O 

OH HN NH HO 

OH 

HO 

O 

N 

O 

O 

NH 

N 

O 

N 

O 

N 

HN 

O 

O O 

O 

O 

OH HN NH HO 

OH 

HO 

OH 

N 

HO 

1 2 

Upon the addition of various metal perchlorate, ligand 1 exhibits a selectivity for Hg 2+ and Pb 2+ 

ions concerning new absorption band at 555 nm. We also observed a visual change from 

colorless to pink with Hg 2+ or Pb 2+ ion in CH3CN. From the titration profile, association constants 

of 1 for Hg 2+ and Pb 2+ ion are found to be 39,070 and 9,850, respectively. Addition of Al 3+ ion to 

1 gave an increase of the pyrene emission by the CHEF effect, but no change of rhodamine. 

This may indicate that the Al 3+ ion is coordinated only to the tetraamide-tren part excluding to the 

rhodamine part. Compared to 1, 2 shows only a small change of the rhodamine band upon Hg 2+ 

ion binding. So, one can conclude that the FRET event takes place in 1·Hg 2+ complex. 

N 

O 

N 

O 

N

PSA 53 

Electronic spectroscopy of emissive cryptophane-based molecules and 

their Xe containing complexes 

Heather A. Fogarty, Thierry Brotin, and Jean-Pierre Dutasta 

Ecole Normale Supérieure de Lyon, Stéréochimie et Interactions Moléculaires UMR 5532 

CNRS/ENS Lyon, 46 Allée d’Italie, 69364 Lyon France 

Many aspects of cryptophanes, such as their ability to encapsulate atoms and small 

molecules,[1] their complexation dynamics,[2] the nature of the interior cavity, and their 

energetically accessible conformations,[3] have been studied extensively using NMR, IR, 

crystallographic and computational methods. Cryptophane-A, 1, and a water soluble derivative 

are known to complex Xe with very high binding constants (3900 M -1 in Cl4C2H2;[4] 6900 M -1 in 

H2O)[5] prompting work toward their application as probes for MRI.[6] The resolution of chiral 

cryptophanes allowed both their CD and VCD spectra to be analyzed.[7] Although their UV-Vis 

electronic excitation energies are known, their behavior upon excitation has yet to be 

elucidated. We have used electronic circular dichroism, UV-Vis and photoluminescence 

spectroscopy to investigate the intrinsic photophysical behavior of the prototypic and most 

intensively studied cryptophane, 1, a 9-ethoxy anthracene substituted derivative, 2, and a new 

cryptophane, as well as the effect of Xe complexation on their emissive behaviour, at room 

temperature and at 77 K. 

H 3CO 

O 

O 

OCH3 H3CO O OCH 

O 

3 

OCH3 O 

O 

O 

R 

1 R = CH 3 

2 R = CH 2 

The presence of a Xe atom inside the cryptophane cavity quenches statically the initially 

excited S1 state reducing the fluorescence yield. At low temperature phosphorescence can be 

observed for certain Xe@cryptophane complexes. An understanding of the photophyscial 

processes occurring among the cryptophane cage, guest and photoluminescent label will be 

used to design a second generation of emissive cryptophanes. It is desired that the nature of 

the environment surrounding the cryptophane cage can be studied by taking advantage of both 

the inherent sensitivity of luminescence techniques and the great sensitivity of the 129 Xe 

chemical shift. 

[1] G. Huber, L. Dubois, H. Desvaux, J.-P. Dutasta, T. Brotin, P. Berthault, J. Phys. Chem. A 

2004, 108, 9608-9615. 

[2] T. Brotin, T. Devic, A. Lesage, L. Emsley, A. Collet, Chem. Eur. J. 2001, 7, 1561-1573. 

[3] P. D. Kirchhoff, J.-P. Dutasta, A. Collet, J. A. McCammon, J. Am. Chem.Soc. 1999, 121, 

381-390. 

[4] K. Bartik, M. Luhmer, J.-P. Dutasta, A. Collet, J. Reisse, J. Am. Chem.Soc. 1998, 120, 784- 

791. 

[5] G. Huber, T. Brotin, L. Dubois, H. Desvaux, J.-P. Dutasta, P. Berthault, J. Am. Chem.Soc. 

2006, 128, 6239-6246. 

[6] L. Schroder, T. J. Lowery, C. Hilty, D. E. Wemmer, A. Pines, Science 2006, 446-449. 

[7] T. Brotin, D. Cavagnat, J.-P. Dutasta, T. Buffeteau, J. Am. Chem.Soc. 2006, 128, 5533- 

5540. 

O 

PSA 54 

Insights on the binding recognition of novel Dioxatetraaza macrocycle by 

G-Quadruplex telomeric DNA: a molecular dynamics investigation. 

N. Fonseca a , P. J. A. Ribeiro-Claro and V. Félix 

Departamento Química, CICECO, Universidade de Aveiro, 3810-193 Aveiro, Portugal. 

a e-mail: nfonseca@dq.ua.pt 

Human telomerase is a ribonucleoprotein composed of a catalytic subunit, human telomerase 

reverse transcriptase and a 451-nucleotide-long RNA (hTR), which acts as a template for the 

addition of the repetitive hexameric motif (5'-GGTTAG-3') at the end of the telomeres. Several 

recent studies show that telomerase expression is associated with cell immortalization and 

tumorigenesis [1, 2]. Telomerase is over expressed in a large number of tumors, whereas it is 

not expressed in most somatic cells, which usually have longer telomeres. Such differential 

expression was used as starting point for the evaluation of telomerase inhibitors as potential 

anticancer drugs. G-Quadruplex DNA has been widely used as a target model for drug design 

of human telomerase inhibitors, since it conserves the 

major properties of telomeric units[3]. 

protonated macrocyclic polyamines, incorporating 

extended aromatic rings, are capable of binding strongly 

the G-quartets of the G-quadruplex DNA, mainly due to 

the multiple cooperative strong electrostatic interactions 

between the positively charged ammonium groups of the 

macrocyclic ligand and the negatively charged phosphate 

groups of the DNA receptor. In addition, the pi - pi 

stacking interaction between the aromatic groups, of both 

species, contributes to the overall binding stability of these 

supramolecular associations. 

In this work the theoretical binding studies between the 

dioxatetraaza macrocycle (Hi[26]phen2N4O2) i + (left) 

incorporating two phenantroline units (H2L 2+ and H3L 3+ 

forms) and G4, are reported. Molecular dynamics 

simulations in explicit water were carried with AMBER8 

and the binding free energies involved in the recognition 

process were estimated by post-processing the MD trajectory files using the MM-PBSA [4] 

methodology. The results obtained demonstrate that (Hi[26]phen2N4O2) i+ Figure 1: Cartoon representation of the G4- 

DNA complexed with the dioxatetraaza 

macrocycle. 

ligand has a highest 

binding affinity to the G-Quadruplex DNA target. 

Acknowledgements: 

Nelson Fonseca thanks FCT – Fundação para a Ciência e Tecnologia – for the financial support 

under the PhD scholarship SFRH/BD/25115/2005. 

[1] Holt S. E., Shay J. W., J. Cell. Physiol. (1999), 180, 10-18. 

[2] McEachern M. J., Krauskopf A., Blackburn E. H., Annu. Rev. Genet. (2000), 34, 331-358. 

[3] Kerwin S.M., Cur. Pharm. Design (2000), 6, 441-471. 

[4] P. A. Kollman et al, Accts. Chem. Res., (2000), 33, 889-897.

PSA 55 

Molecular Recognition of Carbohydrates: New Synthetic Tripodal Receptors 

Featuring Pyrrolic Binding Groups. 

Cristina Nativi, a,b Martina Cacciarini, a Oscar Francesconi, a Alberto Vacca, c Gloriano Moneti, d 

Andrea Ienco, e and Stefano Roelens. f 

a Dipartimento di Chimica Organica, b Centro Risonanze Magnetiche (CERM), c Dipartimento di 

Chimica, d Centro Interdipartimentale di Spettrometria di Massa (CISM), Universita` di Firenze, 

e Istituto di Chimica dei Composti OrganoMetallici (ICCOM), f Istituto di Metodologie Chimiche 

(IMC), Consiglio Nazionale delle Ricerche (CNR), Polo Scientifico e Tecnologico, I-50019 Sesto 

Fiorentino, Firenze, Italy. 

Carbohydrates are involved in many key processes in biological systems, like metabolism and 

transport, cell-to-cell adhesion, immune response, cell infection by pathogens and enzyme 

regulation. [1] All these processes are based on molecular recognition of carbohydrates, mainly 

exploiting H-bonding interactions. To understand the chemical basis of these phenomena, 

synthetic receptors mimicking the interaction between natural receptors and carbohydrates 

were widely employed. [2] However, the design of effective receptors for selective recognition of 

carbohydrates is yet an open challenge, for the achievement of which the comprehension of 

structural and functional requirements for recognition is a crucial issue. Among the multitude of 

artificial receptors reported in the chemical literature, benzene based tripodal structures have 

been often employed giving interesting results. Effective recognition requires the establishment 

of multiple binding interactions. In order to achieve the formation of an array of H bonds 

between the host and the saccharidic guest, we have designed a receptor architecture that 

O 

HO 

HO 

OH OR 

OH 

HN 

OH 

NH 

HN 

NH 

O HN 

H 

N 

HN 

H 

N 

HN 

HO 

HO HNOH 

NH HN 

OR 

combines both aminic and pyrrolic functional groups into an acyclic tripodal benzene-based 

scaffold. Indeed, aminic groups have been shown to be coordinatively complementary to 

hydroxyl groups, [3] while pyrroles are well-established H-bonding donors. [4] Their combination 

into a carefully designed architecture is thus believed to be effective for the recognition of 

carbohydrates. In this communication we wish to describe the synthesis and the binding 

properties of newly designed tripodal receptors, showing affinities for biologically relevant 

monosaccharides among the largest reported in literature for neutral synthetic H-bonding 

receptors. 

[1] 

B. Ernst, W. Hart, P. Sinay, Carbohydrates in Chemistry and Biology; Wiley-VCH: Weinheim, 

Germany, 2000. 

[2] A. P. Davis, T. 

D. James, In Functional Synthetic Receptors; T. Schrader, , A. Hamilton, D., 

Eds.; Wiley-VCH: Weinheim, Germany, 2005; pp 45-109. 

[3] S. Hanessian, M. Simard, S. Roelens, J. Am. Chem. Soc. 

1995, 117, 7630 – 7645. 

[4] J. L. Sessler, P. A. Gale, W. S. Cho, Anion Receptor Chemistry, RSC Publishing, UK, 

2006. 

Synthesis of Peptoid-containing Macrocycles by Multiple Ugi-type 

Multicomponent Reactions 

Daniel G. Rivera and Ludger A. Wessjohann* 

Department of Bioorganic Chemistry, Leibniz Institute of Plant Biochemistry, Weinberg 3, 

06120, Halle/Saale, Germany. Fax: +49 345 5582 1309; Tel: +49 345 5582 1301; E-mail: 

wessjohann@ipb-halle.de 

PSA 56 

A versatile strategy towards peptoid-containing macrocycles, termed multiple multicomponent 

macrocyclizations including bifunctional building blocks (MiBs), has been recently developed. [1] 

In this approach, the building blocks are allowed to undergo a cyclooligomerization process 

based on multiple Ugi four-component reactions (Ugi-4CR) to afford macrocycles including 

varied peptoid moieties. [1] Macrocycles of different sizes, shapes, and presenting varied 

functional appendages have been produced in one pot by implementing the different 

combinations of bifunctional building blocks. [1,2] The rapid generation of skeletal and appendage 

diversity is a key feature of this approach, which enables the creation of parallel and 

combinatorial libraries of macrocycles with very low synthetic cost. [2] 

An extension of the MiB methodology to the third dimension allowed to obtain peptoidcontaining 

cryptands, cryptophanes, and steroid-based cages. [2a,3] This procedure comprises 

the performance of threefold Ugi-4CR-based macrocyclizations to assemble the macrobicyclic 

frameworks in one pot. The peptide-like skeletons and the variable functional appendages make 

these compounds amenable for applications in catalysis, coordination and supramolecular 

chemistry. 

[1] a) L. A. Wessjohann, B. Voigt, D. G. Rivera, Angew. Chem. Int. Ed., 2005, 44, 4785-4790; 

b) L. A. Wessjohann, E. Ruijter, Mol. Diversity, 2005, 9, 159-169. 

[2] a) D. G. Rivera, O. E. Vercillo, L. A. Wessjohann, Synlett, 2007, 308-312; b) L. A. 

Wessjohann, D. G. Rivera, F. Coll, J. Org. Chem., 2006, 71, 7521-7526. 

[3] D. G. Rivera, L. A. Wessjohann, J. Am. Chem. Soc. 2006, 128, 7122-7123.

PSA 57 

Self-assembly of calixarene/CsI/diiodoperfluorocarbon supramolecular 

salts: structural studies and fluorous phase extraction 

Giuseppe Gattuso, a Andrea Pappalardo, a Melchiorre F. Parisi, a Pierangelo Metrangolo, b 

Giuseppe Resnati, b Tullio Pilati, c Sebastiano Pappalardo d 

a Dipartimento di Chimica Organica e Biologica, Università di Messina, salita Sperone 31, 

I-98166 Messina, Italy 

b DCMIC “G. Natta”, Politecnico di Milano, via L. Mancinelli 7, I-20131 Milano 

c CNR-ISTM, via C. Golgi 19, I-20133 Milano, Italy 

d Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, I-95125 Catania, 

Italy 

Inorganic, organic and perfluorinated compounds usually display a low affinity for each other. 

Recent studies have however demonstrated that formation of supramolecular aggregates driven 

by halogen bonding [1] between diiodoperfluorocarbons and iodide anions is possible, providing 

that ion-pairing effects (of the salt used) are outweighed by using an appropriate ionophore 

acting as a selective cation sequestering agent. [2] 

In this report we show that the self-assembly of hybrid supramolecular salts compounded of 

CsI, calixarenes, and diiodoperfluoroalkanes can be induced, both in the solid state and in 

solution, by harnessing a set of non-covalent forces. [3] In the solid state, the caesium ion is 

nested in the crown loop of the receptor, and shielded by a picolyl unit and a phenol ring 

involved in cation- interactions. The iodide anion, on the other hand, assembles into discrete 

aggregates held together by the concomitant action of hydrogen bonding (ethanol-iodide) and 

halogen bonding (diiodoperfluorocarbon-iodide). Single crystal X-ray analysis as well as 19 F 

NMR techniques show that the ‘naked’ iodide anion is a strong halogen bonding acceptor even 

in the presence of protic solvents. In keeping with these observations, we have used calixcrown 

1 in conjunction with a number of (di)iodoperfluoroalkanes to force the selective uptake of 

caesium iodide from aqueous into fluorous phase. 

[1] P. Metrangolo, G. Resnati, Halogen bonding, Encyclopedia of Supramolecular Chemistry; 

Marcel Dekker, New York, 2004. 

[2] G. Gattuso, R. Liantonio, F. Meyer, P. Metrangolo, G. Resnati, A. Pappalardo, M. F. Parisi, 

T. Pilati and I. Pisagatti, Supramol. Chem., 2006, 18, 235–243. A. Casnati, R. Liantonio, P. 

Metrangolo, G. Resnati, R. Ungaro, and F. Ugozzoli, Angew. Chem. Int. Ed. 2006, 45, 1915– 

1918. 

[3] G. Gattuso, A. Pappalardo, M. F. Parisi, I. Pisagatti, F. Crea, R. Liantonio, P. Metrangolo, W. 

Navarrini, G. Resnati, T. Pilati, S. Pappalardo, Tetrahedron, doi:10.1016/j.tet.2007.03.136. 

Properties of Deep-Cavity Cavitands 

Corinne L. D. Gibb, Srinivasan Kannupal, and Bruce C. Gibb* 

Department of Chemistry, University of New Orleans, New Orleans, LA, USA. 

PSA 58 

We will discuss two aspects of our research into deep-cavity cavitands. In organic solvents, 

these bowl-shaped molecules readily form 1:1 complexes with suitable guest molecules (below 

left). We will report on the synthesis [1,2] and properties of cavitands possessing functionalized 

concavity that are capable of selectively reacting with complementary guests. We will also 

discuss water-soluble cavitands that form capsular complexes capable of entrapping one or 

more guests (2:1 complex shown below right).[3,4] We will report on some of the unusual 

properties of these complexes, and our recent efforts to understanding the thermodynamics 

driving their formation. 

[1] Kannupal, S.; Gibb, B. C., Org. Lett. 2007, 9, 745-748. 

[2] Laughrey, Z. R.; Gibb, B. C., J. Org. Chem 2006, 71, 1289-1294. 

[3] Gibb, C. L. D.; Gibb, B. C., Chem. Comm. 2007, Advanced Atricle (DOI: 10.1039/b618731e) 

[4] Gibb, C. L. D.; Gibb, B. C., J. Am. Chem. Soc. 2006, 128, 16498-16499.

Aryl calix[4]pyrroles. Scaffolds to obtain evidences of anion- interaction. 

Guzman Gil-Ramirez, ‡ Mª Angeles Sarmentero ‡ , and Pablo Ballester. § 

‡ Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 

Tarragona, Spain. § ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain 

Supramolecular chemistry of host – guest complexes for cations or neutral species has 

received much attention in the last two decades. Nevertheless, the chemistry of anion - 

interactions is much less developed. In fact, this term was coined only five years ago by 

Frontera and Deyà [1]. Theoretical investigations have been reported on the interaction of 

halides with electron deficient -systems, like fluorobenzene, fluoro-s-triazine [2] and s-tetrazine 

[3] derivates. All the calculations indicate clearly a favourable non covalent interaction between 

the halide and the system. Few experimental evidences, however, have been reported in 

support to the theoretical calculations and most of them are based on solid state structures. 

Although calix[4]pyrroles were discovered more than a century ago [4], it was not until 

1996 when Sessler [5] re-discovered them as receptors capable of interacting with anion and 

neutral substrates. Calix[4]pyrroles present four NH groups that can act simultaneously and in a 

convergent manner, generating an interaction centre suitable for electron rich neutral molecules 

or anions. In particular, isomer of meso- tetraaryl substituted calix[4]pyrroles adopts a 

cone conformation with a deep cavity. The presence and chemical modification of the aryl rings 

alters the electronic properties of the cavity and modifies its binding affinity towards the anion. 

This presentation will describe the synthesis of several calix[4]pyrrole receptors 

containing deep aromatic cavities. The complexation process of these receptors with several 

anions have been probed using 1 H and 19 F NMR ,as well as, ITC techniques. Furthermore, we 

have obtained several crystal structures of the anionic complexes which are in complete 

agreement with the results obtained in solutions. The electronic richness of the aromatic cavity 

influences the association constants, following a clear trend that can only be explained through 

the establishment of favourable anion- interactions. 

CN 

R R 

N 

H 

R= 

NH HN 

H 

N 

1 2 3 4 

R 

R 

Figure 1 –Left – Minimized structure of the complex formed by a calyx[4]pyrrole with a 

deep aromatic cavity and clhoride. CPK representation with chloride anion in green. Right – 

Molecular structure of of the receptors used in this study. 

[1] Quinonero, D.; Garau, C.; Rotger, C.; Frontera, A.; Ballester, P.; Costa, A.; Deya, P. M., 

Angew. Chem., Int. Ed. 2002, 41, (18), 3389-3392. 

[2] Mascal, M.; Armstrong, A.; Bartberger, M. D., J. Am. Chem. Soc. 2002, 124, (22), 6274- 

6276. 

[3] Garau, C.; Quinonero, D.; Frontera, A.; Costa, A.; Ballester, P.; Deya, P. M., Chem. Phys. 

Lett. 2003, 370, (1,2), 7-13. 

[4] Baeyer, A., Ber. Dtsch. Chem. Ges. 1886, 19, 2184. 

[5] Gale, P. A.; Sessler, J. L.; Kral, V.; Lynch, V., J. Am. Chem. Soc. 1996, 118, (21), 5140- 

5141. 

NO 2 

PSA 59 

NH 2 

PSA 60 

Hexa-Phosphorylated Triphenylenes (HPT) for aromatics and carbohydrates 

recognition 

Cécile GIVELET a ; Brigitte BIBAL a 

c.givelet@ism.u-bordeaux1.fr 

a University of Bordeaux 1, Institut des Sciences Moléculaires, UMR CNRS 5255 

351 cours de la Libération, 33405 Talence, France. 

CH- and - interactions are widespread in Nature. 1 They play a crucial role in numerous 

biological processes such as the helical structuration of DNA, proteins folding, cellular 

recognition, and enzyme-substrate recognition. 

A better knowledge of these interactions would bring a major breakthrough in the field of 

molecular detection, transport and separation of aromatic and aliphatic compounds. 

Our concept is based on hexasubstituted -extended architectures which are able to interact 

with biological targets (catecholamine, sugars) or water pollutants (Alachlor, 

pentachlorophenol). 

-extended platform 

(HPT) 

GUEST 

CH- or - interactions 

( ) 

We designed and efficiently synthesised, a new class of molecular receptors: the Hexa- 

Phosphorylated Triphenylenes (HPT) 1a-d. 

R 

O P R 

O 

O 

O P R 

R 

R 

P 

O 

O 

R 

R 

O 

P 

R 

O 

HPT 1a-d 

O 

O 

P 

R 

R 

O 

R 

P 

O 

R 

1a : R = Ph 

1b : R = C 6H 4 -p-OMe 

1c : R = C 6H 4 -p-OH 

1d : R = C 6H 4 -p-O(CH 2CH 2) 3OMe 

We studied 1a-d in different media using NMR (2D, 1D), UV-Visible Absorption and 

Fluorescence Emission spectroscopies. For instance receptor 1c shows high affinity for 

Dopamine (Ka H2O/MeOH: 96/4 = 3,56x10 +4 M -1 ) and D-Glucose (Ka H2O/MeOH: 96/4 = 2x10 +4 M -1 ). 

Selectivity and nature of the interactions are questioned. 

[1] Hunter, C. A.; Lawson, K. R.; Perkins, J. Urch, J. C. J. Chem. Soc. Perkin Trans. 2, 

2001,651-669. Hunter, C. A. Sanders, K. M. J. Am. Chem. Soc. 1990, 112, 14, 5525-5534.

PSA 61 

Piperazine Containing Polyamino and Polyamino-amido Receptors of Open- 

Chain and Cyclic Topology 

José M. Vistos, a J. M. Llinares, b Jorge González, a E. García-España, a C. Sorianob and K. 

Rissanen. c 

a) Departament de Química Inorgànica, Instituto de Ciencia Molecular, Facultat de 

Química,Universitat de València. 

b) Departament de Química Orgánica, Instituto de Ciencia Molecular, Universitat de València, 

Burjassot. 

c) Univ Jyvaskyla, Nanosci Ctr, Dept Chem, FIN-40014 Jyvaskyla, Finland 

Piperazine moieties behave as reinforcing component when inserted into polyamine structures. 

Their low energy-chair conformation usually favors the formation of macrocycles of large 

size.1,2 Change from chair to boat conformation is an energy demanding step that usually 

needs of the binding of appropriate guest species to the piperazine nitrogens. Alternatively, this 

energetic barrier can be overcome in the synthetic procedure by connecting the piperazine rings 

to appropriate building blocks. 

Herewith we report on the synthesis and anion coordination capabilities of a series of new 

polyamine or polyamine-amide open-chain and cyclic molecules having the tetraamine N,N’bis(aminopropyl)piperazine 

and different aromatic spacers as basic constituents. 

1) K. Rissanen, J. Huuskonen, A. Koskinen, J. Chem. Soc., Chem. Commun. 1993, 731. 

2) J. A. Aguilar, E. García-España, J. A. Guerrero, J. M. Llinares, J. A. Ramírez, C. Soriano, S. 

V. Luis, A. Bianchi, L. Ferrini, V. Fusi, J. Chem. Soc., Dalton Trans. 1996, 239-246 

PSA 62 

Cooperativity of inclusion by macrocyclic receptors for vapor sensing and 

storage 

Valery V. Gorbatchuk, Marat A. Ziganshin 

Chemical Institute, Kazan State University, Kremlevskaya 18, 420008 Kazan, Russia 

Cooperativity of inclusion observed in systems with solid receptors and substrate vapors 

contributes much in their actual and possible applications. While used in vapor sensors, 

clathrate-forming hosts have the additional selectivity linked to cooperative change of guest 

inclusion threshold. The volatile substrates, when bound, are held in clathrates with crystal 

cooperativity, which is important for gas storage. The inclusion properties of hydrophilic 

receptors cooperatively depend on their hydration, which gives a guide for a design of 

biomimetic and biocompatible organic hosts. 

The present work provides experimental data on the above-mentioned and a number of other 

practically useful effects related to the cooperativity of clathrate formation and decomposition for 

such macrocyclic receptors as calixarenes and cyclodextrins. For example, the guest inclusion 

threshold of tert-butylcalix[4]arene was found to decrease practically to zero in the presence of 

small impurities of some other guests. This effect can be used to reduce the pressure threshold 

for gas inclusion. Another possibility to reach this goal is to use receptor phase having loose 

packing. Such stable materials with large pores of molecular size and a wide range of thermal 

stability were prepared for several calixarene derivatives. The size and stability of pores are 

tunable. 

Another type of cooperative effects for solid macrocyclic receptors is clathrate memory. Being 

caused by enhanced clathrate stability compared with the properties of liquid solutions, the 

memory effects were observed for calixarenes in sensors. A simple regeneration technique was 

offered together with its quantitative criteria. 

Quantitative thermodynamic description is given for all observed cooperative phenomena, which 

makes their prediction and understanding easy and comprehensive. 

The inclusion cooperativity defines specific selectivity and molecular recognition in solid-phase 

host-guest interactions.[1] Corresponding structure-property relationships for inclusion 

parameters can be reasonable if clathrates compared have the same preparation history. In the 

present work, the effect of host and guest structure on parameters of guest inclusion was 

studied for a number of calixarenes under strictly the same conditions. Several simple 

relationships were found, which may be used in a directed design of new macrocyclic receptors. 

This work was supported by RFBR (05-03-33012) and BRHE (REC-007). 

[1] M. A. Ziganshin, A. V. Yakimov, G. D. Safina, S. E. Solovieva, I. S. Antipin, and V. V. 

Gorbatchuk Org. Biomol. Chem., 2007, 5, 1472 - 1478

PSA 63 

A fluorescent-indicator displacement assay for detection of ATP and GTP 

employing the cyclobisintercaland-type receptors 

Anton Granzhan and Marie-Paule Teulade-Fichou 

UMR 176 CNRS, Institute Curie, F-91405 Orsay, France 

The detection of nucleotides and nucleosides represents an active research area, since these 

analytes are involved in many biological processes. Along these lines, especially attractive are 

the fluorescence-based detection strategies, particularly the ones based on the enhancement of 

the fluorescence signal upon binding of the analyte [1,2]. The previous works from our group 

have shown that the cyclobisintercaland-type hosts, such as BisA [3] and BisNP [4], bind 

nucleotides with high binding constants. However, the quenching of the fluorescence of these 

receptors, which accompanies the binding event, is not optimal for the fluorimetric applications, 

since the quenching of fluorescence may be also caused by other stimuli, such as heavy ions, 

functional groups that assist intersystem crossing, and others. 

NH 

NH 

NH 

N 

N 

H 

N 

HN 

NH 

BisA 

O 

NH 

NH 

BisNP 

HN 

HN 

O 

O 3S 

OH 

O3S SO3 3 Na 

In the present work, we show that the cyclobisintercaland receptors bind the fluorescent 

indicator HPTS (8-hydroxy-1,3,6-pyrenetrisulphonate, pyranine) with a 1:1 stoichiometry and 

high binding constants in aqueous solutions (e.g. log K = 7.0 at pH 6 for BisA), which leads to 

almost complete quenching of the fluorescence of the indicator. Remarkably, addition of 

nucleotide triphosphates, such as ATP and GTP, to the BisA–HPTS complex leads to an 

efficient displacement of the indicator, as these analytes bind to the receptor, and is 

accompanied by a drastic recovery of the fluorescence. Thus, the fluorescence of the 1:1 BisA– 

HPTS complex is enhanced about 2000-fold in the presence of only 0.2 mM ATP or GTP. In 

contrast, much weaker enhancement of the fluorescence was observed in the case of other 

nucleotide tri-, di-, and monophosphates. These data indicate that the BisA–HPTS complex 

represents a highly sensitive fluorescent-indicator displacement assay [5] which may be used 

for the detection of ATP and GTP. 

[1] S. Atilgan, E. U. Akkaya, Tetrahedron Lett. 2004, 45, 9269–9271. 

[2] P. P. Neelakandan, M. Hariharan, D. Ramaiah, J. Am. Chem. Soc. 2006, 128, 11334–11335. 

[3] M.-P. Teulade-Fichou, J.-P. Vigneron, J.-M. Lehn, Supramol. Chem. 1995, 5, 139–147. 

[4] M. Dhaenens, J.-M. Lehn, J.-P. Vigneron, J. Chem. Soc., Perkin Trans. 2 1993, 1379–1381. 

[5] B. T. Nguyen, E. V. Anslyn, Coord. Chem. Rev. 2006, 250, 3118–3127. 

HPTS 

PSA 64 

The supramolecular architecture of a guanosine derivative as a scaffold for 

persistent radicals 

Carla Graziano, Stefano Masiero, Silvia Pieraccini, Marco Lucarini, Gian Piero Spada 

a Dipartimento di Chimica Organica "A. Mangini", Alma Mater Studiorum - Università di Bologna, 

Via San Giacomo 11, 40126 Bologna, Italy (E-mail: carla.graziano@studio.unibo.it); 

G-quartets formed by guanosines with an Hoogsteen like hydrogen bonding network are 

observed in different environments such as telomeres of the human genome or G-quadruplex 

formed by semisynthetic lipophilic guanosines (LipoG) in organic solvent in presence of alkali 

ions. 

Actually, LipoG’s are able to extract salts, like potassium picrate, by formation of G-quartets 

stacked in columnar chiral aggregates whose stochiometry (figure 1) depends on the relative 

amount of nucleobase and cation. 1 

In particular, 2’,3’-O-isopropylideneguanosines differently substituted on either the nucleobase 

or the ribose moiety, are able to self-assemble in solution by K + templation to give a 

G-quadruplex with formula [LipoG]8K + Picr - . It consists in two G-quartets kept together by 

coordination of the cation. 2 . 

Here we report for the first time the synthesis and the supramolecular behaviour of a 

2’,3’-O-isopropylideneguanosine derivative functionalized in 5’ position with a persistent 

nitroxide radical 1. 

Both EPR and circular dicroism studies confirm the formation in solution of the expected 

octameric G-quadruplex after extraction of potassium picrate and sodium picrate. A more 

detailed structural assignment was obtained by NMR on derivatives 2 and 3. The octamer 

consists in two G-quartets templated by the central cation with D4-symmetry. 

Figure 1 

RO 

H 

H 

O 

O 

H 

N 

N 

H 

O 

O 

N 

NH 

NH 2 

O 

1 R= 

2 R= COC 9H 19 

[1] J.T: Davis and G. P. Spada, Chem. Soc. Rev.; 2007, 36, 296-313. 

[2] M.S. Kaucher, Y. Lam, S. Pieraccini and G.Gottarelli, J.T. Davis, Chem. Eur. J., 2004, 11, 

164-173; X. Liu, I.C.M. Kwan, S. Wang and G. Wu, Org. Lett., 2006, 8, 3685-3688. 

3 R= 

O 

N 

O

PSA 65 

Synthesis of Self-Assembly Systems through Multiple Hydrogen Bonding 

Interactions between DNA modified bases for Supramolecular Applications 

Elisabetta Greco a , Abil E. Aliev a , Kason Bala b , Peter Golding b and Helen C. Hailes a . 

a Department of Chemistry, University College London, 20, Gordon Street, London WC1H 0AJ, 

UK; b AWE, Aldermaston, Reading, Berkshire, RG7 4PR, UK. (e.greco@ucl.ac.uk) 

Supramolecular hydrogen-bonded polymers have numerous applications in materials chemistry, 

including use as reversible polymers that respond to changes in temperature or solvent 1 .The 

properties of such materials can be tailored according to the type of hydrogen-bonding array 

utilised, or the polymeric units inserted. The design of novel supramolecular materials requires 

the synthesis of core modules capable of forming strong hydrogen bonding interaction. Despite 

considerable progress in this area, the synthesis of supramolecular polymers based on the selfassembling 

DDAA modules has been predominantly restricted to materials incorporating the 

ureidopyrimidinone (Upy) unit reported by Meijer et al. 2 

We have recently reported the synthesis and characterisation of a novel quadruple 

hydrogen-bonding system incorporating a cytosine unit as a DDAA module 3 . The cytosine 

module was designed such that it does not undergo tautomeric changes which are observed 

with UPys. It formed quadruple hydrogen bonded assemblies both in solution and in the solid 

state, and the dimerization constant was estimated to be > 9 10 6 M -1 in C6D6. 

One major advantage of the cytosine-based arrays are that bifunctional cytosine motifs 

can readily be prepared through incorporation of a group R in addition to the polymeric or 

spacer unit. Recent results on the synthesis of cytosine modules possessing alternative R group 

will be described, together with the utilisation of different hydroxyl and amine terminated 

spacers or telechelic polymers (Figure 1). 

R 

N 

O N N 

H 

O 

N 

H 

n 

N 

H 

O 

O 

Polymer 

O 

O N H 

A A D D Polymer or small unit in the middle linked by 

a flexible spacer to the Cytosine unit 

Figure 1: R = alkyl chain 

The synthesis of polymers incorporating single and double urea units will also be reported and 

the physical properties of the materials prepared. Our results will highlight that the new cytosine 

module can be used successfully for the generation of novel supramolecular polymers. 

[1] J.M.Lehn, Supramolecular Chemistry, Science, 1993, 260, 1762-63. 

[2] A.T. Ten Cate, H. Kooijman, A.L. Spek, R.P. Sijbesma, E.W. Meijer, J. Am. Chem. Soc., 

2004, 126, 3801-08. 

[3] V.G.H. Lafitte, A.E. Aliev, P.N. Horton, M.B. Hursthouse, K. Bala, P. Golding, H.C. Hailes, J. 

Am. Chem. Soc., 2006, 128, 6544-45. 

n 

N 

H 

O 

N 

H 

N 

N R 

O 

A New Schiff Base Expanded Porphyrin Derived from Carbazole 

Jonathan L. Sessler, Dustin E. Gross and Vincent M. Lynch 

Department of Chemistry and Biochemistry, 1 University Station, The University of Texas at 

Austin, Austin, TX, 78712, USA 

Schiff base oligopyrrole macrocycles (so-called ‘expanded porphyrins’) 1 have attracted much 

attention for use as ligands for the coordination of various lanthanide, actinide, and transition 

metal cations. 2 The resulting complexes have been studied for a variety of applications, 

including those associated with drug development. Complementing these ongoing studies is 

the recognition that Schiff base expanded porphyrins, especially when protonated, may have a 

role to play as easy-to-modify receptors for neutral and anionic substrates. 3 This awareness 

has prompted us to focus on the construction of new, rationally designed Schiff base 

oligopyrrolic anion receptors. In this context, we have synthesized and characterized through 

X-ray diffraction means the new expanded, non-aromatic Schiff base macrocycle 3. As shown 

in the scheme below, it was prepared by condensing 1,8-diaminocarbazole 1 with a diformyl 

tripyrrane 2 in the presence of an acid catalyst. Macrocycle 3, containing sp 3 -hybridized meso 

bridging carbon centers, could be readily oxidized to afford 4. This latter product was found to 

bind chloride anions effectively in the solid state. Based on these findings, macrocycle 4 has 

been studied as a potential anion receptor and as a possible cation coordinating ligand in 

organic media. The results of these investigations will be detailed in this presentation. 

R 

R' R' 

H 2N 

O 

NH 

N 

H 

1 

+ 

H 

N 

2 

NH 2 

O 

HN 

R 

HCl 

MeOH 

R 

R' R' 

N 

NH 

N 

H 

Cl - 

H 

N 

3 HCl 

N + 

H 

HN 

R 

air, TEA 

acetone 

R 

R' R' 

N 

NH 

N 

H 

Cl - 

H 

N 

4 HCl 

N + 

H 

HN 

R = CH 2CH 3, CH 2CH 2CH 2OH, CH 2CH 2CH 2OCOCH 3 

R' = Cl, alkyl 

[1] Callaway, W. B.; Veauthier, J. M.; Sessler, J. L. J. Porphyr. Phthalocy. 2004, 8, 1-25. 

[2] Sessler, J. L.; Seidel, D. Angew. Chem., Int. Ed. 2003, 42, 5134-5175. 

[3] Sessler, J. L.; Gale, P. A.; Cho, W. S., Anion Receptor Chemistry. Royal Society of 

Chemistry: Cambridge, 2006. 

PSA 66 

R

Hierarchical self-assembly of dimeric coordination cages 

Francesca Gruppi a , Marco Busi a , Enrico Dalcanale a 

a Dipartimento di Chimica Organica ed Industriale, Università di Parma, Viale G.P. Usberti 17/a, 


Metal-directed self-assembly is a powerful tool for the construction of nanosize architectures 

performing specific functions. In previous works we have studied the quantitative self-assembly 

of stable organopalladium and organoplatinum coordination cages. [1, 2] The aim of the present 

work is the definition of hierarchical self-assembly protocols leading to assembly of coordination 

cages networks. As a first step in this direction, we have designed and synthesized tetradentate 

cavitand ligand 1, presenting three cyanophenyl and one ethynylpyridine ligands. The different 

affinity of cavitand 1 ligands toward Pt(II) and Pd(II) complexes has been investigated. Among 

the several possibilities, the hierarchical self-assembly protocol of scheme 1 has been selected 

as the most valid approach to quantitative formation of a dimeric coordination cage in solution. 

4 

4 

N N N 

O O 

O O O O O O 

R R R R 

6 Pd(dppp)OTf 2 

N 

O O 

Ph Ph Ph Ph 

NN N N 

P P 

N N 

NN 

PdL PdL 

PdL Pt 

Pt PdL PdLPdL 

NN N N 

O O 

Pt(tppb)OTf 2 

R R R R 

OOO 

O 

OOO O OO 

R R R R 

OO 

Ph 

P 

O O 

O O 

Ph 

R R R R 

O OO O 

N N N N 

O OO O OO 

R R R R 

Ph 

P 

Ph 

OO 

N N N N 

R 

O O O OOO O O 

N N 

OO O OOO OO 

R 

Pt 

Ph 

Ph 

P 

P 

R R 

R R 

Ph 

Ph 

R 

NN 

R 

Ph 

Ph 

P 

P 

Ph 

16 

Pt 

Ph 

R 

O O O OO O O O 

N N 

N N 

OO O OO O 

OO 

[1] R. Pinalli, V. Cristini, V.Sottili, S. Geremia, M. Campagnolo, A. Caneschi, E. Dalcanale, 

J.Am. Chem.Soc., 2004, 126, 6516 – 6517 

[2] F. Fochi, P. Jacopozzi, E. Wegelius, K. Rissanen, P. Cozzini, E. Marastoni, E. Fisicaro, P. 

Manini, R. Fokkens, E. Dalcanale, J. Am. Chem. Soc., 2001,123, 7539 – 7552 

1 

R 

R R 

R R 

PSA 67 

R 

N 

N 

N N 

R 

PSA 68 

Circular Polarization of Fluorescence Emitted from a Supramolecular 

Complex of Achiral Conjugated Polymers and Neutral Polysaccharides 

S. Haraguchi 1 , M. Numata 1 , C. Li 1 , M. Fujiki 2 , K. Sakurai 3 and S. Shinkai 1 

1 

Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu 

University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan 

2 

Graduate School of Materials Science, Nara Institute of Science and Technology, Takayama, 

Ikoma, Nara 630-0101, Japan 

3 

Department of Chemical Processes and Environments, Faculty of Environmental Engineering, 

The University of Kitakyushu, 1-1 Hibikino, Wakamatsu-ku, Kitakyushu, Fukuoka 808-0135, 

Japan -Conjugated polymers are nowadays used as the active layer in polymer light-emitting 

diodes (PLEDs). Several research groups have tried to control the linear polarization of the light 

output from the device by orienting the polymer chains in the film that are acting as the active 

layer. Hight degrees of linear polarization can be obtained in this way. As well as linearly 

polarized light sources, circularly polarized sources also find many applications in modern 

display technologies. In principle, it may be possible to construct a PLED that directly emits 

circularly polarized light by introducing molecular chirality into the conjugated polymer. Due to 

the break in the mirror-image symmetry, left or right circularly polarized light is then emitted and 

absorbed with different probabilities. For example, by substituting poly(p-phenylene vinylene) 

with chiral side chains, PLEDs were indeed found to emit circularly polarized light. However, in 

such cases, dichroism (CD) and circularly polarized luminescence (CPL) in the -* transition 

region has generally been observed only when the polymer is in aggregated and solid film 

states, due to chiral supramacromolecular ordering resulting from intermolecular - stacking. 

For this reason the emission of the aggregated phase is weaker by 1 order of magnitude than 

that of the free chains. Therefore, the backbone helix structure, which does not depend on the 

aggregated phase, is believed to achieve a high quantum yield of circularly polarized 

luminescence. Recently, we demonstrated that supramolecular chiral insulated molecular wire 

can be formed between achiral water-soluble conjugated polymers and neutral polysaccharides 

(schizophyllan; SPG)(1). In the present work, we have focused on the use of this 

supramolecular chiral complex as a PLED that directly emits circularly polarized light. 

[1] C. Li, M. Numata, A. -H. Bae, K. Sakurai, S. Shinkai, J. Am. Chem. Soc., 127, 4548 (2005).

PSA 69 

Assembly of Metallomacrocycles from Ditopic 2,2:6,2-Terpyridine Ligands 

with Flexible Spacers. 

Edwin C. Constable, Kate Harris, Catherine E. Housecroft, Markus Neuburger and Silvia 

Schaffner 

Department of Chemistry, University of Basel, Spitalstr. 51, 4056 Basel, Switzerland 

The reaction of ditopic ligands containing two 2,2’:6’,2”-terpyridine metal-binding domains linked 

by a variable spacer with transition metal ions can give metallopolymers [1] (copolymers with 

alternating metal centres and ligands), discrete molecular macrocycles [2], or mixtures of the 

two. The outcome of the coordination depends on the precise reaction conditions as well as the 

nature of both the spacer and the transition metal ion. 

Examples will be presented of metallomacrocycles of various sizes and nuclearities formed from 

the reaction of such ditopic ligands containing a flexible oligo- or poly(ethylene glycol) spacer 

with various cobalt salts. 

N 

N 

N 

O 

O 

0 n 65 

n O N 

Also presented will be a novel exchange reaction resulting from the reaction of these or 4’alkoxy-2,2’:6’2”-terpyridine 

ligands with cobalt(II) ions in the presence of alcohols. 

[1] S. Schmatloch, A. M. J. van den Berg, H. Hofmeier and U. S. Schubert, Designed 

Monomers and Polymers, 2004, 7(1-2), 191-201. 

[2] E. C. Constable, C. E. Housecroft, M. Neuburger, S. Schaffner and C. B. Smith, Dalton 

Trans., 2005, 2259-2267. 

N 

N 

PSA 70 

Metal-Assembled Cages Observed by Sonic Spray Mass Spectrometry 

Roger G. Harrison, Joseph S. Gardner, John D. Lamb, David V. Dearden 

Department of Chemistry and Biochemistry, Brigham Young University, C100 BNSN, Provo, 

Utah, 84602, USA 

Supramolecular compounds are often difficult to characterize and metal-assembled 

cages are no exception. We have found sonic spray ionization mass spectrometry (SSI MS) to 

be effective in characterizing metal-assembled cages that are not easily observed using 

conventional electrospray ionization mass spectrometry (ESI MS) techniques. 1 A palladiumassembled 

resorcinarene-based cage first assembled by the Dalcanle group, 2 and a 

palladium(II) triazine cage, first assembled by the Fujita group, 3 were characterized and their +1 

molecular ion peaks observed using SSI MS. Along with these cages, new N,Nbis(pyridylmethyl)amine 

resorcinarene cavitand-metal ion complexes were observed to have 

peaks corresponding to tetranuclear complexes and cage complexes. 4 The molecular ion 

peaks for these complexes were not detected with ESI MS. The soft ionization in SSI MS and its 

relatively simple design provide another tool to characterize such supramolecular assemblies. 

12 0 

10 0 

80 

60 

40 

20 

0 

N 

N 

N 

O O 

O 

O 

1500 2000 2500 3000 3500 4000 

m/v 

O 

OO O 

O O O O 

N 

N 

N 

N N N 

N N 

N 

Fe Fe N N N 

Fe 

Fe N 

N N N N N 

N 

N 

N 

O O O 

11 Cl- [1] Z. Takats, S. C. Nanita, R. G. Cooks, G. Schlosser, K. Vekey, Anal. Chem., 2003, 75, 1514- 

1523. 

[2] F. Fochi, P. Jacopozzi, E. Wegelius, K. Rissanen, P. Cozzini, E. Marastoni, E. Fisicaro, P. 

Manini, R. Fokkens, E. Dalcanale, J. Am. Chem. Soc., 2001, 123, 7539-7552. 

[3] S. Sakamoto, M. Yoshizawa, T. Kusukawa, M. Fujita, K. Yamaguchi, Org. Lett., 2001, 3, 

1601-1604. 

[4] J. S. Gardner, R. G. Harrison, J. D. Lamb, and D. V. Dearden, New J. Chem. 2006, 30, 

1276-1282.

Constrained cyclam derivatives as ligands for copper(II). 

Jan Plutnar, Jana Havlíková, Petr Hermann, Jan Kotek, Vojtch Kubíek 

PSA 71 

Department of Inorganic Chemistry, Universita Karlova (Charles University), Hlavova 2030, 128 

43 Prague 2, Czech Republic 

Copper radiopharmaceuticals utilizing 64 Cu or 67 Cu isotopes are increasingly investigated and 

used in experimental cancer treatment due to convenient properties of the isotopes [1]. The 

copper isotopes have been attached to several biological vectors including e.g. antibodies or 

small peptides. Most of ligands suitable for stable copper(II) complexation are based on cyclen 

or cyclam skeleton. Among them, DOTA and TETA derivatives are widely employed. However, 

properties of the ligands and the complexes are far from ideal ones. 

Some years ago, cross-bridged cyclam ("CB", at positions 1,8-) derivatives were 

suggested to improve chemical and pharmacological properties of their copper(II) complexes 

and Cu-based radiopharmaceuticals [2]. It was shown that in vivo stability was increased due 

higher stability of the complexes induced by the additional constrain added to the cyclam ring. 

There is another possibility to rigidity cyclam ring by addition of a carbon chain between "cis" 

nitrogen atoms, e.g. at 1,4-positions (side-bridged, "SB"). Despite ongoing activity in this field 

[3], thermodynamic stability of any such derivatives has not been investigated. 

In our contribution, we synthesized several CB- and SB-cyclam derivatives containing 

nitrobenzyl and/or coordinating groups (carboxylic or phosphonic/phosphinic acid groups). The 

ligands were prepared from cyclam-glyoxal aminal through selective alkylation and reduction 

followed by Mannich reaction (for phosphorus containing ligands). The ring amine dissociation 

constants are generally higher (the first protonation) and lower (the second protonation) than 

those of cyclam itself. Stability constants with divalent copper are lower than those of cyclam 

mainly due a less favourable arrangement of nitrogen atoms. Thermodynamic equilibrium was 

reached only after days at room temperatures (SB-cyclams) or at 80 C (CB-cyclams). 

Several crystal structures of the ligands and complexes was determined. Among them, 

unusual quarternary salt of SB-cyclam derivative has acetate group attached on piperazine 

nitrogen atoms. Copper(II) complex of nitrobenzyl derivative of SB-cyclam is five-coordinated 

(square pyramid) with benzene ring located close to the "sixth octahedral" position. 

Bis(methylphosphonate) derivative of CB-cyclam forms octahedral copper(II) complex where 

both phosphonate groups are monoprotonated. 

[1] Handbook of Radiopharmaceuticals. Radiochemistry and Applications, Ed. M. J. Welch and 

C. S. Redvanly, Wiley, Chichester, UK, 2003. 

[2] C. A. Boswell, X. K. Sun, W. J. Niu, G. R.Weisman, E. H.Wong, A. L., Rheingold and C. J. 

Anderson, J. Med. Chem., 2004, 47, 1465–1474. 

[3] J. D. Silversides, .C. C. Allan and S. J. Archibald, Dalton Trans., 2007, 971–978 

PSA 72 

Molecular Tectonics: STM Study of 2D Nanostructures and Design of Chiral 

Networks. 

Fatima Helzy, Adam Duong, James D. Wuest. 

Département de chimie, Université de Montréal, C.P. 6128, succursale. Centre-ville Montréal, 

Québec Canada H3C 3J7 

Molecular tectonics is a strategy for the design and construction of new ordered materials from 

special molecules called tectons. These subunits are able to associate strongly with the help of 

non-covalent bonds to generate robust, adjustable architectures by the process of spontaneous 

self-assembly. This strategy has proven to be an efficient way to direct arrangement of 

molecules in the solid state and to form predictable 3D frameworks. 1 

Recently, we have been interested in applying this approach to program the construction of 2D 

molecular networks on surface. Scanning tunnelling microscopy (STM) is an effective tool for 

characterizing the structures of the resulting nanopatterned surfaces. 

We will describe the self-assembly of 2D network formed by 2,2’-bipyridine-4,4’-dicarboxylic 

acid when deposited from solution on highly oriented pyrolytic graphite (HOPG). STM images 

suggest that each molecule is bound flat on the surface and forms hydrogen bonds with four 

neighbours. The 2D organization is different from the one found in 3D crystals of the compound, 

although both structures feature similar pyridine-carboxylic acid interactions. 2 

We are also interested in the introducting chirality into networks bproduced by the strategy of 

molecular tectonics. In particular, we have targeted tectons bearing a sulfoxide group as a 

stereogenic center. 

A series of enantiomerically pure tectons of this type have been prepared in good yield by 

efficient methods. 

We are optimistic that 3D networks resulting from the assocaition of thes compounds will 

provide a source of new chiral porous materials with interesting properties, such the 

enantioselective inclusion of guests. 

[1] J.D Wuest, Chem. Commun., 2005, 5830-5837 and references cited therein. 

[2] E. Tynan, P. Jensen, P. E. Kruger, A. C. Lees and M. Nieuwnhuyzen, Dalton Trans., 2003, 

1223-1228

Supra-Biomolecular Tandem Assays – Application Examples 

Andreas Hennig, Hüseyin Bakirci, and Werner M. Nau 

Jacobs University Bremen, School of Engineering and Science, Campus Ring 1, D-28759 

Bremen, Germany, E-mail: w.nau@jacobs-university.de 

PSA 73 

The chemical and pharmaceutical community has great interest in simple, fast and reliable 

screening methods to determine the activity of catalysts and enzymes. 1 Established methods 

require antibodies which need to be raised for a specific analyte by time-consuming and 

expensive methods. 2,3 In addition, the laborious chemical derivatization of substrates, which 

presents an alternative approach, is often accompanied by a change (or even loss) in activity. 4,5 

We present a novel label-free supramolecular method, in which macrocyclic hosts mimic the 

role of antibodies for assaying enzymatic activity. A simple and versatile concept has been 

developed based on the dynamic equilibria of a fluorescent dye, a substrate and a product as 

well as their respective host-guest complexes. Accordingly, as the enzymatic reaction proceeds, 

the conversion of the substrate to the product is coupled with a change in the host-guest 

complexation equilibrium of the fluorescent dye with the macrocycle (supra-biomolecular 

tandem). The latter can be detected continuously with high sensitivity in enzyme assays. We will 

present application examples for enzymatic decarboxylation and hydrolysis as well as an 

inhibitor screening. 

[1] Reymond, J. L., Enzyme Assays. Wiley-VCH: Weinheim, 2005. 

[2] Tawfik, D. S.; Green, B. S.; Chap, R.; Sela, M.; Eshhar, Z., Proc. Natl. Acad. Sci. USA 1993, 

90, 373-377. 

[3] MacBeath, G.; Hilvert, D., J. Am. Chem. Soc. 1994, 116, 6101-6106. 

[4] Hennig, A.; Roth, D.; Enderle, T.; Nau, W. M., ChemBioChem 2006, 7, 733-737. 

[5] Hennig, A.; Florea, M.; Roth, D.; Enderle, T.; Nau, W. M., Anal. Biochem. 2007, 360, 255- 

265. 

PSA 74 

Synthesis of large polyazamacrocycles by the [3+3] cyclocondensation 

Jana Hodaová a,b , Petr Hadrava a , Jií Hlinka a 

a Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 

Flemingovo nám. 2, 166 10 Prague 6, Czech Republic 

b Department of Organic Chemistry, Institute of Chemical Technology, 166 28 Prague 6, Czech 

Republic 

Condensation reaction of diamines with dicarbonyl compounds has been frequently used 

for the preparation of macrocyclic Schiff bases. Usually, the [2+2] cyclocondensation prevails 

leading to the cyclic tetra Schiff bases. The macrocycle formation is often supported by use of a 

metal cation template. [1-3] Only recently, the first example of the [3+3] cyclocondensation 

product obtained in the absence of a template has been reported. [4] Finding that the reaction of 

trans-1,2-diaminocyclohexane with terephthaldehyde affords the triangular [3+3] hexa Schiff 

base in practically quantitative yield in the absence of a template [5,6] attracted our attention to 

the [3+3] cyclocondensation reaction studies. Due to reversible character of the condensation 

reaction, the equilibrium composition in solution can differ from that in the solid, which is 

obtained upon evaporation of the solvent. Our studies have revealed that the rigid rod-like 

dialdehydes give on the reaction with trans-1,2-diaminocyclohexane exclusively the [3+3] hexa 

Schiff bases both in solution and in the solid phase. The cyclocondensations have been carried 

out in the absence of a template, and without use of the high-dilution method. The results 

indicate superior thermodynamic stability of the [3+3] cyclocondensation products. 

The [3+3] cyclocondensation of the rigid rod-like aromatic dialdehydes with trans-1,2diaminocyclohexane 

is a highly efficient atom-economy approach to the preparations of large 

polyazamacrocycles. Various rigid dialdehydes have been used in the cyclisation reaction in 

order to extend systematically the macrocycle size as well as to introduce the additional binding 

sites into the macrocycle structure. Novel macrocyclic [3+3] hexa Schiff bases have been 

reduced to the corresponding hexaamines. These macrocyclic polyamines can be utilised in 

anion binding, [7] chiral molecular recognition, and catalysis. 

[1] S. M. Nelson, Pure Appl. Chem. 1980, 52, 2461-2476. 

[2] P. Guerriero, P. A. Vigato, D. E. Fenton, P. C. Hellier, Acta Chem. Scand. 1992, 46, 1025- 

1046. 

[3] W. Radecka-Paryzek, V. Patroniak, J. Lisowski, Coord. Chem. Rev. 2005, 249, 2156-2175. 

[4] S. R. Korupoju, P. S. Zacharias, Chem. Commun. 1998, 1267-1268. 

[5] J. Gawronski, H. Kolbon, M. Kwit, A. Katrusiak, J. Org. Chem. 2000, 65, 5768-5773. 

[6] M. Chadim, M. Budšínský, J. Hodaová, J. Závada, P. C. Junk, Tetrahedron Asymmetry 

2001, 12, 127-133. 

[7] J. Hodaová, M. Chadim, J. Závada, J. Aquilar, E. García-España, S. V. Luis, J. F. Miravet, 

J. Org. Chem. 2005, 70, 2042-2047. 

The authors thank the Czech Science Foundation (Reg. No. 203/05/0702) for financial support 

of this research project.

Binding of uranyl and lanthanide cations by azacalix[n]arenes : 

thermodynamic and kinetic approach 

V. Hubscher-Bruder a , F. Arnaud-Neu a , C. Ambard a , P. Jost b , G. Wipff b 

a Laboratoire de Chimie-Physique, Département des Sciences Analytiques, Institut 

Pluridisciplinaire Hubert Curien, ULP, CNRS - ECPM, 25 rue Becquerel, 67087 Strasbourg 

Cedex 02, France 

b Laboratoire de Modélisation et de Simulations Moléculaires, Institut de Chimie, ULP, CNRS - 

4 rue Blaise Pascal, 67070 Strasbourg, France 

Azacalix[n]arenes are calix[n]arenes derivatives in which at least one methylene bridge is 

replaced by a –CH2-N(R)-CH2- group.[1, 2] Compared with calixarenes, they have a larger more 

flexible cavity and possess two different kinds of potential binding sites. Previous structural 

studies on azacalixarenes showed their ability to complex uranyl and lanthanide cations even 

without the presence of a base, by internal transfer of the phenolic protons to the nitrogen 

atoms.[3-5] 

We present here the thermodynamic and kinetic studies 

of the binding of uranyl and some trivalent lanthanides 

(La 3+ , Nd 3+ , Eu 3+ and Yb 3+ ) by the two azacalixarenes, pmethyl-N-tetrahomodiazacalix[4]arene 

[1] and p-chloro- 

N-benzylhexahomotriazacalix[3]arene [2]. These 

calixarenes are locked in cone conformation by strong 

intramolecular hydrogen bonds.[6] 

H3C 

H 3C 

OH 

N 

HO 

OH HO 

N 

CH 3 

CH3 

Cl 

N OH N 

OH HO 

N 

Cl Cl 

[1] [2] 

PSA 75 

In the first part, the stoichiometry and the stability constants of the different complexes formed in 

acetonitrile determined using UV absorption spectrophotometry will be presented. The results 

showed the formation of strong 1:1 complexes in all cases (log in the range 3.8 - 6.4), whose 

stability constants were strongly dependent on the ligand and medium (10 -2 M Et4NNO3 as 

supporting electrolyte, presence or absence of Et3N as base). They could be explained by 

considering the size and protonation state of the ligand, the coordination mode, the nature of 

the interactions, in the light of molecular modelling studies using molecular dynamics in 

explicitely represented solutions. 

In the second part, the stopped-flow spectrophotometric technique was used to study the fast 

kinetics of complexation of uranyl (25°C). The rate constants of the complexation reaction were 

determined from the exponential variations of the absorbances vs. time according to the 

pseudo-first order method. They were observed to depend on the presence or absence of base. 

The results could be interpreted on the basis of previous X-ray studies of the complexes 

isolated in the solid state [3-5], ESI-MS data and molecular dynamics modelling studies and a 

mechanisms were proposed showing the formation in one or more steps of either external or 

internal complexes. 

[1] Takemura H., J. Inclusion Phenom., 2002, 42, 169. 

[2] Niikura K., Anslyn E. V., J. Chem. Soc., Perkin Trans. 2, 1999, 2769. 

[3] Thuéry P., Nierlich M., Vicens J., Takemura H., J. Chem. Soc., Dalton Trans., 2000, 279. 

[4] Thuéry P., Nierlich M., Vicens J., Takemura H., Polyhedron, 2000, 19, 2673. 

[5] Thuéry P., Nierlich M., Vicens J., Masci B., Takemura H., Eur. J. Inorg. Chem., 2001, 637. 

[6) Masci B., in “Calixarenes 2001”, Asfari Z., Böhmer V., Harrowfield J., Vicens J., Eds, Kluwer 

Academic Publishers, Dordrecht, 2001, p.235. 

Anion recognition by triurea based macrocycles 

PSA 76 

E. Jobin a , V. Hubscher-Bruder a , F. Arnaud-Neu a , S. Michel a , V. Böhmer b , D. Meshcheryakov b , 

M. Bolte c 

a Laboratoire de Chimie-Physique, Département des Sciences Analytiques, Institut 

Pluridisciplinaire Hubert Curien, ULP, CNRS - ECPM, 25 rue Becquerel, 67087 Strasbourg 

Cedex 02, France 

b J.-Gutenberg-Universität, 55099 Mainz, Germany 

c J.-W.-Goethe Universität, 60439 Frankfurt/Main, Germany 

Anion recognition is today an increasingly topical field in supramolecular chemistry due to the 

possible applications in ion selective sensors for biological and environmental concerns. The 

design of efficient and selective synthetic anion receptors is not an easy task because of 

specific anion properties (negative charge, large size, various geometries, high solvation free 

energies, pH-dependent forms) which have to be taken into account. [1-4] Urea functions 

which are powerful hydrogen bond donors can be used to design neutral macrocyclic 

receptors. Some of these receptors have already shown selective recognition of anions.[5-6] 

We report here the synthesis and the binding properties of four cyclic trimers in which urea 

functions are linked by all combinations of rigid xanthene (X) and flexible diphenylether (D) 

subunits. 

The complexing abilities of these molecules towards different anions (Cl - , Br - , SCN - , NO3 - , 

H2PO4 - , HSO4 - , ClO4 - and AcO - ) have been assessed by 1 H NMR, UV-absorption 

spectrophotometry and microcalorimetry in various solvents. In acetonitrile, complexes with 

different stoechiometries are formed depending on the ligand and the anion. Their 

thermodynamic parameters (stability constants, complexation enthalpies and entropies) are 

discussed in terms of rigidity or flexibility of the ligands and of geometry and basicity of the 

anions. 

[1] S. Mangani, M. Ferraroni, in “Supramolecular Chemistry of Anions”, A. Bianchi, K. Bowman- 

James, E. Garcia-Espana (Editors), Wiley-VCH, New-York, 1997, 63. 

[2] P.D. Beer, P.A. Gale, Angew. Chem. Int. Ed., 2001, 40, 486. 

[3] P.A. Gale, Coord. Chem. Rev., 2003, 240, 191. 

[4] R.S. Dickins, D. Parker, in “Macrocyclic Chemistry: Current Trends and Future 

Perspectives”, K. Gloe (Editor), 2005, 121. 

[5] C.R. Bondy, P.A. Gale, S.L. Loeb, J. Am. Chem. Soc., 2004, 126, 5030 

[6] D. Meshcheryakov, V. Böhmer, M. Bolte, V. Hubscher-Bruder, F. Arnaud-Neu, H. 

Herschbach, A. Van Dorsselaer, I. Thondorf, W. Mögelin, Angew. Chem. Int. Ed., 2006, 45, 

1648.

PSA 77 

Synthesis and molecular recognition studies of new enantiopure BODIPY 

linked monoaza-18-crown-6 ligands 

Ildikó Móczár a , Péter Huszthy a,b , Mihály Kádár c , Klára Tóth c 

a Department of Organic Chemistry and Technology, Budapest University of Technology and 

Economics, H-1111 Budapest, Szent Gellért tér 4, Hungary 

b Research Group for Alkaloid Chemistry of the Hungarian Academy of Sciences 

H-1111 Budapest, Szent Gellért tér 4, Hungary 

c Department of Inorganic and Analytical Chemistry and Research Group for Technical 

Analytical Chemistry of the Hungarian Academy of Sciences, Budapest University of 

Technology and Economics, H-1111 Budapest, Szent Gellért tér 4, Hungary 

The use of fluorescent sensor molecules for the detection of metal ions, organic and biological 

analytes has attracted much research interest from synthetic point of view as well as from the 

point of view of understanding the photophysical mechanisms governing the spectroscopic 

behaviour of such systems [1, 2]. Among others BODIPY dyes are used as fluorescent 

signalling moiety of sensor molecules because of their advantageous spectroscopic properties. 

R 

* 

O 

O 

N 

O 

R=H, alkyl 

Figure 

N 

N 

B F 

F 

OMe 

O 

O 

* 

R 

According to the literature [3] BODIPY linked 

monoaza-18-crown-6 ether (Figure, R=H) is 

a K + and Ca 2+ selective fluorescent ICT 

(internal charge transfer) type sensor 

molecule and provides information about the 

complexation via spectral shifts of the 

absorption and emission bands with 

enhancement of the fluorescence intensity. 

Based on the advantageous properties of 

the above mentioned crown ether (Figure, 

R=H), we synthesized its enantiopure 

analogues (Figure, R=alkyl) bearing two 

alkyl groups on their chiral centers. The 

complexation of the BODIPY linked ligands 

(Figure, R=H and alkyl) with the 

enantiomers of chiral primary ammonium 

salts and also metal ions have been studied 

by UV-Vis and fluorescence spectroscopies. 

Financial support of the National Scientific Research Fund of Hungary (OTKA: K 62654, T 

46403) is gratefully acknowledged. 

[1] Handbook of Photochemistry and Photobiology, ed. by H. S. Nalwa, Volume 3: 

Supramolecular Photochemistry, Chapter 5,6, American Scientific Publishers, Stevenson 

Ranch, California, USA, 2003 

[2] J. F. Callan, A. P. de Silva and D. C. Magri, Tetrahedron, 2005, 61, 8551-8588 

[3] M. Baruah, W. Qin, R. A. L. Vallée, D. Beljonne, T. Rohand, W. Dehaen and N. Boens, 

Organic Letters, 2005, 7, 4377-4380 

PSA 78 

Copper(I) Complexes with Reversibly-Formed Imine Bonds : Synthetic 

Control via Self-Assembly 

Marie Hutin a , Gérald Bernardinelli b , Jonathan R. Nitschke a 

a Sciences II, University of Geneva, 30 quai Ernest Ansermet, 1211 Geneva 4, Switzerland. 

b Laboratory of X-Ray crystallography, University of Geneva, 24 quai Ernest Ansermet, 1211 

Geneva 4, Switzerland. 

Our group has developed a self-assembly methodology that allows unusual structures to be 

created in excellent yield. Amine and aldehyde subcomponents are held together by reversiblyformed 

imine (C=N) bonds that self-assemble around copper(I) templates. 

The reaction of aldehyde A with diamine B and copper(I) in aqueous solution gave the single 

macrocyclic structure 1. X-ray crystallography confirmed the presence of this structure in the 

solid state. The addition of sulfanilic acid (4 equiv) to an aqueous solution of macrocycle 1 

resulted in its conversion to helicate 2. By changing the pH, it was thus possible to switch 

dynamically between the open topology of a helicate and the closed topology of a 

macrocycle.[1] 

HN 

H 

N 

O O O O 

NH HN 

N N 

N N 

Cu Cu 

N N 

N N 

O O 

3 

H 

N 

H 

N 

NH2 2 

C 

NH 2 

2 

A 

N 

N 

O 

O 

2 Cu(I) 

O 

2 

B 

O 

NH2 NH2 N N 

N Cu N 

N Cu N 

N N 

When dianiline C was employed instead of diamine B as a subcomponent, a single product was 

observed by NMR spectroscopy. Based upon the length and flexibility of the diamine spacer, we 

were able to select catenate 3 as the unique product of this self-assembly reaction.[1] 

The 

reaction of diformylpyridine and copper(I) 

with diamine B or 8-aminoquinoline in 

acetonitrile solution generated 

“undersaturated” macrocycle 4 (only three 

nitrogen donors per copper) or 

“oversaturated” helicate 5 (five such donors), 

respectively. When diamine B, 

diformylpyridine and 8-aminoquinoline are 

present simultaneously, the possibility exists 

N N 

Cu 

N N 

Cu 

N N 

O O 

N N 

Cu 

N N 

N 

N N 

Cu 

N N 

N 

Cu 

N N 

N N 

Cu 

N N 

of creating a heterocomplex in which both copper(I) 

ions and ligands are valence-satisfied 

(complex 6). This complex could also be prepared through mixing macrocycle 4 and helicate 5 

together in acetonitrile solution.[2] 

N 

O O 

4 5 

2 

O O 

6 

[1] 

M. Hutin, C.A. Schalley, G. Bernardinelli, J.R. Nitschke, Chem. Eur. J., 2006, 12, 4069-4076. 

[2] M. Hutin, G. Bernardinelli, J.R. Nitschke, Proc. Natl. Acad. Sci. USA, 2006, 103, 17655- 

17660. 

O 

O 

O O 

1 

4 H 3N SO 3 - 

+ 

2 O 

O -O3S H3N NH3 2 O 

H 2N 

+ 

+ 

NH2 

O 

4 H 2N SO 3 - 

N N 

N Cu N 

N Cu N 

N N 

SO 3 - 

-O3S - 

2 SO3

Multi-chromophoric assemblies obtained via metallo-porphyrins and 

bisimide dyes coordination 

Elisabetta Iengo a , Gregory J. E. Davidson a , G. Dan Pantos a , Jeremy K. M. Sanders a 

a 

University of Cambridge, Department of Chemistry, Lensfield Road, Cambridge CB2 1EW, 

UK. (email: ei212@cam.ac.uk) 

The selective affinity of different metallo-porphyrins towards nitrogen or oxygen has been 

exploited for the efficient construction of stable multi-chromophoric assemblies. In particular, 

Al(III)-porphyrins can axially bind one -COOH or one -OH moiety, whereas Ru(II)(CO)porphyrins 

can bind one pyridyl group [1-3]. Therefore, a very flexible strategy can be used to 

assemble units with different functionalities. A variety of building blocks, including bisimide dyes 

bearing appended pyridyl and/or carboxylic functionalities, as well as Al(III)(OH)-monopyridyl or 

tetrapyridyl porphyrins and Ru(II)(CO)-tetraphenyl porphyrins have been prepared. These units 

have been successfully combined to produce a variety of multi-component systems with 

increasing complexity (some examples are reported in the figure below). All the adducts have 

been fully characterized in solution and are very stable (at least up to 10 -5 M). For some of them 

the X-ray crystal structure has been obtained. Such systems gathers together different types of 

chromophores, and are currently object of photophysical studies. 

N N 

Al 

N N 

O 

O 

N 

O 

O 

O 

N 

O 

O 

N 

O 

[1] J. K. M. Sanders, N. Bampos, Z. Clyde-Watson, S.L. Darling, J.C. Hawley, H-J. Kim, C. C. 

Mak and S. J. Webb in The Porphyrin Handbook; K. M. Kadish, K. M. Smith and R. Guilard 

Eds.; Academic Press New York, 2000, 3, 1-48. 

[2] P. P. Kumar and B. G. Maiya New J. Chem. 2003, 27, 619-625. 

[3] G. J. E. Davidson, L. H. Tong, P. R. Raithby and J. K. M. Sanders Chem. Commun. 2006, 

29, 3087-3089. 

O 

N 

O 

O 

O 

Al N 

PSA 79 

Ru CO 

PSA 80 

Enantiodiscrimination of Carboxylic acid Anions by Abiotic Guanidinium 

Receptors 

Vinod D. Jadhav and Franz P. Schmidtchen 

Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, 85747, 

Garching, Germany. e-mail: vinod.jadhav@ch.tum.de 

Chiral differentiation of carboxylic acid anions has gained importance due to its presence in 

biologically related processes. Towards this goal chiral bicyclic guanidinium anchor groups (cf. 

1-3) gained particular prominence recently. The chiral macrocyclic guanidinium host 1 was 

shown to effectively differentiate the antipodal tartrate and aspartate anions 1 compared to its 

iso-structural open chain analogue 2. The macrocyclic host 1 also forms complexes of higher 

stoichiometry with carboxylic anions, thus indicating its structural adaptability. This originates 

from its flexibility and the possibility of self-satisfying intramolecular interactions. The great 

variety of options for guest binding modes weakens and almost annihilates the chiral recognition 

capacity. 

N 

NO2 

O 

O 

N 

H 

NH 

N 

H 

N 

H N 

H 

HN 

+ + 

NH 

H 

N 

H 

N 

H 

N 

HN 

H 

N 

O 

O 

NO 2 

1 

N 

In an effort to emphasize the uniqueness of the binding mode host 3 was constructed. The 

design is based on accessibility restrictions of the guanidinium anchor sites formed by rigid 

annellation of congested benzimidazole heterocycles. The synthetic strategy started from an 

achiral guanidinium building block which after annelation was separated into diastereomeric and 

enantiomeric anion hosts. We report on the preparation and preliminary host-guest binding 

properties of these novel anion receptors. 

N 

S 

N 

N 

H 

N 

R 3 

N 

H 

S 

N 

(1) Jadhav, V. D.; Schmidtchen, F. P. Org. Lett. 2006, 8, 2329-2332. 

N 

R 

N 

NH 

NH 

O 

NH 

NH 

O 

2 

N 

H 

H 

N 

NO 2 

NO 2 

X-ray structure of 3-S-mandelate (R=H)

PSA 81 

Reaction of phthalic aldehydes with a,w-diamines for generation of Dynamic 

Combinatorial Libraries 

Magdalena Jarosz, a Janusz Jurczak a,b 

a) Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland 

b) Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 

01-224 Warsaw, Poland 

Dynamic Combinatorial Chemistry[1] [2] explores various reversible reactions and thus is a 

useful tool in supramolecular chemistry. As a result of such reaction the dynamic combinatorial 

library, consisting of various components, is obtained. By changing the conditions, e.g. 

templating cation, distribution of obtained products can be changed favouring the desired one. 

We present our studies on imination reaction between phthalic aldehydes and three different in 

length linear diamines exemplified by that shown in Scheme 1. 

Scheme 1 

Dynamic Combinatorial Libraries of obtained macrocyclic imines were analysed using 

electrospray ionization mass spectrometry (ESI-MS). The libraries were "frozen" by the 

reduction reaction (NaBH4) and obtained amines protected and analysed by HPLC technique. 

[1] J.M. Lehn, Science, 2002, 295, 2400-2403 

[2] S. Otto, R.L.E Furlan, J.K.M Sanders, Drug Discovery Today, 2002, 7, 117-125 

Chemical Detection of Explosives 

Jan O. Jeppesen, 1 Kent A. Nielsen, 1 Lise G. Jensen, 1 Andrew D. Bond, 1 

Won-Seob Cho, 2 Vincent M. Lynch, 2 and Jonathan L. Sessler 2 

PSA 82 

1 

The University of Southern Denmark, Odense University, Campusvej 55, 5230 Odense M, 

Denmark; e-mail: joj@chem.sdu.dk 

2 

The University of Texas at Austin, Austin, 1 University Station-A5300, Texas 78712-0165, USA 

The advent of supramolecular chemistry [1] has stimulated the interest in developing 

chemosensors capable of recognizing [2] specific chemical species through weak, non-covalent 

interactions. Calix[4]pyrroles [3] – first synthesized in the nineteenth century by Baeyer – are 

endowed with four pyrrole NH hydrogen bond functionalities and have recently received 

extensively attention as receptors for anionic and neutral substrates. The incorporation of redoxactive 

components into chemosensors is one means of enhancing the recognition process via, 

e.g., increased donor-acceptor interactions. In this context, the use of tetrathiafulvalene [4] (TTF) 

appears particularly attractive and a calix[4]pyrrole incorporating four appended TTF units has 

recently been synthesized. [5,6] It will be demonstrated, that this tetra(TTF)-calix[4]pyrrole is an 

excellent chemosensor capable of detecting explosives – such as trinitrotoluene (TNT) 

commonly used in landmines – through a simple color change from yellow to green (see figure). 

[1] J.-M. Lehn, Supramolecular Chemistry, VCH, Weinheim, Germany, 1995. 

[2] (a) P. D. Beer, P. A. Gale Angew. Chem. Int. Ed. 2001, 40, 486−516. (b) K. A. Nielsen, J. 

O. Jeppesen, E. Levillain, J. Becher Angew. Chem. Int. Ed. 2003, 42, 187–191. 

[3] J. L. Sessler, P. A. Gale in The Porphyrin Handbook, Vol. 6 (Eds.: K. M. Kadish, K. M. 

Smith, R. Guilard), Academic Press, San Diego, 2000, pp. 257–278. 

[4] (a) J. L. Segura, N. Martín Angew. Chem., Int. Ed. 2001, 40, 1372–1409. 

(b) J. O. Jeppesen, J. Becher Eur. J. Org. Chem. 2003, 3245–3266. 

[5] K. A. Nielsen, W.-S. Cho, J. O. Jeppesen, V. M. Lynch, J. Becher, J. L. Sessler J. Am. 

Chem. Soc. 2004, 126, 16296–16297. 

[6] K. A. Nielsen, W.-S. Cho, J. Lyskawa, E. Levillain, V. M. Lynch, J. L. Sessler, J. O. 

Jeppesen J. Am. Chem. Soc. 2006, 128, 2444–2451.

New Amido-Based Multicyclic Hosts for Anions 

Sung Ok Kang, Victor W. Day, Kristin Bowman-James 

Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence KS 66045. 

Anions play very important roles in biochemical systems as well as in the environment. Since 

anion coordination chemistry has become an intense research area, hosts for anions with 

elegant architectures have developed rapidly over several decades.[1] Because anions have 

several different distinguishing aspects compared to cations, such as larger size, high solvation 

energy, various shapes (spherical, linear, trigonal planar, and tetrahedral), and sometimes pH 

dependence, designing anion receptors is even more challenging.[2] In order to achieve the 

goal of designing highly selective hosts for anions, both the choice of functional groups as a 

hydrogen bonding sites and their arrangements in host frameworks will be crucial. 

Even though multicycles have tended to bind anions strongly due to their increased 

dimensionality as well as their increased number of binding sites, only a few amido-based 

multicyclic hosts for anions have been published to date.[3] These reported hosts include a 

bicycle and tricycle based on the prototype 1 reported by our group.[4,5] Recently we modified 

the design strategy to obtain two new classes of bicyclic and tricyclic hosts, 2 and 3, the 

frameworks of which are also based on monocycle 1. 

H 3 C 

O 

N 

H 

N 

H 

N 

O 

O 

X 

N 

H 

A N CH3 H 

N 

X 

O 

- A- A- A- 1 X=CHorN 

Monocycle 

2 

Bicycles 

3 

Tricycles 

PSA 83 

Each of the new multicyclic hosts displays its own unique structural and chemical binding 

properties in terms of anion binding. NMR and crystallographic studies of the new anion hosts 

will be described. 

[1] A. Bianchi, K. Bowman-James, E. García-España (Eds.), Supramolecular Chemistry of 

Anions, WILEY-VCH, New York, 1997. 

[2] P. D. Beer, P. A. Gale, Angew. Chem. Int. Ed. 2001, 40, 486-516. 

[3] S. O. Kang, M. A. Hossain, K. Bowman-James, Coord. Chem. Rev. 2006, 250, 3038-3052. 

[4] S. O. Kang, J. M. Llinares, D. Powell, D. VanderVelde, K. Bowman-James, J. Am. Chem. 

Soc. 2003, 125, 10152-10153. 

[5] S. O. Kang, D. Powell, V. W. Day, K. Bowman-James, Angew. Chem. Int. Ed. 2006, 45, 

1921-1925. 

Prodigiosin Analogues and Related Polypyrrolic Anion Receptors; 

Thermodynamic and Kinetic Studies 

Jonathan L. Sessler † , Elizabeth T. Karnas † , Dustin E. Gross † , Leah R. Eller † , Won-Seob Cho † , 

Sergios Nicolaou † , Apolonio Aguilar † , Jeong Tae Lee † , Vincent M. Lynch † , Darren J. Magda, ‡ 

Kenneth A. Johnson † 

† Univeristy of Texas at Austin, 1 University Station A5300, Austin, TX 78712, USA 

‡ Pharmacyclics, Inc. 995 East Arques Avenue Sunnyvale, California 94085, USA 

The prodigiosin alkaloid is a natural product consisting of a pyrrolylpyrromethene core 

and has been shown to have a broad range of biological activity 1 , including pH modulation, cell 

cycle inhibition, DNA cleavage, 2 and mitogen-activated protein kinase inhibition. 3 We are most 

interested in the role of prodigiosin as a pH modulator, which it accomplishes by H + /Cl - symport 

activity. 4,5 

Our group has sought to provide chemical evidence for this binding/transport event by 

synthesizing a basic series consisting of a ‘natural’ prodigiosin 1, and simple prodigiosin 

analogues. 6 Binding constants were determined through isothermal titration calorimetry (ITC), 

transport efficiency was determined by efflux across a phospholipid membrane as a function of 

time and anticancer activity was tested in vitro with A549 human lung and PC3 human prostate 

cancer cells. These studies 6 revealed a correlation between transport efficiency and anticancer 

activity, while the binding constants (Ka), a thermodynamic parameter, was not found to be a 

predictor of biological activity. This leads us to suggest that kinetic effects, associated with 

anion complexation or decomplexation, play a dominant role. 

Ongoing detailed analyses, which will be the subject of this presentation, have served to 

underscore the fact that prodigiosin analogues 2, as well as several other oligopyrrolic systems, 

are characterized by complex thermodynamic and kinetic anion binding interactions that are a 

function of not only the structure itself, but also the counter-ion and solvent as well. 

N 

H 

X- 

N 

H 

H + 

OMe 

N 

1 2 

[1] Fürstner, A. Angew. Chem. Int. Ed. 2003, 42, 3582-3603. 

[2] Melvin, M.; Tomlinson, J.; Saluta, G.; Kucera, G.; Lindquist, N.; Manderviller, R. J. Am. 

Chem. Soc. 2000, 122, 6333-6334. 

[3] Tomas, R.; Montaner, B.; Llagostera, E.; Soto-Cerrato, V. Biochem. Pharmacol. 2003, 66, 

1447-1452. 

[4] Sato, T.; Konno, H.; Tanaka, Y.; Kataoka, T.; Nagai, K.; Wasserman, H.; Okhuma, S. J. Bio. 

Chem. 1998, 273, 21455-21462. 

[5] Seganish, J.; Davis, J. Chem. Commun., 2005, 5781-5783 

[6] Sessler, J.; Eller, L.; Cho, W.S.; Nicolau, S.; Aguilar, A.; Lee, J.T.; Lynch, V.; Magda, D. 

Angew. Chem. Int. Ed. 2005, 44, 5989-5992. 

N 

H 

N 

H 

H 

N 

+ X- 

PSA 84

Binding of perrhenate and pertechnetate anions by bipyrrole based 

receptors 

Evgeny A. Katayev a , Patricia Melfi b , Nikolay V. Boev a , Grigory V. Kolesnikov a , Ivan G. 

Tananaev c and Jonathan L. Sessler b 

a A. N. Nesmeyanov Institute for Organoelement Compounds, Russian Academy of Sciences, 

Vavilova st. 28, 119991, Moscow, Russian Federation 

b Department of Chemistry & Biochemistry, The University of Texas at Austin, 1 University 

Station A5300, Austin, TX 78712-0165 USA 

c Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Science, 

Leninskiy pr. 31, 119991, Moscow, Russian Federation 

Development of highly efficient systems capable of binding specific anions selectively is 

recognized as being a key predicate to solving a number of fundamental problems, including 

anion sensing, extraction, and separation. A number oxoanions are also recognized as toxic or 

undesirable in certain situations. Sulfate can interfere with the vitrification processes that have 

been proposed for long-term containment and storage of low activity wastes (LAW). 

Pertechnetate anion is the most common form of the long-lived isotope 99 (t1/2 = 2.13 x 10 5 

years) that is formed from 235 U or 239 Pu. Our previous investigations showed the ability of 

oligopyrrolic macrocycles to bind tetrahedral oxoanions efficiently [1]. The aim of the work that 

will be summarized in this presentation is to examine the fundamental determinants of our 

macrocyclic molecules as applied to the areas of recognition, binding, and extraction. Towards 

this end, the anion-binding properties of a series of bipyrrole containing receptors were 

measured using UV-VIS titration methods. From this analysis, two bipyrrole-containing 

receptors, namely 1 and 2, were identified that proved effective for the ReO4 - anion (used as 

non-radioactive analogue of TcO4 - ). These receptors were studied as their tetrafluoroborate 

salts for extraction experiments and both were found to extract pertechnetate efficiently over a 

wide range of pH without the need for phase transfer agents. Follow-up competitive extraction 

studies revealed that receptor 1 effected a high level of pertechnetate extraction at neutral pH 

even in presence of the potentially competing anions, sulfate and perchlorate anions. 

NH 

NH 

NH 

N 

N 

HN 

HN 

HN 

Ph Ph 

O N 

H 

HN O 

NH HN 

n-Pr 

N N 

NH 

1 2 

[1] Evgeny A. Katayev, Nikolay V. Boev, Victor N. Khrustalev, Yuri A. Ustynyuk, I. G. Tananaev, 

and Jonathan L. Sessler, J. Org. Chem., 2007, 10.1021/jo0624849 

HN 

n-Pr 

PSA 85 

Host-Assisted Guest Protonation with Cucurbit[7]uril 

Apurba L. Koner a , Na'il Saleh b , Werner M. Nau* a 

a Jacobs University Bremen, Campus Ring 1, D-28759 Bremen, 

Germany 

b Yarmouk University, Department of Chemistry, 21163 Irbid, 

Jordan 

The tuning of molecular properties by supramolecular complexation is of prime interest in 

supramolecular chemistry. Recently, we explored the complexation-induced shift of the 

protonation equilibria of guest molecules, particularly fluorescent dyes and drugs, by 

macrocycles [1,2,3]. In this presentation, the potential of cucurbit[7]uril (CB7), a water-soluble 

macrocyclic host molecule comprised of seven methylene-bridged glycoluril units is being 

explored with respect to (i) its effect on the protonation equilibria of included guests, (ii) solubility 

enhancement, (iii) photostabilization, and (iv) fluorescence enhancement, compare Scheme 

below. 

H 

Dye Dye 

H 

N 

N 

CB7•DyeH + 

H 

N 

Benzimidazole Thiabendazole 

N 

N 

Solubility 

Enhancement 

Photostabilization 

Fluorescence 

Enhancement 

The hydrophobic cavity along with the cation receptor properties of the two portals of 

CB7 causes a considerable shift of protonation equilibrium of fluorescent dyes. This hostassisted 

guest protonation, along with its supramolecular confinement, results in novel and 

desirable photophysical properties. Solubility and fluorescence enhancement of poorly soluble 

benzimidazole-based fungicides (see above) are observed. A significant photostabilization for 

these guests is also observed due to the host-assisted guest protonation by CB7. The altered 

photophysical properties can be used for improved applications to create new sensors based on 

a protolytic displacement assay principle [3]. 

[1] H. Bakirci, A. L. Koner, T. Schwarzlose, and W. M. Nau, Chem. Eur. J., 2006, 12, 4799 - 

4807. 

[2] J. Mohanty, A. C. Bhasikuttan, W. M. Nau, and H. Pal, J. Phys. Chem. B., 2006, 110, 5132 - 

5138. 

[3] A. L. Koner and W. M. Nau, Supramol. Chem., 2007, 19, 53 - 65. 

S 

H 

N O 

N 

Fuberidazole 

PSA 86

PSA 87 

Luminescence of terbium and dysprosium complexes with p-sulfonatothiacalix[4]arene 

in aqueous and surfactant media 

Svetlana Kost a , Natalya Rusakova a , Asiya Mustafina b , Rustem Amirov c , Rustem Zairov c , 

Svetlana Solovieva b , Igor Antipin b , Alexander Konovalov b , Yuriy Korovin a 

a A.V. Bogatsky Physico-Chemical Institute, 86 Lustdorfskaya doroga, 65080 Odessa, Ukraine 

b A.E. Arbuzov Institute of Organic&Physical Chemistry, 8 Arbuzov str., 420088 Kazan, Russia 

c Kazan State University, 18 Kremlevskaya str., 420008 Kazan, Russia 

Molecular design of a sensing reagent capable of recognition the cations, anions, specific 

analytes, pH, etc. is one of cardinal approaches to innovation of chemical analysis. It is wellknown 

that calixarenes (cyclic products of phenol and formaldehyde condensation) are versatile 

molecular scaffolds for design of highly efficient receptors, self-assembling systems such as 

molecular capsules and well defined functional nanostructures. At the same time the chemistry 

of the thiacalixarenes is very recent compared to the similar calixarenes that have been known 

for over 20 years. Several papers have recently reported interesting progress in the field of the 

chemistry and application of thiacalixarenes [1,2]. 

In this work we describe the 4f-luminescence behavior of the terbium and dysprosium watersoluble 

complexes with p-sulfonatothiacalix[4]arene (TCAS) (Fig.) at room temperature in 

aqueous and surfactant media. 

SO 3 - Na + 

S 

- O 

S 

SO 3 - Na + 

SO 3 - Na + 

O - 

Ln 3+ 

S 

O - 

S 

OH 

SO 3 - Na + 

n H 2O, n =2-3 

The spectral-luminescent characteristics of corresponding complexes are determined at the 

presence of some neutral, anionic and cationic surfactants. It was determined that a change of 

pH shows a highly sensitive influence on the luminescence of complexes with TCAS. Therefore 

we considered the luminescent properties of the complexes with a view to the potential use in 

sensor systems, in particular, for control of pH. 

It has been shown that the presence of neutral and anionic surfactants have no influence on 

luminescence intensity of complexes Tb(Dy)-TCAS. Presence of cationic surfactants in their 

concentration is lower as compared to CMC (critical micelle concentration) results in formation 

of associates with complexes due to an electrostatic attraction between SO3 - - groups of the 

TCAS and molecules of cationic surfactants. These associates are characterized by more 

intensive 4f-luminescence than complexes Tb(Dy)-TCAS in aqueous medium. The various 

approaches to the increasing of the 4f-luminescence in these complexes are described and 

discussed. 

[1] N. Iki, S. Miyano, J. Incl. Phenom. Macrocycl. Chem., 2001, 41, 99-105. 

[2] P. Lhotak, S. Shinkai, J. Phys. Org. Chem., 1997, 10, 273-282. 

PSA 88 

Photo-Responsive Structure of Supramolecular Polymers Constructed by a 

Stilbene Cyclodextrin Dimer 

Paul Kuad, Yoshinori Takashima, Hiroyasu Yamaguchi and Akira Harada 

Department of Macromolecular Science, Graduate School of Science, Osaka University, 

Toyonaka, Osaka 560-0043, Japan; e-mail: paul@chem.sci.osaka-u.ac.jp 

Stilbene derivatives are expected to provide useful applications for optical switching, image 

storage devices or molecular function regulation because their C-C double bond photoisomerisation 

can induce 

changes of various chemical and 

physical properties. Previously, 

we reported the formation of 

supramolecular polymers based 

on homo and hetero cyclodextrin 

(CD) dimer and various ditopic 

guests. [1] 

In this work, we prepared 

supramolecular polymer based 

on β-CD dimer with functional 

stilbene linker as new stimuliresponsive 

systems and studied 

its chemical and physical 

properties. The guest dimer 

consists of two adamantyl 

groups linked by a pyridinium 

derivative. We observed 

interaction of the stilbene host 

dimer with the guest dimer. The 

Figure 1. Diffusion coefficient (D) of trans and cis stil-β-CD 

dimer alone and C3 guest with trans and cis stil-β-CD dimer in 

D2O at 30 ºC. 

results indicate different complexation behaviour for the trans and cis form of the CD dimer. 

ROESY NMR spectra of the mixture of host and guest showed correlation peaks between 

adamantyl groups and inner protons of CDs for both isomers, indicating that the adamantyl 

groups were included in the CD cavities. On the other hand, PFG NMR measurements, 

Figure 1, reveal that the diffusion coefficient of the cis isomer complex was significantly lower 

than that of the trans isomer at high concentration, indication the formation of a supramolecular 

polymer with cis isomer whereas trans isomer forms smaller assemblies. Direct observation of 

the different isomer mixture by AFM allows us to propose structures for the complexes 

(Figure 2). 

O 

O 

NH 

N+ 

O 

O 

NH 

N+ 

N + 

O 

N 

O 

N + 

O 

N 

O 

hυ 

HN 

O 

NH 

O 

O 

Figure 2. Proposed structures of 1/1 complex and supramolecular polymer. 

N + 

[1]. (a) Ohga K., Takashima Y., Takahashi H., Kawaguchi Y., Yamaguchi H., Harada A., 

Macromolecules, 2005, 38, 5897-5904. (b) Hasegawa Y., Miyauchi M., Y., Takashima Y., 

Yamaguchi H., Harada A., Macromolecules, 2005, 38, 3724-3730. (c) Takahashi H., Takashima 

Y., Yamaguchi H., Harada A., J. Org. Chem., 2006, 38, 3724-3730. 

N + 

O 

HN 

O 

NH 

O 

O 

N + 

N + 

O 

HN 

O 

NH 

O

PSA 89 

Supramolecular assemblies of the crown-containing 2-styrylpyridine with 

amino acids. 

Labazava I.Ya 1 , Mashura M.M 1 , Gulakova E.N 1 , Fedorov Yu.V 1 , Fedorova O.A 1 , Alfimov M.V 1 , 

J.Saltiel 2 . 

1 Photochemistry Center of RAS, 7a Novatorov str, 119421 Moscow, Russia 

2 Chemistry Departments, The Florida State University 32306 Tallahassee, Florida 

In the present investigation the assemblies of 2-styrylpyridines containing 18-crown-6 and 

aza-18-crown-6 ether fragments with perchlorates of amino acids ClO4 - NH3 + (CH2)nCOOH (n=2, 

5, 10) were studied by optical methods, mass-spectrometry and NMR- spectroscopy. The 

simultaneous binding of ammonium and carboxylate group is required for the recognition of 

amino acids. In this work, we selected benzo-18-crown-6 ether as ammonium binding site and 

pyridine residue as carboxylate binding site. The two binding centers are connected with each 

other through the ethylenic double bond. 

N 

ClO 4 - 

I 

O O 

H 

O O 

H H 

O O 

N+ 

COOH 

COO- 

H 

H 

N 

H 

+ 

N + O O 

H 

O O 

O O 

IV 

ClO 4 - 

COO- H 

NH 3 + 

N + 

ClO 4 - 

II 

O O 

O O 

O O 

N + 

O 

H 

O 

O N O 

O O 

H 

+ 

+ 

COO- H N 

O O 

H 

O 

N 

O 

O O 

H 

H 

OOC 

+ 

H 

H 

2ClO - 

4 

The obtained data showed that complex formation of the crown-containing 2-styrylpyridine 

with amino acids occurs through the mono- or ditopic coordination.The irradiation of the 

receptor with light results in the reversible reaction of E-Z-isomerization around the double C=C 

bond what substantially changes the structure of the receptor. The formation of ditopic complex 

influences the E-Z-photoisomerization reaction of the 2-styrylpyridine The occurrence of the 

phototransformation will change the ability of the receptor to bind with amino acids 

Acknowledgment. The study was supported by CRDF (Grant RUC(2-2656-MO-05)), INTAS 

(Grant 03-51-4696), RFBR (06-03-32899 and 05-03-32268), Russian Academy of Sciences and 

the Ministry for High Education of Russia. 

III 

Self-assembly of a guanosine derivative bearing a terthienyl pendant 

Stefano Lena a 

, Stefano Masiero a 

, Silvia Pieraccini a 

, Paolo Samorì b 

, Gian Piero Spada a 

, 

Mathieu Surin c 

a Dipartimento di Chimica Organica “A. Mangini”, Alma Mater Studiorum - Università di 

Bologna, Via S. Giacomo 11, I-40126 Bologna, Italy 

b ISIS-ULP, 8, allée Gaspard Monge, F-67083 Strasbourg, France & ISOF-CNR, via Gobetti 

101, I-40129 Bologna, Italy 

c Service de Chimie des Matériaux Nouveaux, Université de Mons-Hainaut 

20, Place du Parc, 7000 Mons, Belgium 

Mimicking nature, hierarchical self-assembly provides a tool for bottom-up nanoconstruction of 

sophisticated functional architetctures as for the unraveling of complex biological arrangements 

and processes, paving the way towards their potential application in the realms of 

nanotechnology. We report on the self-assembly of a guanosine derivate bearing an 

oligothiophene side group under different environmental conditions. This derivative was found 

to spontaneously form, in solution state and on flat surfaces, ordered supramolecolar 

nanoribbons, and in the presence of metal cations G-quartet-based aggregates, in which the 

individual nucleobases are interacting through H-bonds. The different architectures were 

investigated using NMR-2D spettroscopy, small angle X-ray scattering, CD spettroscopy and 

scanning probe microscopy. These results are truly important in view of the electronic 

properties of these supramolecolar anisotropic architectures and thus for potential applications 

in the fields of nano- and opto-electronics [1] . 

H 2N 

R = 

HN 

O 

O 

N 

(H 2C)3 

N 

N 

O 

H H 

H H 

O O 

S 

OR 

S 

S 

C 10H21 

[1] Maruccio, G.; Visconti, P.; Arima, V.; D’Amico, S.; Blasco, A.; D’Amone, E.; Cingolani, R.; 

Rinaldi, R.; Masiero, S.; Giorgi, T.; Gottarelli, G. Nano Lett. 2003, 3, 479-483. 

PSA 90

Application of a new classes podands in solid-liquid phase transfer 

catalysis 

Bogusawa ska, Radosaw Pankiewicz and Grzegorz Schroeder 

Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Pozna, Poland 

Phase transfer catalysis (PTC) is now a well established method in organic synthesis 

applicable to reactions of inorganic and organic anions and other active species with organic 

compounds. Phase transfer catalysis is a general technique widely used in organic chemistry, 

which usually, but not always, based on the reactions involving transfer of anion from an 

aqueous or solid phase into an organic phase followed by the reaction of anion with the 

substrate in organic phase. Reacting anions are continuously introduced into non-polar organic 

phase as ion pairs with complexed cations supplied by the catalyst. Further reactions of these 

ion pairs proceed in the organic phase. Nowadays the term “phase transfer catalysis” refers to 

several effective techniques whose typical advantages are simplicity, mild conditions, high 

reaction rates and rather inexpensive reagents. It is also one of the most versatile preparative 

methods. The search for new catalysts, their use in PTC asymmetric synthesis and the attempts 

to understand their mechanistic role are exciting topics of investigation. 

In this presentation we report a systematic study of boron polypodands 1-4 and podands 

2-8 synthesized on the base of Triton-X with B, Si and P as central atoms in the molecule, 

obtained in high yield by the reaction presented in Scheme 1. We used podands as catalysts in 

some phase transfer catalysis processes and they have been found excellent catalysts in some 

anion promoted reactions (nucleophilic substitution, reduction, alkylation, ect.) under solid-liquid 

conditions in chlorobenzene as low polarity medium and acetonitrile as polar aprotic solvent. A 

comparison is planned with the well known PTC catalysts: crown ethers DCH18C6 (9), 

PEG400Me2 (10) and Si-podand (11), studied previously by us [1, 2]. 

B-podands 

O 

O 

B 

O 

Triton’s podands 

O CH3 2 

O CH3 2 

O CH3 2 

O 

O 

B 

O 

O CH3 7 

O CH3 7 

O CH3 7 

O 

O 

B 

1 2 3 4 

Tr = 

n = 10 

Tr 

Tr 

Tr 

O 

O 

O 

O 

nO 

Si 

nO 

O 

n 

O CH3 12 

O CH3 12 

O CH3 12 

O 

O 

Si 

O 

O 

O 

B 

O 

O 

B 

O 

O Tr 

n 

O Tr 

n 

O Tr 

n 

O 

O 

P 

O 

O Tr 

n 

O Tr 

n 

O Tr 

n 

O 

O 

Si 

O 

O Tr 

n 

O Tr 

n 

O Tr 

n 

5 6 7 

O 

O Tr 

n 

O Tr 

n 

O Tr 

n 

O CH3 16 

[1] A. Maia, D. Landini, B. ska and, G. Schroeder, Tetrahedron, 2004, 60, 10111-10115. 

[2] B. ska, R. Pankiewicz, G. Schroeder, A. Maia, Tetrahedron Lett., 2006, 47, 5673-5676. 

8 

O 

O 

CH 3 

16 

CH3 16 

PSA 91 

New DOTP analogue for possible medical applications 

Luís M. P. Lima a , Rita Delgado a,b , Petr Hermann c , Jan Kotek c 

a Instituto de Tecnologia Química e Biológica, UNL, Oeiras, Portugal 

b Instituto Superior Técnico, UTL, Lisboa, Portugal 

c Department of Inorganic Chemistry, Charles University, Prague, Czech Republic 

Cyclen derivatives with coordinating pendant arms are suitable ligands for transition metal and 

lanthanide ions. In particular, lanthanide (III) complexes of ligands such as DOTA, DOTP and 

others have found important applications in the field of medicinal chemistry, namely as contrast 

agents for Magnetic Resonance Imaging and as radiopharmaceuticals for diagnosis or therapy. 

However, available data from the studies of such ligands are frequently obtained in different 

experimental conditions, which makes it difficult to compare the properties of different ligands. 

To overcome that problem we have recently studied the solution behaviour of a series of 

macrocycles functionalized with acetic and methylphosphonic acid pendant arms [1]. 

The synthesis of macrocycles bearing mixed pendant arms is an important tool for developing 

ligands with improved chemical and biological properties or suitable for use as bifunctional 

chelators. During recent years we have focused on the synthesis and study of such macrocyclic 

derivatives [2]. 

(HO)2OP 

(HO)2OP 

N N 

N N 

R 

PO(OH)2 

PSA 92 

A new ligand analogue of DOTP was synthesized by 

introducing one pendant arm of a different type on the 

DOTP structure. The protonation sites of the ligand 

were studied by 31 P NMR titration. Protonation 

constants of the ligand as well as thermodynamic 

stability constants for some transition metal and 

lanthanide complexes were determined by 

potentiometric titrations. This ligand shows a very high 

overall basicity, and its metal complexes present also a very high stability. The discussed 

properties are compared with those published for DOTP and other similar ligands. 

[1] R. Delgado, J. Costa, K. P. Guerra, and L. M. P. Lima, Pure Appl. Chem., 2005, 77, 569- 

579. 

[2] V. Kubiek, J. Rudovský, J. Kotek, P. Hermann, L. Vander Elst, R. N. Muller, Z. I. Kolar, H. 

Th. Wolterbeek, J. A. Peters, and I. Lukeš, J. Am. Chem. Soc., 2005, 127, 16477-16485.

Polytopic Ligands for the Recovery of Metal Chlorides 

Tai Lin, Vesna Gasperov and Peter A. Tasker 

School of Chemistry, The University of Edinburgh, Edinburgh, EH9 3JJ, UK. 

E-mail: T.Lin-4@sms.ed.ac.uk 

Hydrometallurgy is becoming increasingly important in the recovery of base metals and solvent 

extraction is very effective in achieving the unit operations of concentration and separation. [1] 

Separation and 

Ore M 

concentration 

0 

Separation and 

Ore Leach Electrolysis M 

concentration 

0 

Leach Electrolysis 

Polytopic ligands capable of the simultaneous coordination of both cationic and anionic species 

have been developed for the potential use in hydrometallurgy, as they could open up new 

flowsheets to transport metal salts. [2] In this work, tetradentate salicylaldimine ligands of the 

“salen” type bearing pendant tertiary amine groups undergo zwitterionic transformation and 

achieve extremely high transport efficiency of both zinc and chloride from ZnCl2 feed solutions; 

3,3’-bis(di-n-hexylaminomethyl)-substituted salen (2) transfers >2 mol of ZnCl2 per mol of ligand 

into chloroform whereas the unsubstituted analogue (1) loads

Nitroxide Radicals as Probes for Exploring the Binding Properties of 

Cucurbit[n]uril Hosts 

Elisabetta Mezzina, Elisabetta Mileo, Gian Franco Pedulli, Marco Lucarini 

Department of Organic Chemistry “A. Mangini”, University of Bologna, Via S. Giacomo 11, 

I-40126 Bologna, Italy 

In the last few years we have shown that the formation of a host-guest complex can be studied 

very conveniently by EPR spectroscopy, by using an appropriate radical probe.[1] Actually, 

benzyl tert-butyl nitroxide and related dialkyl nitroxides were found to be suitable probes to 

investigate host-guest interactions in cyclodextrins, calixarenes, and protected nanoparticles. 

Evidence for the formation of paramagnetic complexes between these radicals and the host 

systems was provided by large spectral changes due to the different environment experienced 

by the radical guest, and to conformational changes occurring upon complexation. In most 

cases, the EPR spectra also showed a strong linewidth dependence on temperature, indicating 

that the lifetime of nitroxides in the associated and free form is comparable to the EPR 

timescale; this enabled us to measure the rate constants for the association and dissociation 

processes. 

In the present communication we show that the use of EPR spectroscopy can be extended to 

the study of paramagnetic supramolecular complexes formed by cucurbiturils (CBn) in 

solution.[2] Evidence for the formation of a complex between nitroxide radicals and 

cucurbit[n]uril (n=7,8) in water solution was provided by large changes of nitrogen hyperfine 

splitting, due to the different polar environment experienced by the radical when included. In the 

presence of alkali cations the EPR spectra of benzyl tert-butyl nitroxide were characterized by 

new signals due to radical hosted in the CB cavity in which one metal cation is in close contact 

with the nitroxidic oxygen. The EPR spectra showed selective line broadening effects due to the 

metal exchange between bulk water and the coordination complex; analysis of the EPR line 

width variations allowed us to measure for the first time the corresponding kinetic rate 

constants. By using NMR spectroscopy it was shown that this behavior is not peculiar to 

X ≡ Guest 

M + =Li + , Na + , K + , Cs + 

M + 

+ M + 

+ X + M + X 

+ M + 

+ X + M + 

M + + 

X 

M + 

M + M + 

 

 

 

 

nitroxides but also to the related 

carbonyl compounds. These data 

allowed us to quantify the template 

effect and to reach the conclusion that 

in the presence of guest having a 

coordinating lone pair the formation of 

ternary metal-guest-CB complexes 

must be taken into account when 

discussing the complexation behavior of 

cucurbituril derivatives in the presence 

of salts.[3] 

[1] P. Franchi, M. Lucarini and G. F. Pedulli, Curr. Org. Chem. 2004, 8, 1831. P. Franchi, M. 

Lucarini, E. Mezzina and G. F. Pedulli, J. Am. Chem. Soc. 2004, 126, 4343. P. Franchi, M. 

Lucarini, G. F. Pedulli and D. Sciotto, Angew. Chem. Int. Ed. 2000, 39, 263. M. Lucarini, P. 

Franchi, G. F. Pedulli, C. Gentilini, S. Polizzi, P. Pengo, P. Scrimin and L. Pasquato, J. Am. 

Chem. Soc. 2005, 127, 16384. 

[2] For a recent review on cucurbiturils see: J. Lagona, P. Mukhopadhyay, S. Chakrabarti and L. 

Isaacs, Angew. Chem., Int. Ed. 2005, 44, 4844. 

[3] E. Mezzina, F. Cruciani, G. F. Pedulli and M. Lucarini, Chem. Eur. J. 2007, in press. 

M + 

M + 

X 

M + 

X 

+ M + 

PSA 95 

PSA 96 

Supramolecular complexes of polythiophene derivatives with different types 

of metal cations 

Elena V. Lukovskaya a , Alla A. Bobylyova a , Olga A. Fedorova a ,Yury V. Fedorov b , Emely 

Marmois c , Gediminas Jonusauskas c , Sergey V. Kardashev a , Anton L. Maksimov a , Y. Didane d , 

Hugues Brisset d , Frederic Fages d , Artem A. Mizerev a , Aleksander V. Anisimov a 

a Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 

119992 Moscow, Russia 

b Photochemistry Center of RAS, Novatorov str., 7a,119421 Moscow, Russia 

Centre de Physique Moleculare Optique et Hertzienne U.M.R. 5798 Universite Bordeaux 1, 

Bordeaux, France 

d Universite de la Mediterranee, Faculte des Sciences de Luminy, GCOM2, Marseille, France 

A very promising approach to electrochemically active compounds with various covalently 

attached functional groups is to use the electrochemically active compounds bearing molecular 

recognizing groups in which very selective host-guest interaction modulate, switch, and amplify 

the electron transport properties. In the present research we synthesized the polythiophene 

derivatives with crown-containing styryl and vinylpyridyne groups in 2 and 3 position of 

thiophene ring. The complex formation of prepared compounds was studied with Mg 2+ and Ba 2+ 

cations by applying of NMR- and optical spectroscopy as well as ESI MASS spectrometry and 

electrochemical studies. It was found that addition of Ba 2+ cations causes the formation of only 

intermolecular sandwich complexes in case of 2-substituted derivatives. On the contrsry in the 

presence of Ba 2+ cations 3-substituted derivatives form only itramolecular sandwich complexes 

of high stability. Formation of complexes causes changes in optical spectra; electrochemical 

response depends on the type of complexes formed by interaction of poythiophene derivatives 

with metal cations. 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

S 

S 

S 

n 

CH 2 

Ba 2+ 

N 

S 

S 

S 

S 

S 

n = 0, 1 

Acknowledgements. The research was done by financial support of INTAS 03-51-4696 

and program of Russian Academy of Sciences 07-03-00724. 

S 

n 

n 

2Ba 2+ 

S 

n 

S 

S 

S 

S 

Ba 2+ 

R 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

S 

S 

N

PSB 1 

Rosette Nanotubes as Scaffolds for Stacked Multi-Porphyrin Assemblies 

Darren A. Makeiff and Hicham Fenniri 

Supramolecular Nanoscale Assembly Group, National Institute for Nanotechnology, University 

of Alberta (Edmonton, Alberta, Canada) 

E-mail: dmakeiff@ualberta.ca, hicham.fenniri@ualberta.ca 

Hierarchical self-assembly is a highly attractive route to well-defined one-dimensional (1D) 

chromophoric arrays, which may resemble natural antennae systems and display new and 

interesting optical or electronic physical properties. 1 The G^C base is a DNA inspired 

supramolecular synthon, which undergoes hierarchical self-assembly to form 1D nanostructures 

called rosette nanotubes (RNTs). 2 Self-complementary hydrogen bonding arrays direct the 

formation of hexamaric rosette supramacrocycles, 3 which can then form linear stacks up to a 

millimeter long. 2 A simple strategy has been developed for functionalizing the surface of RNTs 

through covalent modification of the G^C base backbone. Here we present the synthesis and 

characterization of a porphyrin functionalized RNTs. RNTs are used as a rigid scaffold to 

preorganize six peripheral porphyrin stacks to generate unique nanomaterials that are expected 

to exhibit attractive photophysical and electronic properties for materials applications. 

Porphyrin 

G^C Base 

Rosette Rosette Nanotubes 

[1] Elemans, J. A. A. W.; Rowan, A. E.; Nolte, R. J. M. J. Mater. Chem. 2003, 13, 2661-2670. 

[2] Fenniri, H.; Mathivanan, P.; Vidale, K. L.; Sherman, D. M.; Hallenga, K.; Wood, K. V.; 

Stowell, J. G. J. Am. Chem. Soc. 2001, 123, 3854-3855. 

[3] Marsh, A.; Silvestri, M.; Lehn, J. -M. Chem. Commun. 1996, 1527-1528. 

PSB 2 

Preparation and characterization of [60]fullerene fibrillar superstructures 

and those polymerization by γ-ray irradiation 

Sudip Malik, Norifumi Fujita, Seiji Shinkai 

Department of Chemistry and Biochemistry, Graduale School of Engineering, Kyushu 

University, 744 Moto-oka, Fukuoka, Japan 

[60]Fullerenes are dissolved in solid and sublimable solvents such as naphthalene, ferrocene 

and camphor, respectively. After removing these solvents by sublimation process the formation 

of fibrillar superstructures of fullerene has been observed. The morphology of these 

[60]fullerene superstructures has been investigated by scanning electron microscopy (SEM) as 

shown in Figure 1. X-ray powder diffraction study and ATR/IR analysis show that [60]fullerene 

superstructures preserve fcc lattice as like in pristine [60]fullerene. NMR together with elemental 

analysis reveals the presence of significantly less amount of solvent in the superstructures. We 

have attempted to polymerize these superstructures by γ-ray irradiation to achieve 

poly[60]fullerene that is the material composed of only [60]fullerenes connected by covalent 

bonds without any additional linkage.[1] We have characterized polymerized [60]fullerene by 

TEM/HRTEM as well as spectroscopic analyses. This approach that provides not only an easy, 

simple and efficient technique for the production of fibrous [60]fullerene or poly[60]fullerene but 

also to control over the morphological aspects will be the promising pathways to prepare 

fullerene-based material for the development of realistic applications. 

(a) (b) (c) 

1.67 µm 37.3 µm 1.67 µm 

Figure 1: SEM images of [60]fullerene superstructure after sublimation of solid solvents :(a) 

naphthalene, (b) ferrocene and (c) camphor, respectively. 

Reference 

[1] F. Giacalone and N. Martin, Chem. Rev., 2006, 106, 5136-5190.

PSB 3 

Enhanced kinetic inertness in the electrochemical interconversion of Cu(I) 

double helical to Cu(II) monomeric complexes 

Piersandro Pallavicini, a Massimo Boiocchi, b Giacomo Dacarro a and Carlo Mangano a 

a: Dipartimento di Chimica Generale, Università di Pavia, v.le Taramelli, 12 – 27100 Pavia, Italy; 

e-mail psp@unipv.it; 

b: Centro Grandi Strumenti, Università di Pavia, via Bassi, 21 – 27100 Pavia, Italy 

Three new ligands made of two imino-quinoline halves separated by an R,R-trans-1,2cyclohexyl 

spacer have been synthesized. These ligands feature –OR functions appended in 

the 8-positions of the quinoline rings (R = n-alkyl). 

The ligands display a behaviour similar to that of their analogues that contain unsubstituted 

quinolines, forming a bistable system with copper.[1] [Cu2L2] 2+ helicates are obtained with Cu(I) 

and [CuL] 2+ monomers with Cu(II), as shown by UV/Vis titrations, determination of complexes 

formation constants, mass and NMR measurements, and X-ray crystallographic analysis. The 

OR groups are found to be non-coordinating, but due to the closed and intertwined nature of the 

complexes, the additional –OR groups sterically hinder the disassembling step and make slow 

the electrochemical interconversion of [Cu2L2] 2+ into [CuL] 2+ . In particular, oxidation of [Cu2L2] 2+ 

gives a reversible two steps profile in Cyclic Voltammetry esperiments, due to the formation of 

the Cu 2+ helicate [Cu2L2] 4+ , that does not evolve into [CuL] 2+ in the CV experiment time scale.. 

[1] a) V. Amendola, L. Fabbrizzi, L. Linati, C. Mangano, P. Pallavicini, V. Pedrazzini and M. 

Zema, Chem. Eur. J., 1999, 5, 3679; b) V. Amendola, L. Fabbrizzi and P. Pallavicini, Coord. 

Chem. Rev., 2001, 216-217, 435; c) V. Amendola, L. Fabbrizzi, L. Gianelli, C. Maggi, C. 

Mangano, P. Pallavicini and M. Zema, Inorg. Chem., 2001, 40, 3579; d) V. Amendola, L. 

Fabbrizzi, P. Pallavicini, E Sartirana and A. Taglietti, Inorg. Chem., 2003, 42, 1632-1636 

PSB 4 

Lanthanide Ion Binding Properties of Homooxacalixarene Diethylamide 

Derivatives 

Paula M. Marcos a, c , José R. Ascenso b , Manuel A. P. Segurado c , Peter J. Cragg d 

a Fac. Ciências Univ. Lisboa, Dept. Química / CCMM, Edifício C8, 1749-016, Lisboa, Portugal 

b Instituto Superior Técnico, Complexo I, Av. Rovisco Pais, 1049-001 Lisboa, Portugal 

c Fac. Farmácia Univ. Lisboa, Av. Prof. Gama Pinto, 1649-003 Lisboa, Portugal 

d School of Pharmacy and Biomolecular Sciences, Univ. Brighton, Brighton BN2 4GJ, UK 

The ability of calixarenes bearing carbonyl groups at their lower rims to bind metal ions has 

been extensively studied [1]. We have been synthesising homooxacalixarene derivatives 

containing carbonyl groups at the lower rim and studying their binding properties towards alkali, 

alkaline earth, transition and heavy metal cations [2, 3]. In the course of these studies, we have 

now extended our research into lanthanide cations. 

In the present work we report the binding properties of p-tert-butyldihomooxacalix[4]arene 

tetra(diethyl)amide (1) [4] and of p-tert-butylhexahomotrioxacalix[3]arene tri(diethyl)amide (2) [5, 

6], both in the cone conformation, towards lanthanide cations (La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , 

Eu 3+ , Gd 3+ , Dy 3+ , Er 3+ and Yb 3+ ). This has been assessed by extraction studies with the 

corresponding lanthanide picrates from aqueous solutions into dichloromethane. Further 

information on some cation binding behaviour of derivatives 1 and 2 was obtained by proton 

NMR titration experiments. Variable amounts of La, Eu and Yb triflates were added into the 

NMR tubes containing the ligands, and the proton spectra recorded after each addition. 

Tetraamide 1 is a very good phase transfer agent, displaying extraction percentages between 

60-90 %. The results obtained with triamide 2 range from 20-30 %. These lower percentages 

should mainly reflect the higher conformational flexibility of derivative 2. 

t -Bu 

t-Bu 

OR 

OR 

1 

OR 

OR 

t-Bu 

O 

t - Bu 

t-Bu 

R = CH 2 CON(Et) 2 

t-Bu 

O OR O 

OR RO 

[1] Calixarenes 2001, Z. Asfari, V. Böhmer, J. Harrowfield and J. Vicens (Eds.), Kluwer 

Academic Publishers, Dordrechet, 2001. 

[2] P. M. Marcos, S. Félix, J. R. Ascenso, M. A. P. Segurado, J. L. C. Pereira, P. Khazaeli- 

Parsa, V. Hubscher-Bruder, F. Arnaud-Neu, New J. Chem., 2004, 28, 748-755. 

[3] P. M. Marcos, J. R. Ascenso, P. J. Cragg, Supramol. Chem., 2007. (in press) 

[4] S. Félix, J. R. Ascenso, R. Lamartine, J. L. C. Pereira, Tetrahedron, 1999, 55, 8539-8546. 

[5] H. Matsumoto, S. Nishio, M. Takeshita, S. Shinkai, Tetrahedron, 1995, 51, 4647-4654. 

[6] P. J. Cragg, M. G. B. Drew, J. W. Steed, Supramol. Chem., 1999, 11, 5-15. 

O 

2 

t-Bu

PSB 5 

Towards the development of new molecular nano-gates controlled via ionic 

and optical inputs 

Elena Aznar a , Rosa Casasús a , María Comes a , María Dolores Marcos a , Ramón Martínez- 

Máñez a , Félix Sancenón a , Juan Soto a , Luis A. Villaescusa a , Pedro Amorós b , Joan Cano c , Eliseo 

Ruiz c 

a) Instituto de Química Molecular Aplicada (IQMA), Universidad Politécnica de Valencia, 

Camino de Vera s/n, 46022, Valencia, Spain 

b) Institut de Ciència dels Materials (ICMUV), Universitat de Vàlencia, 46071, Vàlencia, Spain. 

c) Departament de Química Inorgànica, Universidad de Barcelona, E-08028 Barcelona, Spain. 

Centre de Recerca en Química Teòrica (CERQT) and Institut de Nanociència i Nanotecnologia 

(IN2UB), Universitat de Barcelona, Barcelona, Spain. 

A nanoscopic gate may be defined as a molecular or supramolecular-based nano-device able to 

control mass transport and that can be “opened” and “closed” at will by certain target ions, 

molecules or other external stimuli. These systems with a molecular-and-material basis are 

inspired in bio-channels and bio-gates and in general in biological processes that utilize 

molecular movable mechanisms triggered by specific chemical species. Yet, the advanced 

control via multiple chemical or physical inputs of motion-based functional processes such as 

translocation, reversible mass movement, controlled molecular transport, etc. at nanometric 

level is a landmark subject at the frontier of the knowledge for the upcoming design of 

supramolecular sophisticated architectures. The development of such nanoscopic scaffoldings 

could be achieved using pre-organised nanoscopic solid structures and supramolecular 

functional units attached on the surface of the inorganic supports in a cooperative fashion. For 

instance, recently reported examples have discovered that the anchoring of molecular entities 

on 3D nanoscopic systems offers the opportunity to develop new supramolecular synergic 

functional concepts that would be hardly achieved on “flat” surfaces (2D systems) or in 

molecular-based systems. [1] This is especially so in the field of gated nanochemistry and its 

relation with the design of nanoscopic supramolecular architectures incorporating chemical 

entities which can act as a functional gate-like architectures and that allow to control the access 

of (or from) a certain nanosite at will. The design of pores with stimuli-activated gating 

mechanism is a potentially fertile research in the nano-chemistry and nano-biology fields. This is 

a timely topic, yet the number of reported examples is still very low and usually of limited 

applicability. We and other have recently reported the development of gate-like structures for 

applications as controlled delivery systems or as new sensing paradigms. [2] 

We report herein new designs of molecular gates on MCM41 mesoporous materials. Gate-1 is 

driven by two different inputs in water; light and pH. It consists of switchable spirobenzopyrane 

derivatives anchored in the pore outlets of a MCM41 support and negatively charged 

dendrimers that acts as molecular stoppers. Gate-2 is both pH- and anion-driven and contains 

simple anion binding sites (i.e. polyamines) anchored on mesoporous supports. Gate-3 consists 

of a polyalcohol anchored on the pore outlets of a mesoporous structure and a nanoscopic tap 

built up with gold nanoparticles functionalised with boronic acid derivatives. We also report 

molecular modelling studies that have been carried out on the supramolecular Gate-2. 

[1] A. B. Descalzo, R. Martínez-Máñez, F. Sancenón, K. Hoffman, K. Rurack, Angew. Chem. 

Int. Ed., 2006, 45, 5924-5948. 

[2] See for instance: R. Casasús, M. D. Marcos, R. Martínez-Máñez, J. V. Ros-Lis, J. Soto, L. A. 

Villaescusa, P. Amorós, D. Beltrán, C. Guillem, J. Latorre, J. Am. Chem. Soc., 2004, 126, 8612- 

8613. S. Giri, B. G. Trewyn, M. P. Stellmaker, V. S. –Y. Lin, Angew. Chem. Int. Ed., 2005, 44, 

5038-5044. 

Noble metal complexes with sulfur-containing calixarenes: 

extraction, complexation and structure 

Mashukov V.I. 1 , Kostin G.A. 1 , Torgov V.G. 1 , Korda T.M. 1 , Kalchenko V.I. 2 

1 Institute of Inorganic Chemistry SB RAS, pr. Lavrent’eva, 3, Novosibirsk, Russia 

2 Institute of Organic Chemistry NAS Ukraine, Murmanskaya str., 5, Kyiv, Ukraine 

PSB 6 

Functionalized calixarenes and thiacalixarenes are effective receptors for metal ions owing to 

their -rich cavity and spatially oriented donor groups. Structure-property relationships have been 

established for the complexation and extraction of Au, Pd, Ag and Pt chloride complexes by 

calix[4,6]arenes-thioethers (1) and thiacalix[4]arenes-thioethers (2) modified by CH2-S-R groups 

at the upper rim. 

DPd DAu DAg 

Size of macrocycle [n] in 1 [6] [4] [6] > [4] [4] [6] 

bridging group (-S- or -CH2-) 2 > 1 1 > 2 2 > 1 

substituents (R) in 1 Me > Bu >> p-Tol Bu> Me >> p-Tol Me > Bu >> p-Tol 

The decrease in Au extraction (1 > 2) is due to the weakening of donor properties of the 

upper-rim groups. Unusual influence of sulfur bridges (2 > 1) on Pd and Ag extraction can be 

explained by additional interactions of metal ions with -aromatic system including S-bridges. 

Slight recovery of Pd by unmodified thiacalix[4]arene-“cone” and the absence of extraction for 

other conformations indirectly confirm the hypothesis of additional -bonding by the cavity. 

The stoichiometry of extracted species and the constants of complex formation for (AuCl3)nL 

(n=1-4), (PdCl2)nL (n=1-2) and AgClL have been determined. The equality of step-by-step 

constants indicates that different sites of the calixarene coordinate metal ions independently 

making the calixarenes very suitable platforms in the construction of polymetallic complexes. 

Partition coefficients from 1-6 M HCl to diluents (toluene, CCl4, 1,2-dichloroethane) decrease 

for all investigated calixarene-thioethers: DAu,DPd>>DAg>DPt. Compared with monodentate 

analogues (R2S), the small increase in Au extraction ( 10) is determined by the structural 

preorganization of receptor while the significant enhancement in Pd, Ag and Pt extraction (10 2 - 

10 3 ) is related to both the structural preorganization and the helate effect. For Pd the 

macrocyclic effect also leads to the acceleration of extraction by 2-3 orders of magnitude. 

Moreover, the ditopic nature of 2 (hydrophobic upper rim and hydrophilic lower rim) promotes 

additional acceleration (at the acidity of the aqueous phase > 3 M) owing to intramolecular 

catalysis by protonated oxygen atoms in the alkoxy-groups. 

The structures of (AuCl)4L and (PdCl2)2L 

(L = 5,11,17,23-tetrakis-(butylthiomethyl) - 

25, 26, 27, 28 -tetrapropoxycalix[4]arene) 

have been determined by X-ray 

crystallography. Monodentate coordination 

of gold and helate coordination of palladium 

to sulfur atoms of the donor groups have 

been confirmed (see Figure). The crystal 

lattice of (AuCl)4L consists of 2D-nets, 

molecules being binded together by Au-Au 

interactions (3,20-3,23 Å). 

On basis of the investigation the parameters (calixarene structure, time of extraction, diluent, 

CHCl) of effective combined or selective extraction of Pd and Au over other heavy metals have 

been supposed. 

The work has been partially supported by Joint SB-RAS-Ukrainian NAS project 4.12.

PSB 7 

Properties of metal complexes of a new dioxadiaza macrocycle containing a 

dibenzofuran unit and acetate pendant arms 

Pedro Mateus a , Judite Costa c , Feng Li a , Rita Delgado a,b 

a Instituto de Tecnologia Química e Biológica, UNL, Apartado 127, 2781-901 Oeiras, Portugal. 

b Instituto Superior Técnico, Departamento de Química, Av. Rovisco Pais, 1049-001 Lisboa, 

Portugal. 

c Faculdade de Farmácia de Lisboa, Av. das Forças Armadas, 1600 Lisboa, Portugal 

A number of polyoxapolyazamacrocycles with a variety of functional pendant side-arms on the 

nitrogen atoms has been prepared in the last two decades. [1] Macrocycles containing 

carboxylate or/and phosphonate pendant arms have widely been studied for the application of 

their paramagnetic lanthanide complexes as contrast agents in magnetic resonance imaging 

(MRI) of soft tissue, or as radiopharmaceutical drugs for tumour imaging and therapy. [2],[3] 

A new dioxadiaza macrocyclic ligand containing a rigid 

dibenzofuran group (DBF) [4] and bearing two acetate 

O 

OH 

N 

O 

O O 

N 

ac 2[17](DBF)N 2O 2 

HO 

O 

pendant arms, ac2[17](DBF)N2O2, has been synthesized 

in good yield by condensation of the parent amine with 

potassium bromoacetate, in aqueous basic solution. 

The protonation constants of ac2[17](DBF)N2O2 and its 

stability constants of complexes with divalent 1 st row 

transition metal and trivalent lanthanide cations were 

determined at 298.2 K in aqueous solution and at ionic 

strength 0.10 mol dm -3 in NMe4NO3. The first two 

protonation constants, corresponding to the protonation 

of the two amine centres within the macrocycle, are lower 

than expected for secondary amines due to the inductive effect of the nearby ether oxygen 

atoms and the electron withdrawing effect of the DBF group. The stability constants revealed a 

preference of ac2[17](DBF)N2O2 for larger metal ions. 

[1] R. D. Hancock, H. Maumela and A. S. Sousa, Coord. Chem. Rev., 1996, 148, 315-347. 

[2] S. Liu, Chem. Soc. Rev., 2004, 33, 445-461. 

[3] F. Marques, L. Gano, M. P. Campello, S. Lacerda, I. Santos, L. M. P. Lima, J. Costa, P. 

Antunes and R. Delgado, J. Inorg. Biochem., 2006, 100, 270-280. 

[4] F. Li, R. Delgado, A. Coelho, M. G. B. Drew and V. Félix, Tetrahedron, 2006, 62, 8550-8558. 

The authors acknowledge the financial support from Fundação para a Ciência e Tecnologia (FCT) and 

POCI, with coparticipation of the European Community fund FEDER (Project n. POCI/QUI/56569/2004). 

PSB 8 

The cleavage of cyclic substituents in derivatives of closo-decaborate anion 

by diaza-crown-ether 

E.Matveev, K.Zhizhin, N.Kuznetsov 

Kurnakov Institute of General and Inorganic Chemistry, RAS, 

31, Leninsky prosp., GSP-1, Moscow, 119991, zhizhin@igic.ras.ru 

Moscow State Academy of Fine Chemical Technology (MIFCT) 

86, Vernadsky prosp., Moscow, 119571 

The number of numerous researches a reactions of cleavage of cyclic sustituents in derivatives 

of closo-decaborate anion with oxonium groups are discussed [1-4]. 

Here we report about the reactions of cleavage of cyclic substituents in anion B10H10O2C4H8 - by 

diaza-crown-ethers. It was showed that as result of reaction the formation of alkoxy spacer 

chain occurs with the subsequent connection of diaza-crown-ether. Compounds were isolated 

as the complexes with ions of alkali metals. In more severe conditions the participation of 

already attached macrocyclic substituent occurs in the reaction of cleavage of another anion 

B10H10O2C4H8 - 

with formation of derivative having the structure of 

B10H9O(CH2)2O(CH2)2NC12H24N(CH2)2O(CH2)2OB10H9 4- , in that two borane clusters are 

connected via alkoxy chains and diaza-macrocyclic group, with cation of metal coordinating in 

its cycle. 

Scheme of described reactions is presented below: 

Produced compounds can act as polydental ligands, at the same time the coordination can be 

2– O 

2– 

2– 

O 

O O N 

O O N 

2– 

O 

O 

O 

O 

K K 

O 

O 

O 

O 

NH 

N O O 

carried out both due to atoms of oxygen and nitrogen, and due to participation of the unusual 

donor centers – cluster anions, possessing ability to form three-central bonds of M-H-B with 

metal. 

Compounds were characterized by IR-, 11 B – NMR - and ESI - spectra. 

This work was supported by RFBR (grants no. 05-03-32885 and 07-03-0000552) and the 

Council for grants of the President of the Russian Federation for support of young scientists 

(grants no. NSh-4895.2006.3, -4987.2006.3).

PSB 9 

A Quantitative [2]Rotaxane Synthesis via “Active-Template” Pd-Catalyzed 

Michael Addition 

Stephen M. Goldup, David A. Leigh, Paul J. Lusby and Roy T. McBurney 


Edinburgh, EH9 3JJ, United Kingdom (R.T.McBurney@sms.ed.ac.uk) 

Recently we introduced the “active-template” approach for the synthesis of interlocked 

structures, in which a metal atom both templates the assembly of the threaded architecture 

AND catalyzes the key covalent bond forming reaction to form a rotaxane (Scheme 1). [1] The 

first example of this strategy exploited the copper(I)-catalyzed cycloaddition of azide- and 

alkyne-functionalized ‘stoppers’ such that in the presence of a metal-binding macrocycle, a 

rotaxane was produced. [2]Rotaxanes were obtained in up to 94% yield using stoichiometric 

amounts of copper and in up to 82% yield when using just 20 mol% loading of the metal in the 

presence of excess pyridine. [1] 

Scheme 1: Schematic representation of a general “active-template” route to [2]rotaxanes. 

To expand on this “active-template” approach for synthesizing interlocked architectures, other 

metal-mediated covalent bond forming reactions are being investigated in our group. Due to 

success of palladium(II) as a classical “passive-template” for the formation of rotaxanes [2] and 

catenanes [3] , and the widespread use of this metal as a catalyst for a variety of bond-forming 

reactions, we have examined its use in various rotaxane-forming reactions. Here we report how 

the Pd-catalyzed double Michael addition of an -cyano-ester to a “stopper” functionalized as a 

,-unsaturated ketone [4] , in the presence of a Pd-coordinating macrocycle, results in 

quantitative formation of a [2]rotaxane (Scheme 2). 

Scheme 2: Rotaxane synthesis via an “active-template” Pd-catalyzed Michael addition. 

[1] V. Aucagne, K. D. Hänni, D. A. Leigh, P. J. Lusby and D. B. Walker, J. Am. Chem. Soc., 

2006, 128, 2186-2187. 

[2] A.-M. Fuller, D. A. Leigh, P. J. Lusby, I. D. H. Oswald, S. Parsons and D. B. Walker, Angew. 

Chem. Int. Ed., 2004, 43, 3914-3918. 

[3] A.-M. L. Fuller, D. A. Leigh, P. J. Lusby, A. M. Z. Slawin and D. B. Walker, J. Am. Chem. 

Soc, 2005, 127, 12612-12619. 

[4] K. Takenaka, M. Minakawa and Y. Uozumi, J. Am. Chem. Soc., 2005, 127, 12273-12281. 

PSB 10 

Binding properties of two amides derivatives of p-phenyl 

tetrahomodioxacalix[4]arene towards alkali and alkaline-earth metal ions 

B. Mellah, a,b R. Abidi, a H. Herschbach, c K. No, d F. Arnaud-Neu b 

a Faculté des Sciences de Bizerte, Université 7 Novembre à Carthage, Bizerte, Tunisia; 

b Laboratoire de Chimie-Physique, UMR 7512 (CNRS-ULP), ECPM, Strasbourg, France; 

c Laboratoire de Spectrométrie de Masse, UMR 7512 (CNRS-ULP), ECPM, Strasbourg, France; 

d Departement of Chemistry, Sookmyung Women’s University, Seoul, Korea; 

Calix[n]arenes are known for their ability to complex selectively a large variety of metal ions [1]. 

Among this family of compounds, homooxacalix[n]arenes bearing extra oxygen atoms in the 

macrocyclic ring are particularly interesting for their conformational flexibility [2-3]. 

We report here our most recent results concerning the binding of alkali, alkaline-earth metal 

ions by two amides derivatives of p-phenyl tetrahomodioxacalix[4]arene differing by the nature 

of the functional groups at the lower rim: phenyle (1) and diethylamide (2), blocked in the 1,2 

alternate conformation [4]. 

Liquid-liquid and solid-liquid extraction of metal picrates 

from water into dichloromethane or chloroform, and 

stability constants determination in acetonitrile have 

been performed using UV-absorption spectrophotometry, 

ESI-MS and 1 N 

N 

NH 

NH 

O O 

O O 

O 

O 

O 

O 

O 

O 

H NMR techniques. The results show the 

O 

O 

O 

O 

O 

O formation of ML or M2L complexes, according to the 

O O 

cation and the ligand. They will be discussed in terms of 

NH 

NH 

O O 

N 

N size and conformational effects. 

(1) (2) 

[1] M. A. McKervey, M. J.Schwing-Weill, F. Arnaud-Neu, in Comprehensive Supramolecular 

Chemistry; J. M. Lehn, G. W. Eds.; 1996, 1, p 534. 

[2] J. M. Harrowfield, M. I. Ogden, A. H. White, J. Chem. Soc., Dalton Trans., 1991, 979. 

[3] C. Bavoux, F. Vocanson, M. Perrin, R. Lamartine, J. Incl. Phenom. Mol. Recogn. Chem., 

1995, 22, 119. 

[4] a/ K. H. No, J. H. Lee, S. H. Yang, S. H. Yu, M. H. Cho, M. J. Kim, J. S. Kim; J. Org. 

Chem. 2002, 67, 3165. b/ K. No, J. H. Lee, S. H. Yang, K. H. Noh, S. K. Kim, J. Seo, S. S. Lee, 

J. S. Kim; J. of Inclusion Phenom. and Macrocyc. Chem., 2003, 47, 167.

PSB 11 

Dual binding properties of polycyclic receptors incorporating 5,12-dioxocyclam 

units: the interplay between amines and amides 

Michel Meyer, Guy-Yves Vollmer, Laurent Frémond, Enrique Espinosa, Roger Guilard 

Institut de Chimie Moléculaire de l'Université de Bourgogne (UMR CNRS 5260), 9, avenue Alain 

Savary, BP 47870, 21078 Dijon, France 

The quest for new macropolycyclic receptors that could serve as functional catalysts or as 

biomimetic models of biological systems is stimulating continuous endeavor aimed to design 

new synthetic strategies. A trans "autodiprotected" tetraazamacrocycle with 5,12-disposed 

carbonyl groups was found to provide a convenient entry into a new class of highly 

preorganized ligands possessing well defined but tunable metal-ion binding cavities. Provided 

that 5,12-dioxocyclam (L 1 ) reacts with the appropriate biselectrophile, macrobicyclic and 

macrotricyclic cages of spheroïdal (A 1 -A 3 ) and cylindrical (T 1 -T 3 ) topologies are obtained. 

O 

R 

N HN 

O 

NH 

N 

R 

L 1 R = H 

L 2 R = CH 3 

X 

Br Br 

X = N or CH 

O 

X 

N 

N 

N 

X 

HN 

N 

NH 

O 

HN 

NH 

O 

O 

O 

HN 

NH 

O 

N 

N 

X 

A 1 X = CH (o-xylyl) 

A 2 X = CH (m-xylyl) 

A 3 X = N 

T 1 X = CH (m-xylyl) 

T 2 X = CH (p-xylyl) 

T 3 X = N (m-pyridyl) 

The peculiar acid-base properties of these amide-based ligands will be discussed in light of 

structural, spectroscopic and potentiometric data [1,2]. Reorganization of intramolecular 

hydrogen bond networks will be invoked to rationalize both the slow protonation kinetics 

exhibited by the strapped dioxocyclams A 1 -A 3 and the unprecedented allosteric regulation and 

cooperative protonation displayed by the barrel-shaped tricyclic receptors T 1 -T 3 . 

Abstraction of the amide protons by a weak base affords remarkably stable and inert copper(II) 

complexes which are able to switch from an amidate to an iminolate binding mode upon 

acidification [3]. Moreover, selective metalation of T 1 enables to isolate both the mono- and the 

dicopper species. Selected structural and spectroscopic properties, including metal-metal 

interactions in the dinuclear species, will also be presented. 

[1] M. Meyer, L. Frémond, A. Tabard, E. Espinosa, G. Y. Vollmer, R. Guilard and Y. Dory, New 

J. Chem., 2005, 29, 99. 

[2] M. Meyer, L. Frémond, E. Espinosa, S. Brandès, G. Y. Vollmer and R. Guilard, New J. 

Chem., 2005, 29, 1121. 

[3] M. Meyer, L. Frémond, E. Espinosa, R. Guilard, Z. Ou and K. M. Kadish, Inorg. Chem., 

2004, 43, 5572. 

PSB 12 

Synthesis and Characterization of the First Paramagnetic [1]Rotaxane 

Michela Fanì, Paola Franchi, Elisabetta Mezzina, Marco Lucarini 

Dipartimento di Chimica Organica “A. Mangini”, Università di Bologna, Via San Giacomo 11, I- 

40126 Bologna, Italy 

Nitroxide radicals are of great importance and interest in many fields of chemistry and related 

sciences whose properties can be exploited in many technological field., i.e. in biomedicine as spin 

traps,[1] in chemical synthesis,[2] and in the assembly of organic radical centers to control 

magnetic interaction in multispin molecular systems.[3] 

Design and dynamics control of new supramolecular host-guest complexes bearing unpaired 

electrons represent one of our research fields.[4] 

When a guest part is covalently attached to a cyclic host, it may form intramolecular and 

intermolecular complexes. Among the cyclic hosts cyclodextrins (CDs) are known to form a wide 

variety of inclusion complexes in aqueous solution. When covalently derivatized at 6 position 

(small anular edge) or at 2/3 position (large anular face) with a substituent of proper size and 

lenght, the CD can form either intramolecular (self-inclusion) or intermolecular complexes with the 

substituent, where the substituent is inserted in the anular cavity of the host. If the substituent 

involved in a self-inclusion complex is blocked into the CD with a bulky paramagnetic group acting 

as a stopper, a [1]rotaxane structure derives in which one side of the guest (the so-called ‘dumbell’ 

of rotaxane) results covalently linked to the cyclic host. 

In the present work we report the synthesis and the 

OH OTs 

SH 

S 

β-CD 6-TsO-β-CD 6-SH-β-CD (2) 3a 

a, Y=CH 2 

b, Y=CH 2 

c, Y=CH 2CH2 

d 

I 

TsCl Thiourea a 

O 

O 

NO 

Br Y O 

Br Y N H 

N 

H 

S 

O N 

O N O 

O 

N 

b, c, d 

3b, 3c, 3d 

O 

characterization of a paramagnetic [1]rotaxane starting 

from a derivative of a β-cyclodextrin monosubstituted at 

C6 position, i.e. mono-6-deoxy-6-mercapto-β-CD (2). 

Reaction of 2 with different linear halides a-d containing 

at one side a persistent radical centre consisting of a 

2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) moiety, in 

basic aqueous medium, allows the preparation of the 

corresponding monoderivatized CDs. 

Self-complexation of the linear component into the CD 

allows the rotaxanation reaction to occur only in the case 

of compound 3a. In the other cases (3b-3d) the new bond 

is formed only outside the cyclic host. The self-included 

structure of the paramagnetic [1]rotaxane 3a was 

obtained by ESI-MS, 1D and 2D NMR and EPR spectra. 

EPR kinetic measurements have evidenced the 

enhanced persistency of the new rotaxaned radicals. 

[1] R. P. Mason, Free Radical Bio. Med. 2004, 36, 1214-1223. 

[2] C. J. Hawker, A. W. Bosman and E. Harth, Chem. Rev. 2001, 101, 3661-3688. C. J. Hawker, 

Acc. Chem. Res. 1997, 30, 373-382. A. Studer, Chem.-Eur. J. 2001, 7, 1159-1164. F. Minisci, 

F. Recupero, G. F. Pedulli, and M. Lucarini, J. Mol. Cat. A 2003, 204-205, 63-90. 

[3] D. B. Amabilino and J. Veciana in Magnetism, Molecules to Materials II, Vol. II (Ed.: J. S. 

Miller, M. Drillon), Wiley-VCH, Weinheim, 2001, pp. 1-60. 

[4] E. Mezzina, M. Fanì, F. Ferroni, P. Franchi, M. Menna and M. Lucarini, J. Org. Chem. 2006, 

71, 3773-3777.

Metal Complexes of the Polyether Ionophore Antibiotic Monensin A : 

coordination mode, spectroscopic study, X-ray structures and 

antimicrobial activity 

PSB 13 

Mariana Mitewa 1 , Ivayla N. Pantcheva 1 , Petar Dorkov 1 , Rumyana Zhorova 1 , Boris Shivachev 2 , 

William S. Sheldrick 3 

1 

Sofia University, Faculty of Chemistry, Department of Analytical Chemistry, 1 J. Bourchier 

blvd., 1164 Sofia, Bulgaria 

2 

Bulgarian Academy of Sciences, Central Laboratory of Mineralogy and Crystallography, Acad. 

Georgi Bonchev Str., bl. 107, 1113 Sofia, Bulgaria 

3 

Lehrstuhl für Analytische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany 

Monensin A is a carboxylic polyether ionophore, employed in veterinary medicine for prevention 

and treatment of coccidiosis in poultry. It is a lipophylic compound due to the alkyl-rich 

backbone and is able to chelate monovalent metal ions thus transporting them across the cell 

lipid membranes. The ligand possesses high selectivity toward alkali and Ag + ions, forming 

stable neutral complexes by adopting a quasi-cyclic conformation [1-3]. 

A profound study on the coordination ability of sodium salt of Monensin A (Mon-Na) to bind 

divalent metal ions was initiated in order to establish i) if complexation occurs, and ii) if Na + ions, 

already bound into the cavity, could be replaced by the corresponding ions introduced 

In the present research the complexation of Mon-Na with transition metal ions M 2+ (M = Cu, Co 

and Mn) was studied both in solution and in solid phase. The reaction of Mon-Na and 

MCl2.nH2O in 1 : 1 ligand-to-metal molar ratio affords the formation of complexes (Mon- 

Na)2MCl2.H2O, which were isolated in solid state from acetonitrile-methanol solutions. Copper(I) 

complex salt of Mon-Na was obtained as a side product from the reaction of Mon-Na with Cu(II). 

The new compounds were studied by various spectroscopic methods (UV-Vis, IR, EPR, FAB- 

MS) and elemental analysis; appropriate crystals 

were analysed using X-ray diffraction. 

The complexes crystallize in monoclinic space group 

O6 

C2 with a tetrahedrally coordinated transition metal 

O4 

attached to oxygen atoms of deprotonated carboxyl 

O7 

O1 Na1 

groups of two Mon-Na molecules and to chloride 

O11 O8 

Cl1 O2 

O9 

ions (Fig. 1). The sodium ion remains in the cavity of 

Cl1 

Mn1 

the ligand and cannot be replaced by Cu(II), Co(II) or 

O2 O11 

Mn(II). A preferable octahedral environment around 

O9 

the transition metal centers is observed in polar 

O1 O10 

Na1 

solvents while the complexes retain their tetrahedral 

O4 

O8 

structure in non-polar media. Copper(I) complex salt 

O7 

of Mon-Na was obtained as a side product from the 

O6 

reaction of Mon-Na with Cu(II). The antimicrobial 

activity of non-coordinated ligand and its transition 

metal complexes was tested against Gram positive 

Fig. 1. ORTEP of (Mon-Na) 2MnCl2.H2O Bacillus subtillis ATCC 6633. 

[1] W. K. Lutz, F. K. Winkler and J. D. Dunitz, Helv. Chim. Acta, 1971, 54, 1103-1108 

[2] D. M. Walba, M. Hermsmeier, R. C. Haltiwanger and J. Hoordik, J. Org. Chem., 1986, 51, 

245-247 

[3] F. A. A. Raz, P. J. Gates, S. Fowler, A. Gallimore, B. Harvey, N. P. Lopes, C. B. W. Stark, J. 

Staunton, J. Klinowski and J. B. Spencer, Acta Cryst., 2003, E59, m1050-m1052 

PSB 14 

Different Types of Supramolecular Structures Resulting from Synthetic 

Procedures 

Atsuhisa Miyawaki, Yoshinori Takashima, Hiroyasu Yamaguchi and Akira Harada * 


Toyonaka, Osaka 560-0043 Japan. 

E-mail: harada@chem.sci.osaka-u.ac.jp 

Assemblies of biomacromolecules formed by noncovalent bonds are ubiquitous in nature. 

Much attention has been focused on self-assembled structures and interlocked molecules such 

as rotaxanes, catenanes and knots, because of their unique structures and properties. Although 

numerous supramolecular structures have been synthesized, to the best of our knowledge there 

are no previous examples of cyclodextrin (CD) based self-assembled complexes and 

poly[2]rotaxanes consisting of same building blocks. 

Previously, we reported preparations and structures of water soluble cyclic tri[2]rotaxanes 

(daisy chain necklaces) and linear supramolecular polymers formed by CDs having a cinnamoyl 

group and a cinnamamide group as a guest part, respectively [1] . In these supramolecular 

systems, substituent moieties were selectively included in CD cavity from its primary or 

secondary hydroxyl side as a guest. 

Herein, we have prepared the novel supramolecular complexes using the host-guest 

interaction of CDs as well as the π-π interaction of the cinnamamide group. p- 

Aminocinnamamide-α-CD (1) formed a linear-type pseudo-poly[2]rotaxane in aqueous solutions. 

Poly[2]rotaxane (poly1) was prepared by the reaction preorganized pseudo-poly[2]rotaxane 

with adamanatane carboxylic acid as a bulky stopper in aqueous solutions (Method 1). It is wellknown 

that the adamantyl group is too bulky to thread through the cavity of α-CD. Accordingly, 

cinnamamide-α-CD having an adamantyl group (2) did not form pseudo-poly[2]rotaxane 

(Method 2), whereas 2 has been found to form novel supramolecular complexes (poly2) as 

being different from pseudo-poly[2]rotaxane. The proposed structures of these supramolecular 

systems were represented in Figure 1. 

Figure 1. Schematic illustration of the supramolecular structures formed by 

same building blocks. 

[1] (a) Hoshino, T.; Miyauchi, M.; Kawaguchi, Y.; Yamaguchi, H.; Harada, A. J. Am. Chem. Soc. 

2000, 122, 9867-9868. (b) Harada, A.; Kawaguchi, Y.; Hoshino, T. J. Incl. Phenom. Macrocycl. 

Chem. 2001, 41, 115-121. (c) Miyauchi, M.; Kawaguchi, Y.; Harada, A. J. Incl. Phenom. 

Macrocycl. Chem. 2004, 50, 57-62.

Novel Copper(II) and Nickel(II) [2×2] Molecular Grids based on a 

Polynucleative Oxime-containing Shiff Base Ligand 

I. S. Moroz a , M. Haukka b and I. O. Fritsky a 

a Department of Chemistry, Kiev National Taras Shevchenko University, 01033 Kiev, Ukraine 

b Department of Chemistry, University of Joensuu, 80101 Joensuu, Finland 

One of the most succesfull approaches for obtaining polynuclear coordination compounds is 

use of well-designed polynucleative ligand systems. In this work we present copper(II) and 

nickel(II) compounds with novel polyfunctional Schiff base ligand 2-(hydroxyimino)-N'-(1- 

(pyridin-2-yl)ethylidene)propanehydrazide (pop), which contain several donor functions (oximic, 

hydrazide, hydrazone and pyridine cycle). 

The synthesized complexes have been characterized by 

a variety of spectral methods; three of them [Cu4(pop- 

2H)4(H2O)4] (1), [Cu4(pop-2H)4(HCOOH)4] (2) and 

[Ni4(pop-H)4(HCOO)4] (3) were studied by X-ray single 

crystal analysis. The complexes 1-3 indicate [22] 

pop 

PSB 15 

molecular grid structure and comprise of tetranuclear sixcoordinated 

metal arrays. In the nickel complex two types 

of chromophors are realized (NiN2O4 and NiN4O2). On the other hand, for the copper complexes 

only one type of chromophor (CuN3O3) is observed. The coordination of pop is realized in a 

tetradentate mode via the pyridine, azomethine and oximic nitrogen atoms and the bridging 

amide oxygen atom. 

Molecular structure of 3 

The average metal-metal separation in all cases is ca. 4 Å, the M--M angles are in the range 

137-139 o for 3 and 139-142 o for 1, 2. 

4-(4-Thiocarbamoyl-1,2,3-triazol-1-yl)benzoannelated Crown Ethers as 

Amino Acid's Receptors. 

PSB 16 

Yuri Yu. Morzherin, Polina E. Kropotina, Tatiana V. Glukhareva, Nadezhda A. Itsikson, Anatoly 

I. Matern 

Urals State Technical University, Chemical Technology Faculty, Mira, 19, 620002, Ekaterinburg, 

Russia 

In the last decade, considerable effort has been devoted to molecular recognition and/or 

selforganization within the field of supramolecular chemistry. One of the most noticeable 

aspects in this interdisciplinary area is the emergence of the wide range of intriguing 

compounds specially designed and created on the basis of complimentary to function as 

sensors and receptors for biological and abiotic particles. Extensive studies of non-covalent 

interactions between synthetic receptors and simple species as cations, anions and small and 

simple neutral molecules have not only led to various molecular and supramolecular devices 

but, more significantly, had a big impact on the development of modern chemistry as well. A 

challenging research area in this field is the design and construction of sophisticated artificial 

receptors with polytopicity and polyfunctionality that would be highly efficient in complexation 

with more complicated molecules. A convenient method for one-step modification of crown 

ether by nitrogen containing heterocycle based on the methodology of rearrangements of 1,2,3thiadiazoles. 

Now we report the synthesis of amino acid's receptor. 

The complexating properties of obtained crown ether toward amino acids have been studied by 

used various methods. We was shown that benzocrown ether containing the 4-thiocabamoyl- 

1,2,3-triazole is receptors for amino acid. 

This work was financially supported by the grants Russian Foundation of Basic Researches 05- 

03-32094

PSB 17 

Metal controlled anion interaction at the thiourea subunit: low-spin iron(II) 

2-formylpyridine-thiosemicarbazone complexes 

Lorenzo Mosca a , Valeria Amendola a , Massimo Boiocchi b , Luigi Fabbrizzi a , Antonio Poggi a 

a Dipartimento di Chimica Generale, Università di Pavia, 27100 Pavia, Italy 

b Centro Grandi Strumenti, Laboratorio di Cristallografia, Università di Pavia, 27100 Pavia, Italy 

Thiourea is a powerful donor of bifurcate H-bonds and its derivatives are currently used for 

anion recognition and sensing in non-aqueous media. However, more basic anions may induce 

deprotonation of one of the two NH fragments. [1] For instance, benzylidenethiourea 

derivatives of type 1 form stable 1:1 H-bond complexes with CH3COO and H2PO4 in MeCN, 

but, in presence of two equiv. of F , undergo deprotonation. [2] 

X 

N 

N 

H 

S 

N 

H 

H + 

X 

N 

S 

N N 

H 

X 

N 

S 

N N 

H 

1 X = CH; 2 X = N 3 4 

We have now observed that system 2 shows a very low affinity towards anions, even in the 

poorly polar solvent CHCl3, probably due to the existence of an intramolecular H-bond 

interactions. On the other hand, 2 (= HL) behaves as a terdentate ligand with transition metals. 

For instance, a crystalline complex salt of formula [Fe II (HL)2](CF3SO3)2 . H2O was isolated, whose 

X-ray structure is shown in the Figure. The low-spin iron(II) complex exhibits a distorted 

octahedral geometry, with the ligand adopting a meridional coordination mode (NFeS angle = 

165°). Moreover, in a CHCl3 solution, on titration with strong 

base, the complex undergoes two stepwise deprotonation 

equilibria, according to the scheme: 

[Fe II (HL)2] 2+ [Fe II (HL)(L)] + [Fe II (L)2] 

It is suggested that deprotonation takes places at the hydrazide 

NH fragment (formula 3), followed by electronic rearrangement 

to the resonance formula 4. Metal coordination by the thiolate 

group has been documented by a number of structures of Fe II 

complexes with analogous ligands. The [Fe II (HL)2] 2+ complex 

exposes two thiourea subunits towards the outside and could act 

as a ditopic receptor for anions. However, on titration with 

oxoanions of varying basicity (e.g. CH3COO , NO2 ), two-step 

deprotonation takes place. Only the poorly basic anion NO3 

forms genuine H-bond complexes with [Fe II (HL)2] 2+ , of 1:1 and 

2:1 stoichiometry, whose logK values differ only for the statistical 

factor. Present results emphasize the role of metals in polarizing 

the NH fragments of the thiourea subunit and open the way to 

the design of metal containing anion receptors of novel selectivity. 

[1] D. Esteban-Gómez, L. Fabbrizzi, M. Licchelli, E. Monzani, Org. Biomol. Chem., 2005, 3, 

1495–1500. 

[2] M. Bonizzoni, L. Fabbrizzi, A. Taglietti, F. Tiengo, Eur. J. Org. Chem., 2006, 3567-3574. 

PSB 18 

Peptides transport through liquid membrane by calix[n]arene derivatives 

Lucia Mutihac a , Hans-Jürgen Buschmann b , Radu-Cristian Mutihac b , Eckhard Schollmeyer b 

a 

University of Bucharest, Department of Analytical Chemistry, 4-12 Regina Elisabeta, 030018, 

Bucharest, Romania 

b 

Deutsches Textilforschungszentrum Nord-West, e.V., Institut an der Universität Duisburg- 

Essen, Adlerstrasse 1, D-47798 Krefeld, Germany 

The investigation of the nature of interactions involved in ligand-peptide complex formation is of 

particular relevance for understanding several specific biomolecular interactions which play a 

key role in regulation of cellular processes [1-4]. Along this topics, the study of factors that 

contribute to the complex formation are of current interest in peptide chemistry. 

In order to outline the possibility of calixarenes acting as an carriers through membrane, we 

have investigated some aspects of the transport through chloroform liquid membrane of 

peptides, namely: glycyl-glycine, glycyl-L-alanine, glycyl-L-leucine, glycyl-L-phenylalanine, Lleucyl-glycine, 

L-leucyl-L-alanine, and glycyl-L-valine with with p-tert-butylcalix[n, n = 4,6, 

8]arenes in the presence of tropaeolin 00. The effects of physicochemical parameters involved 

in the process transport such as the structure of calixarene, the nature of the anion used as 

counterion, and the structure of peptide have been studied. Additionally, the influence of the 

composition and the structure of the compounds under study upon the partition processes 

occurring in triphasic systems have been reported. A relationship between the transport yields 

through liquid membrane of peptides and their structural characteristics has been pointed out. 

The results showed that the inclusion abilities of the investigated hosts were correlated with 

their conformational properties. 

[1] M. W. Peczuh, A. D. Hamilton, Chem. Rev. 100, 2479 (2000). [2] C.D. Gutsche, Calixarenes 

Revisited, The Royal Society of Chemistry, Cambridge, UK, 1998. [3]. J. Vicens, V. Böhmer, 

Calixarenes- A Versatile Class of Macrocyclic Compounds, Kluwer Academic Publishers, 

Dordrecht, 1991. [4] L. Mutihac, H.-J. Buschmann, R.-C. Mutihac, E. Schollmeyer, J. Incl. 

Phenom. Macrocyclic Chem. 51, 1, 2005.

Some analytical applications of modified cyclodextrins 

PSB 19 

Lidia Kim a , Cristian Baltariu a , Ana Delia Stancu a , Radu-Cristian Mutihac c , Elena Diacu b , Hans- 

Jürgen Buschmann c , Lucia Mutihac a 

a 

University of Bucharest, Department of Analytical Chemistry, 4-12 Regina Elisabeta, 030018, 

Bucharest, Romania 

b 

University Politehnica, Faculty of Applied Chemistry and Materials Science, Polizu 1, 011061, 

Bucharest, Romania, 

c 

Deutsches Textilforschungszentrum Nord-West, e.V., Institut an der Universität Duisburg- 

Essen, Adlerstrasse 1, D-47798 Krefeld, Germany 

There are studies dedicated to the molecular inclusion of biological substrates, like biogenic 

amines, amino acids, and peptides by cyclodextrins [1-3]. The interactions involved in 

cyclodextrin complexes (hydrogen bonding, van der Waals forces, release of conformational 

strain, change–transfer, electrostatic and hydrophobic interactions) are known to play an 

important role in pharmaceutical science, biochemistry, immunochemistry and also in analytical 

chemistry. Thus, cyclodextrins and their derivatives form inclusion complexes with aromatic 

amino acids or their oligopeptides, being well known that the aromatic amino acid residues are 

responsible for interaction of proteins/peptides. 

The analytical applications in extraction and transport processes of biological compounds such 

as amino acids by using modified cyclodextrins are presented. In order to outline the possibility 

of modified cyclodextrins acting as carriers through membrane, we have investigated some 

aspects of the solvent extraction and the transport through chloroform liquid membrane of some 

amino acid methylesters in the presence of picric acid or tropaeolin 00. The effects of 

physicochemical parameters involved in extraction and transport processes such as the 

structure of cyclodextrin, the nature of the anion used as counterion, and the structure of amino 

acid have been studied. Moreover the influence of the composition and the structure of the 

compounds under study upon the partition processes occurring in triphasic systems have been 

reported. 

[1] J.-M. Lehn, Supramolecular Chemistry, Concepts and Perspectives, VCH, Weinheim, 1995. 

[2]. J. Szejtli, T. Osa, Comprehensive Supramolecular Chemistry, Elsevier, Oxford, Vol. 3, 

Cyclodextrins, 1996. 

[3]. H.-J. Buschmann, L. Mutihac, E. Schollmeyer, Supramol. Chem. 2005, 17, 447- 451. 

PSB 20 

4-(3-(Phtalhydrazide) azo)N-phenylaza-15-crown-5. Synthesis and properties 

Rodica D. Baratoiu a , Radu Socoteanu a , Lucia Mutihac b , Titus Constantinescu a 

a 

Roumanian Academy, “Ilie G. Murgulescu” Institute of Physical Chemistry, Laboratory of 

Supramolecular Chemistry and Interphase Processes, Splaiul Independentei 202, 060021, 

Romania; e-mail: titelconstantinescu@yahoo.com 

b 

University of Bucharest, Departament of Analytical Chemistry, 4-12, Regina Elisabeta, Blvd., 

030018, Bucharest, Romania 

A new compound 1 with hydrophobic properties, low acidity, and important chromogenic and 

ionophoric properties due to the molecular design, has been synthesized [1]. 

25 24 23 22 

O 

21 

26 O 20 

27 

19 

O 

N 

28 O 29 

30 31 32 33 

15 14 

16 13 

17 18 

1 

12 

11 

9 

10 

N 

7 

N 

5 4 

O 6 3 O 

1 

N 

2 

N 

H H 

The relative hydrophobic character due to the azo-N-phenylaza-15-crown-5 moiety (compared 

with N-phenylaza-15-crown-5 and 5-amino-2,3-dihydro-1,4-phtalazine-dione), has been 

estimated, by determination of molecular hydrophobicity (RM0) using reverse phase thin-layer 

chromatography (RP-TLC). On attempting to calculate log P values using fragmental constants 

(Hansch and Leo), a relatively good correlation (R 2 =0.858) with experimental data for R M0 was 

obtained. Compound 1 is a weak acid (pKa = 6.7 in water) and exhibits positive solvatochromy, 

depending on the solvent polarity (ET(30), Dimroth-Reichardt’s parameters). The chromogenic 

properties as function of pH were established by spectral measurements, meaning (NMR and 

UV-vis), which indicate : i) in acidic medium, the quaternization by protonation of macrocyclic 

nitrogen (N 19 ) atom took place (this process was put in evidence by recording the 1 H- and 13 C- 

NMR spectra at different temperatures, in the presence of trifluoroacetic acid; the free energy 

of the rotation barier around the double bond N 19 =C 16 that was formed, G * = 15.2 kcal mol -1 ), 

respectively a significant batochromatic shift (23 nm) in UV-vis spectrum was observed; ii) in 

alkaline medium, a significant hipsochromatic shift (85 nm) took place (due to the acidity of the 

2,3-dihydro-1,4-phtalazine-dione moiety). The ionophoric properties of compound 1 (due to the 

N-phenylaza-15-crown-5 moiety) towards Li + , Na + , K + , Rb + and Cs + ions, were investigated by 

UV-vis measurements in acetonitrile and chloroform as solvents. 

[1] R. D. Baratoiu, A. E. Barbu, L. Mutihac, M. T. Caproiu, C. Draghici, R. Socoteanu, T. 

Constantinescu, Rev. Roum. Chim., 2006, 51, 261-267. 

8

Crown Ether-tert-Ammonium Salt Complex Fixed as Rotaxane and its 

Derivation to Neutral Rotaxane 

Kazuko Nakazono and Toshikazu Takata 

Department of Organic and Polymeric Materials, Tokyo Institute of Technology, 2-12-1 

Ookayama, Meguro-ku, Tokyo 152-8550, JAPAN 

Complex formation between crown ethers and ammonium salts is well known and often 

applied to synthesis of supramolecular compounds and molecular recognition systems. 

However, no complex between tert-ammonium salts and crown ethers has been reported, 

probably because of very small association constant of them. Tert-ammonium salt has a proton 

to participate in the hydrogen bonding leading to the complexation, so that the complex 

becomes quite unstable. We have recently succeeded in fixing the crown ether-tert-ammonium 

complex as rotaxane structure which might be an appropriate substance enable to study the 

complexation, since it is an intramolecular recognition system. This paper discusses the 

formation, structure, and property of such rotaxane, along with its neutralization to “free” 

rotaxane. 

To a mixture of tert-ammonium salt 1 and dibenzo-24-crown-8-ether (DB24C8) were 

added a catalytic amount of tri(butyl)phosphine and 3,5-dimethylbenzoic anhydride. The 

mixture was allowed stand for 48 h to give [2]rotaxane 2 in 3% yield. This yield is much higher 

than that when wheel and axle had no attractive interaction. The 1 H NMR spectrum of 2 in 

CDCl3 showed that DB24C8 stayed on the tert-ammonium nitrogen. This result suggested that, 

the hydrogen bond is strong enough to keep the complex due to the intramolecular system. 

O 

O 

PF6 H 

N 

Me 

1 

OH 

+ 

O O 

O O 

O O 

O O 

2 

Bu3P CHCl3, 0 ºC 

3 % >> Statistical yield 

O O 

O H O 

N 

O Me O 

O O 

PF6 2 

Rotaxane 2 was deprotonated by treating with a base to give a neutral rotaxane 3 having 

tert-amine group. The 1 H NMR spectra of 2 and 3 suggested the deprotonation caused the 

movement of DB24C8 from the ammonium nitrogen to the ester group. Protonation of 3 with 

HCl aq resulted in the re-transfer of DB24C8 from the ester group to the ammonium nitrogen. 

These results show the possibility of a molecular switch controlled by pH. 

tert-Ammonium 

salt 

O O 

O H O 

N 

O Me O O 

O O 

O 

2 - PF6 , Cl 

-H + 

H 

quantitative 

+ 

Switching 

tert-Amine 

3 

N 

Me 

O O 

O O 

O OO 

O O O 

pH control 

A B A B 

O 

O 

PSB 21 

PSB 22 

Supramolecular Receptor Design – Anion Triggered Differentiation Between 

Substrates 

Kent A. Nielsen, 1 Won-Seob Cho, 2 Ginka Sarova, 3 Bo M. Petersen, 1 Jan Becher, 1 

Frank Jensen, 1 Dirk M. Guldi, 3 Jonathan L. Sessler, 2 and Jan O. Jeppesen 1 

1 

The University of Southern Denmark, Odense University, Campusvej 55, 5230 Odense M, 

Denmark; e-mail: kan@chem.sdu.dk 

2 

The University of Texas at Austin, Austin, 1 University Station-A5300, Texas 78712-0165, USA 

3 

Institute for Physical and Theoretical Chemistry, Universität Erlangen-Nürnberg, Egerlandstr. 3, 

91058 Erlangen, Germany 

Self-assembled structures are wide spread in Nature and are a key feature of many biological 

small molecule recognition motifs. Not surprisingly, therefore, considerable effort has been 

devoted to developing synthetic self-assembled receptor systems, multi-component molecular 

hosts, that are able to interact with and binding specifically targeted substrates. To date, 

systems based on metal-coordination [1] and hydrogen bond recognition features [2] have received 

the greatest attention. Singularly lacking from the lexicon of known self-assembled receptor 

systems are ones where anion recognition plays a key structural or controlling role. In this 

report, we show how an synthetic receptor systems – a tetrathiafulvalene-functionalized 

calixpyrrole [3] – interact with and differentiate between different target substrates (See Figure) 

as a result of a conformational change induced by chloride anion. This differentiation produces 

an easy-to-visualize color change between brown and green that arises from charge transfer 

(CT) interactions between receptor and substrates in question. 

[1] (a) N. Takeda, K. Umemoto, K. Yamaguchi, M. Fujita Nature 1999, 398, 794−796. (b) B. 

Olenyuk, J. A. Whiteford, A. Fechtenkötter, P. J. Stang Nature 1999, 398, 796−799. 

(c) D. Fiedler, D. H. Leung, R. G. Bergman, K. N. Raymond Acc. Chem. Res. 

2005, 38, 349−360. 

[2] (a) B. Linton, A. D. Hamilton Chem. Rev. 1997, 97, 1669−1680. (b) T. Heinz, D. M. 

Rudkevich, J. Rebek Jr. Nature 1998, 394, 764−766 (c) J. Rebek Jr. Angew. Chem. 

Int. Ed. 2005, 44, 2068−2078. 

[3] (a) K. A. Nielsen, W.-S. Cho, J. O. Jeppesen, V. M. Lynch, J. Becher, J. L. Sessler 

J. Am. Chem. Soc. 2004, 126, 16296–16297. (b) K. A. Nielsen, W.-S. Cho, G. H. Sarova, 

B. M. Petersen, A. B. Bond, J. Becher, F. Jensen, D. M. Guldi, J. L. Sessler, J. O. 

Jeppesen, Angew. Chem. Int. Ed. 2006, 45, 6848–6853.

Template-assembled synthetic G-quartets (TASQs) 

Mehran Nikan, David Perrin, John C. Sherman* 

Department of Chemistry, 6174 University Blvd., Vancouver, British Columbia 

Guanine bases, present in guanosine compounds, guanine-rich strands of DNA and RNA, or 

DNA-like polymers are able to self-associate and form a tetrameric structure called a G-quartet 

[1]. To date it has been shown that G-quartets are templated and stabilized by cations [2]. 

Guanine aggregation in the absence of cations results in the formation of ribbon-like structures 

[3]. We investigated the assembly of guanosine compounds by coupling them to an external 

rigid template. This method proved to be helpful and organized guanosines into a G-quartet 

without the need of templating cations. The cavitand places guanosines in close proximity for Hbonding 

and compensates for the entropy loss in organizations of four guanines into a single 

unit. 

H2N N 

HN 

N 

O 

N 

O 

O 

O 

N 

N N 

O 

O 

O 

H 2N 

O 

O H 

N 

NH2 N N 

N 

O 

O 

N N 

N 

O 

O 

O 

O 

N 

H 

R 

O 

R R 

O 

N 

O 

N N 

O 

R 

O 

O 

N 

N N 

O 

O 

O 

N N 

N 

O 

O 

O 

N 

N 

N 

NH 

The synthesis, structural features, solution behavior and stability of this system will be reported, 

and the results of the cation extraction experiments will be briefly discussed. 

O 

NH 2 

PSB 23 

[1] Davis, J. T., Angewandte Chemie-International Edition 2004, 43, (6), 668-698. 

[2] Pinnavaia, T. J.; Marshall, C. L.; Mettler, C. M.; Fisk, C. I.; Miles, H. T.; Becker, E. D., Journal 

of the American Chemical Society 1978, 100, (11), 3625-3627. 

[3] (a) Gottarelli, G.; Masiero, S.; Mezzina, E.; Pieraccini, S.; Rabe, J. P.; Samori, P.; Spada, G. 

P., Chemistry-a European Journal 2000, 6, (17), 3242-3248. (b) Sessler, J. L.; Sathiosatham, 

M.; Doerr, K.; Lynch, V.; Abboud, Angewandte Chemie-International Edition 2000, 39, (7), 1300. 

(c) Kotch, F. W.; Sidorov, V.; Lam, Y. F.; Kayser, K. J.; Li, H.; Kaucher, M. S.; Davis, J. T., 

Journal of the American Chemical Society 2003, 125, (49), 15140-15150. 

Application of Dynamic Combinatorial Chemistry in the synthesis of 

polyazamacrocycles containing furan or thiophene units 

Aleksandra Obrocka, a Krzysztof Ziach, a Janusz Jurczak a,b 

a) Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland 

b) Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 

01-224 Warsaw, Poland 

PSB 24 

One of the crucial problems in supramolecular chemistry is an effective synthesis of macrocyclic 

compounds of desired size and structure. Another difficulty is designing a ligand able to bind the 

specific guest molecule. Dynamic Combinatorial Chemistry (DCC), new synthetic methodology, 

can solve both of these problems.[1] DCC bases on reversibility of a reaction used to create the 

Dynamic Combinatorial Library (DCL). Addition of a substance that interacts noncovalently with 

members of the library changes the equilibrium position in the system. The imination reaction, 

as a fast reversible process, is good candidate for a model reaction for DCC.[2] [3] 

Herein we present the study on the imination reaction (Scheme 1) between aromatic 

dialdehydes (2,5-diformylfuran and 2,5-diformylthiophene) and a,w-diamines used as building 

blocks in the presence of variety of inorganic (alkaline metal) cations as templates 

DCLs of resulting Schiff bases were analysed using electrospray ionization mass spectrometry 

(ESI-MS). The dynamic imine libraries were “frozen” by means of NaBH4 reduction to 

corresponding polyamines. HPLC technique was successfully adopted, allowing for quantitative 

template effect determination. 

[1] S. J. Rowan, S. J. Cantrill, G. R. L. Cousins, J. K. M. Sanders and J. F. Stoddart, Angew. 

Chem. Int. Ed., 2002, 41, 899-952 

[2] O. Storm and U. Luning, Chem. Eur. J., 2002, 8, 793-798 

[3] A. González-Álvarez, I. Alfonso, F. López-Ortiz, A. Aguirre, S. García-Granda and V. Gotor, 

Eur. J. Org. Chem. 2004, 1117

PSB 25 

A Minimalist Design for Self-Assembled Rosette Nanotubes based on 

Mascal’s Motif 

Martins Oderinde, Grigory Tikhomirov and Hicham Fenniri* 

National Institute for Nanotechnology (NINT-NRC), Department of Chemistry, 

University of Alberta, 11421 Saskatchewan Dr, Edmonton, Alberta T6G 2M9, Canada 

H 

H 

N 

H 

N 

O 

H H 

1 

N 

N 

H 

N 

O 

N 

N 

N O 

O N N 

H H 

N 

H 

N O 

H 

N 

H 

H H H 

O N 

N N 

H H 

N N 

O 

H 

N N O 

H H H 

H H 

H H H 

O N N 

H 

O 

N N 

H H 

H H 

N N 

N O 

H 

H H H 

H 

N 

H 

H 

O N 

H 

N 

H 

H H H 

N 

H 

N O 

O N 

H 

N 

H H 

N 

H H 

Rosette of 1 

G/C base 1, based on Mascal’s motif, was synthesized and its ability to self-assemble into 

rosette nanotubes in water was investigated. This presentation will focus on the synthesis and 

characterization of compound 1 by SEM, TEM, AFM and UV-VIS. Consistent with the calculated 

diameter of 2.2 nm, the TEM-measured diameter of a single tube was 2.2 0.2 nm. This value 

is also consistent with height profiles obtained from TM-AFM images, which give slightly 

compressed diameter of 2.0 0.2 nm. 

[1] (a) Fenniri, H.; Mathiavanan, P.; Vidale, K. L.; Sherman, D. M.; Hallenga, K.; Wood, K. V.; 

Stowell, J. G. J. Am. Chem. Soc. 2001, 123, 3854-3855. (b) Fenniri, H.; Deng, B. L.; Ribbe, A. 

E. J Am. Chem. Soc. 2002, 124, 11064-11072. (c) Fenniri, H.; Deng, B. L.; Ribbe, A. E.; 

Hallenga, K.; Jacob, J.; Thiyagarajan, P. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 6487-6492. 

[2] (a) Mascal, M.; Hext, N.; Warmuth, R.; Moore, M. H.; Turkenburg, J. P. Angew. Chem. 1996, 

35, 2204-2206. (b) Mascal, M.; Farmer, S. C.; Arnall-Culliford, J. R. J. Org. Chem. 2006, 71, 

8146-8150 

PSB 26 

Chemically-Responsive Sol-Gel Transition of Supramolecular Single-Walled 

Carbon Nanotubes (SWNTs) Hydrogel Made by SWNTs-Cyclodextrins 

Hybrids 

Tomoki Ogoshi a , Tada-aki Yamagishi a , Yoshiaki Nakamoto a , and Akira Harada b 

a 

Department of Chemistry and Chemical Engineering, Graduate School of Natural Science and 

Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan and 

b 


Toyonaka, Osaka 560-0043, Japan 

Single-walled carbon nanotubes (SWNTs) have received a great deal of interests because of 

their unique structural, electrical, and mechanical properties. However, their applications have 

been extremely limited due to their low solubility in solvents. Therefore, solubilization of SWNTs 

has been one of hot topics for the past few years. Soluble SWNTs in aqueous media are 

obtained using interaction between pyrene having ionic groups and SWNTs. Herein, we 

report novel chemically-responsive supramolecular SWNT hydrogel by using soluble SWNTs 

functionalized cyclodextrin (CD) moieties on SWNT surface. Since CD shows high solubility in 

water, water-soluble SWNTs carrying CDs are obtained by using interaction between 

pyrene modified -CDs and SWNTs (Py--CD/SWNT hybrids) [1]. 

By utilizing host-guest interactions between poly(acrylic acid) carrying dodecyl groups (PAA2) 

and -CDs of Py--CD/SWNT hybrids, nanocomposites of polymer and SWNTs were prepared. 

By mixing Py--CD/SWNT hybrids and PAA2 in aqueous media (Scheme 1a), a homogeneous 

SWNT hydrogel formed, indicating that host-guest complexes between -CD moieties 

immobilized on the SWNT surface and dodecyl groups in PAA2 act as cross-links to form 

network structures which showed gel-like behavior. Furthermore, SWNT hydrogels composed of 

Py--CD/SWNT hybrids and PAA2 changed to sol by adding competitive guests or host 

compounds. When sodium adamantane carboxylate (AdCNa, 100 eq. to dodecyl moieties of 

PAA2) was added to the hydrogel as a competitive guest, gel to sol transition was observed 

(Scheme 1b). This result indicates dissociation of the host-guest complexes between -CDs of 

Py--CD/SWNT hybrids and dodecyl groups of PAA2 because AdCNa strongly interacts with - 

CD compared with dodecyl group. Upon addition of -CD (100 eq. to dodecyl groups of PAA2) 

as a competitive host, the gel also changed to sol (Scheme 1c). It is because dodecyl moieties 

form complexes with -CD more favorably than with -CD. 

(b) (a) 

(c) 

+ 

+ -CD 

sol 

gel 

sol 

Supramolecular SWNT Hydrogel 

Scheme 1. Supramolecular SWNT Hydrogel Prepared from Py--CD/SWNT Hybrids and 

Guest Modified Polymer (PAA2). 

[1] Ogoshi, T. et al. J. Am. Chem. Soc. 2007, in press. 

PAA2 

Py--CD

High Order Bistable [n]Rotaxane Architectures 

Ivan Aprahamian, William Dichtel, Travis Gasa, John-Carl Olsen, J. Fraser Stoddart 

California NanoSystems Institute and Department of Chemistry and Biochemistry, University of 

California Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095, USA 

(jcolsen@chem.ucla.edu) 

The efficient preparation of high order interlocked structures will facilitate the development of 

sophisticated molecular machinery. For example, three-fold symmetric bistable [4]rotaxanes 

might form the basis of electrochemically switchable elevators 1 , artificial muscles 2 , or stimuliresponsive 

nanovalves. 3 We recently found that the kinetically controlled synthesis of [2]-, [3]-, 

and [4]rotaxanes 4 and catenanes 5 proceeds with excellent yield from relatively simple 

precursors. This success has recently been extended to bistable rotaxanes. 6 The synthesis 

and characterization of a variety of bistable [4]rotaxane architectures including tripods (Figure 

1), capsules, and elevators will be presented. 

Figure 1. A fully-synthesized, bistable, tripodal [4]rotaxane incorporating tetrathiafulvalene (TTF), 1,5-dioxynaphthalene 

(DNP), and cyclobi s(paraquat-p-phenylene) (CBPQT 4+ ) components. 

+ N 

+ 

N 

O O 

S 

S 

S 

S 

O O O 

O O N 

N 

N 

O 

H 3C 

O 

O 

O 

N 

O 

N 

O 

O 

N 

+ + 

+ + 

N 

S S 

O 

S S 

O O O 

N 

S 

S 

+ + 

+ N 

N + 

S 

S 

N 

+ N 

N+ 

O O O 

O O N 

N 

N 

O O N 

N 

N 

[1] Badjic, J. D.; Balzani, V. Credi, A.; Silvi, S.; Stoddart. J. F. Science, 2004, 303, 1845 

[2] Liu, Y.; Flood, A. H.; Bonvallet, P. A.; Vignon, S. A.; Northrop, B. H.; Tseng, H.-R.; 

Jeppesen, J. O.; Huang, T. J.; Brough, B.; Baller, M.; Magonov, S.; Solares, S. D.; 

Goddard, W. A.; Ho, C.-M.; Stoddart, J. F. J. Am. Chem. Soc. 2005, 127, 9745 

[3] Hernandez, R.; Tseng, H.-R.; Wong, J. W.; Stoddart, J. F.; Zink, J. I. J. Am. Chem. Soc. 

2004, 126, 3370 

[4] Dichtel, W. R.; Miljanic, O. S.; Spruell, J. M.; Heath, J. R.; Stoddart, J. F. J. Am. Chem. 

Soc. 2006, 128, 10388 

[5] Miljanic, O. S.; Dichtel, W. R.; Mortezaei, S.; Stoddart, J. F. Org. Lett. 2006, 8, 4835. 

[6] [6] Aprahamian, I.; Dichtel, W. R.; Ikeda, T.; Heath, J. R.; Stoddart, J. F. Org. Lett. 2007, 

9, 1287 

12PF 6 

- 

O 

O 

PSB 27 

PSB 28 

Polymerization of Lactones and Lactides Initiated by Cyclodextrins in Bulk: 

Effects of Cyclodextrins on the Initiation and Propagation 

Motofumi Osaki, Yoshinori Takashima, Hiroyasu Yamaguchi, Akira Harada 


Toyonaka, Osaka 560-0043, Japan. e-mail: harada@chem.sci.osaka-u.ac.jp 

Cyclodextrins (CDs) have attracted 

much attention of many researchers as 

enzyme models. Previously, cyclodextrins 

(CDs) were found to accelerate the hydrolysis 

of some lactones in aqueous solutions. 1 Here, 

the authors found that CDs initiate the 

polymerization of lactones in bulk at 100 o C to 

give CD-tethered polyesters. 2 

The order of the polymerization activity 

for δ-valerolactone (δ-VL) with CDs was β-CD 

> γ-CD >> α-CD (no CD), depending on the 

cavity size of CDs (Figure 1). Polymerizations 

of DL-lactide (DL-LA) were also initiated by CDs. 

The order of the activity for DL-LA was γ-CD > 

β-CD > α-CD > (no CD). These results indicate 

that the formation of the inclusion complexes 

between CD and monomer plays an important 

role in the polymerizations. 

The details of the polymerization of 

lactones by CDs were investigated to propose 

the mechanism (Scheme 1). 3 The included 

lactone in the CD cavity is activated by the 

formation of a hydrogen bond between the 

carbonyl oxygen of the lactone and the 

hydroxyl group of CD. A secondary hydroxyl 

group attacks the activated carbonyl carbon of 

the lactone in the CD cavity, cleaving the CO 

bond of δ-VL to give the monomer-attached CD 

in the initial step. In the propagation step, the 

monomer recognition, the activation of the 

monomer and the insertion of monomers are 

serially repeated to give CD-tethered poly(δ- 

VL). 

In the presentation, the authors would 

talk about the detail of the polymerization 

mechanism. 

Figure 1. Yields of the poly(δ-VL) as a 

function of time. δ-VL was initiated by 

various CDs in bulk at 100 o C. 

Scheme 1. Proposed mechanism for the 

polymerization of δ-VL initiated by CD. 

[1] Takashima, Y.; Kawaguchi, Y.; Nakagawa, S.; Harada, A. Chem. Lett. 2003, 32, 1122-1123. 

[2] Takashima, Y.; Osaki, M.; Harada, A. J. Am. Chem. Soc. 2004, 126, 13588-13589. 

[3] Osaki, M.; Takashima, Y; Yamaguchi, H.; Harada, A. Macromolecules 2007, in press.

PSB 29 

Control of Translation of the Cyclic Component onto the Rotaxane bearing 

2-Pyridinium Moieties 

Tomoya Oshikiri, Hiroyasu Yamaguchi, Yoshinori Takashima, Yasushi Okumura, Akira Harada. 

Department of Macromolecular Science, Graduate School of Science, 

Osaka University, Toyonaka, Osaka 560-0043, Japan Email: oshikiri@chem.sci.osaka-u.ac.jp 

In recent years, designing and constructing “molecular machines” and “molecular 

devices” have received much attention. Interlocked 

molecules such as rotaxanes and catenanes have 

been extensively used as models for “molecular 

machines” and “molecular devices” due to the 

relative mobility of each component. Cyclodextrin 

(CD) has a rigid, well-defined "non-symmetric" ring 

structure. 

Previously, we reported kinetic control of the 

face direction of cyclodextrin in the construction of 

Figure 1. Structures of axle molecules. 

pseudo-rotaxane with the alkyl chain bearing pyridyl 

end caps. 1,2 faster 

We report here the face-direction 

control of CD in the threading and the sliding 

process of pseudo-rotaxane with the alkyl chain 

bearing the bulky and the non-symmetric linker 

moiety. Figure 1 shows axle molecules prepared by 

the reaction of α, ω-dihalodecane with pyridine 

derivatives. 

slower 

After the addition of α-CD to the aqueous 

solution of axle 1, the NMR spectra showed obvious changes. First, the protons of the 

decamethylene moiety bound to the 4-position of 2methylpyridinium 

were splitted. And then, the 

protons of decamethelene moiety in the vicinity of 

3,5-dimethylpyridinium were separated into the free 

guest and the complex. These results mean α-CD 

threads on the first station rapidly, and then slides 

to the station close to the stopper gradually. 

Furthermore, the 2D ROESY spectrum revealed 

that α-CD formed an inclusion complex at the 

station close to the stopper moiety in a unique 

direction where the secondary side in the α-CD 

faces to the 3,5-dimethylpyridine moiety. The 

kinetic analysis revealed that the rate constant of 

the translation from the first station to second station 

by the wider side is 10 times larger than that by the 

Figure 2. Schematic representation of 

shuttling process of α-CD with 1. 

Figure 3. Degree of complex formation 

of 1 with α-CD as a function of time.. 

narrow side. In the case of 2, the 2-methylpyridinium linker also could control the rate of the 

translation of CDs. 

These results indicate that the 2-methylpyridinium linker bearing axle molecules could 

control the face direction of α-CD in the sliding process. 

[1] Oshikiri, T.; Takashima, Y.; Yamagushi, H.; Harada, A J. Am. Chem. Soc. 2005, 127(35), 

12186-12187. 

[2] Yamaguchi, H.; Oshikiri, T.; Harada, A.J. Phys. Condens. Matter 2006, 18(33), S1809- 

S1816. 

A fluorescent micellar lipophilicity-meter for carboxylates 

PSB 30 

Giacomo Dacarro, a Franck Denat, b Yuri Diaz Fernandez, a Piersandro Pallavicini, a Luca Pasotti a , 

Stefano Patroni, a and Yoann Rousselin b 

a:Dipartimento di Chimica Generale, Università di Pavia, v.le Taramelli, 12 – 27100 Pavia, Italy; 

b: Institut de Chimie Moléculaire de l'Université de Bourgogne, UMR CNRS 5260, 9 avenue 

Alain Savary - BP 47870 - 21078 DIJON cedex - France 

Sensing processes signalled by the variation of fluorescence may take advantage of the use of 

micelles, exploiting their ability to self-assembling in water and to host a huge number of 

different lipophilic species.[1] The sparingly water-soluble Pyrenecarboxylic acid, PyrCOOH, 

can be dissolved easily in TritonX-100 micelles. The fluorescence of PyrCOOH is intense, while 

deprotonation (pKa = 5.22 in micelles) leads to the poorly fluorescent PyrCOO - species. Working 

at pH > 6.5, addition of the lipophilic Zn 2+ complex of the N-dodecyl-N’,N’’,N’’’-trimethylcyclen 

ligand, [Zn(C12-Me3-CYC)] 2+ , results in an intense fluorescence reviving, due to the 

coordination of PyrCOO - to the apical position of the Zn 2+ complex. The process takes place 

exclusively inside micelles (no reviving is observed in water), and it is promoted both by local 

overconcentration of [Zn(C12-Me3-CYC)] 2+ and PyrCOO - , and by the poorly efficient 

competition of water, that inside micelles is less concentrated with respect to the bulk solution. 

[Zn(C12-Me3-CYC)(PyrCOO)] + may be considered as the ON state of an ON-OFF fluorescent 

meter for the lipophilicity of carboxylates. 

Addition of carboxylates results in a decrease of the system IF that is proportional to the quantity 

(and nature) of their carbon content. Fluorescence decrease is due to an intra-micellar 

competition for coordination to the Zn 2+ centre that is efficient only if the R group appended to 

R-COO - is lipophilic enough to result in a significant micellar inclusion of R-COO - . As an 

example, the acetate anion does not influence IF at all, while dodecanoate gives a dramatic 

fluorescence decrease. A correlation between the measurable IF and the observed micellar 

pKa of a series of carboxylic acids may also be put forward. 

[1] a) Y. Diaz Fernandez, A. Perez Gramatges, V. Amendola, F. Foti, C. Mangano, P. Pallavicini 

and S. Patroni, Chem. Commun., 2004, 1650; b) Y. Diaz-Fernandez, F. Foti, C, Mangano, P. 

Pallavicini, S. Patroni, A. Perez-Gramatges and S. Rodriguez-Calvo, Chem. Eur. J., 2006, 12, 

921; c) P. Pallavicini, Y. A. Diaz-Fernandez, F. Foti, C. Mangano and S. Patroni, Chem. Eur. J., 

2007, 13, 178

Interconversion between a supramolecular polymer and a discrete 

octameric species from a guanosine derivatives at surfaces 

Omar Pandoli a , Stefano Masiero a , Silvia Pieraccini a , Paolo Samorì b and Gian Piero Spada a 

a 

Dipartimento di Chimica Organica “A. Mangini”, Alma Mater Studiorum Università di Bologna, 

Via San Giacomo 11, 40126 Bologna, Italy 

b 

ISIS-ULP, 8 allèe Gaspard Monge, 67000 Strasbourg, France & ISOF-CNR, via Gobetti 101, 

40129 Bologna, Italy 

Lipophilic guanosines are unique building blocks which are capable of self-assembling into 

different structures depending on the experimental conditions 1 . In the presence of certain 

cations, they can form G-quartet-based octamers or columnar aggregates depending on the 

concentration of the cation and nucleobase. We have recently proven that it is possible to 

externally trigger in solution a tuneable interconversion between two highly ordered guanine 

based supramolecular motifs, i.e. G-ribbons into G-quartet columns 2 (Figure1). With the final 

goal of obtaining a prototype of a molecular device, we are investigating the transfer of this 

“switch” from solution to a surface. 

In this communication we describe the self-assembly of 1 onto the HOPG surface either as neat 

compound or in the presence of metal cations. The obtained sub-molecularly resolved STM 

results were corroborated by molecular modelling. 

1 

N 

N 

N 

N 

N 

H H 

N N 

N 

N H N 

N 

HN 

N 

N 

N 

N 

N H H 

O H 

O 

N 

N 

N H 

H N 

O 

N 

HO 

H 

NH 

N H 

N 

N 

H 

H 

O N 

O 

N H 

H N 

N 

O N 

H OH 

H 

NN 

N 

N 

N 

N 

HN 

N H 

N 

N 

N 

N 

H H 

N 

H H 

N N 

N 

N H N 

N 

HN 

N 

N 

N 

N 

N H H 

O H 

O 

N 

N 

N H 

H N 

O 

N 

HO 

H 

NH 

N H 

N 

N 

H 

H 

O N 

O 

N H 

H N 

N 

O N 

H OH 

H 

NN 

N 

N 

N 

N 

HN 

N H 

N 

N 

N 

N 

H H 

N 

H H 

N N 

N 

N H N 

N 

HN 

N 

N 

N 

N 

N H H 

O H 

O 

N 

N 

N H 

H N 

O 

N 

HO 

H 

NH 

N H 

N 

N 

H 

H 

O N 

O 

N H 

H N 

N 

O N 

H OH 

H 

NN 

N 

N 

N 

N 

HN 

N H 

N 

N 

N 

N 

H H 

N 

H H 

N N 

N 

N H N 

N 

HN 

N 

N 

N 

N 

N H H 

O H 

O 

N 

N H 

H N 

O 

N 

HO 

H 

H 

N HN 

H 

H 

O N 

O 

N H 

H N 

O N 

H OH 

H 

NN 

N 

N 

N 

N 

HN 

N H 

N 

N 

N 

N 

H H 

Figure 1 

NN 

NN 

NN 

NN 

NN NN NN 

NN 

HH 

HH 

N O 

H 

N O 

N H N O 

H 

N O 

N H N O 

H 

N O 

N H N O 

H 

N O 

N H 

N H 

N H 

N H 

N H 

N H 

N H 

N H 

N H 

NN 

NN 

HH 

HH 

N 

H N 

N H N 

H 

N H N 

H N 

N H N 

H 

H 

OO 

N N 

H N 

N H N 

H 

N H N 

H N 

N H N 

H 

H 

OO 

N 

OO 

OO 

NN 

NN 

HH 

HH 

HH 

HH 

NN 

NN 

NN 

NN 

NN 

NN 

NN 

NN 

PSB 31 

[1] a) G.P. Spada, G. Gottarelli, Chem. Rec 2004, 4, 39-49; b) G.P. Spada, J.T. Davis, Chem. 

Soc. Rev. 2007, 36, 296-313 

[2] S.Pieraccini, S. Masiero, O. Pandoli, P. Samorì, and G.P. Spada, Organic Letters 2006, 8, 

3125-8 

Spectroscopic study of of lasalocid ester with 2-thio-1-ethanol and its 

complexes with monowalent cations 

Radosaw Pankiewicz, Grzegorz Schroeder, Bogumi Brzezinski 

Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, PL-60780 Pozna, Poland 

e-mail: radek@px.pl 

HO 

O 

SH 

O 

OH 

Lasalocid ester with 2-thio-1-ethanol 

Ionophorous antibiotics are a group of bioactive molecules able to transport monovalent and 

bivalentmetal cations across natural and artificial lipid membranes. A polyether antibiotic – 

Lasalocid belongs to this class of compounds. Lasalocid (isolated from Streptomyces 

lasaliensis) is a good anticoccidial agent for cattle, sheep and chicken. In the cell membrane 

lasalocid exchanges metal ions against H + , leading to changes in the pH values and to an 

increase in osmotic pressure inside the cell, which finally leads to the cell death. A new ester of 

lasalocid with 2-thio-1-ethanol has been synthesised and its complexation of monovalent 

cations has been studied by ESI mass spectrometry as well as the 1 H, 13 C NMR and FT-IR 

spectroscopic methods. The ESI-MS spectra show that ester forms stable 1:1 complexes with 

Li + , Na + , K + , Rb + and Cs + cations. With his lasalocid derivative self-assembled monolayers on 

silver and gold have been obtained. Densely packed monolayers have remained stable and 

have not desorbed from the Ag or Au electrode on the potential cycling. The structure of 

ionophores and their complexes with monovalent cations were calculated and visualized by the 

AM1d and PM5 semi-empirical methods. Modification of the monolayers by strong complexation 

agents, like ionophores, allows their application in many areas: in electrodes, bio-sensors or 

affinity chromatography. 

[1] H. Tsukube, Cation – Binding by macrocycles; Marcel–Dekker: New York, 1990, 497 

[2] R. Pankiewicz, G. Schroeder, B. Brzezinski, J. Mol. Struct., 2005, 733 217. 

[3] B. ska, G. Schroeder, T. uczak, P. Przybylski, R. Pankiewicz, M. Betowska- 

Brzezinska, B. Brzezinski, Thin Solid Films, 2006, 515, 152 

[4] R. Pankiewicz, G. Schroeder, B. Brzezinski, unpublished results 

O 

O 

O 

OH 

PSB 32

PSB 33 

Multinuclear NMR, ESI MS and PM5 studies of a new derivative of Gossypol 

with 2-thiophenecarbohydrazide as well as its complexes with monovalent 

cations 

P. Przybylski, R. Pankiewicz, W. Schilf, G. Schroeder, B. Brzezinski 

Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland 

Gossypol, a yellow pigment from cottonseeds, has drawn the attention of many scientists 

because of its interesting physico-chemical properties as well as a number of biological and 

medical applications. The main obstacle in the application of gossypol in medical therapy is its 

relatively high toxicity evoked by the presence of two aldehyde groups in its molecule. The main 

aim of our study is to search for such modifications of gossypol that would be characterised not 

only by low toxicity but also high antibiotic activity related to the ability of complexation of 

monovalent cations. For the purpose of our studies gossypol was extracted from cottonseeds 

(Gossypium Herbaceum) and further converted into its new derivative with 2thiophenecarbohydrazide 

(GHHT) [1]. 

O 

S 

N H 

GHHT 

H N 

(N-imine-N-imine tautomer) 

O H 

H 

O 

O H 

O 

H O 

H O 

N H 

H 

N 

H 

S 

O 

The structure of GHHT and its complexes with Li + , Na + , K + , Rb + and Cs + cations have been 

investigated by multinuclear NMR and PM5 methods. The stoichiometry of the complexes 

formed between GHHT and monovalent cations was determined by the ESI MS method. The 

structures of the complexes are stabilized by three types of intramolecular hydrogen bonds. 

Derivatives of gossypol like its Schiff bases or hydrazones can occur in various tautomeric 

forms [2-3]. The spectroscopic methods have provided clear evidence that GHHT and GHHT in 

its complexes exist in the DMSO-d6 solution in the N-imine-N-imine tautomeric form. The 

structures of the GHHT and its complexes with Li + , Na + , K + , Rb + , and Cs + cations were 

visualized and discussed in details. 

[1] P. Przybylski, W. Schilf, W. Lewandowska, B. Brzezinski, Biopolimers, 2006, 83, 213-225. 

[2] P. Przybylski, G. Schroeder, B. Brzezinski, Phys. Chem. Chem. Phys., 2002, 4, 6137-6143. 

[3] P. Przybylski, G. Schroeder, R. Pankiewicz, B. Brzezinski, F. Bartl, J. Mol. Struct., 2003, 658, 

193-205. 

Polycapsular assembly of exo-ditopic xylyl bridged bicalix[5]arenes with 

long chained ,-alkanediammonium ions † 

PSB 34 

Yoram Cohen, a Sarit Slovak, a Giuseppe Gattuso, b Anna Notti, b Andrea Pappalardo, b 

Melchiorre F. Parisi, b Ilenia Pisagatti, b Sebastiano Pappalardo c 

a School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Ramat Aviv 

69978, Tel Aviv, Israel 

b Dipartimento di Chimica Organica e Biologica, Università di Messina, Salita Sperone 31, 

I-98166 Messina, Italy 

c Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, I-95125 Catania, 

Italy 

The reversible and thermodynamically controlled construction of supramolecular assemblies 

from couples of building blocks displaying complementary molecular affinities is a current 

challenge in noncovalent synthesis. Supramolecular aggregates can be designed by choosing 

topological features and/or chemical surfaces of the interconnecting modules, capable of 

establishing a number of noncovalent intermolecular interactions typical of host–guest and 

coordination chemistry. [1] 

Among potential building blocks, calixarenes are especially attractive for their availability and 

easy chemical alteration at both the wide and narrow rims. We have already shown that p-tertbutylcalix[5]arenes 

in a fixed C5V cone-like arrangement form strong 1:1 inclusion complexes 

with linear alkylammonium ions [2a] and discrete dimeric capsules in the presence of long 

chained ,–alkanediammonium ions. [2b] Here we report that, when two such calix[5]arenes 

are covalently linked via an o-, m-, or p-xylyl spacer at their lower rims as in 1, their cores 

diverge and inclusion of suitable ,–alkanediammonium ions eventually results in the 

formation of discrete bis-endo-cavity complexes and/or capsular assemblies along a polymer 

chain, according to the length of the connector. [3] The assembly modes of 1 to 

,–alkanediammonium ions have been ascertained by 1 H NMR spectroscopy, NMR diffusion 

and ESI MS studies. 

† This work was supported by MiUR (PRIN-2006 project). 

[1] Supramolecular Polymers, 2 nd Edition, A. Ciferri Ed.; CRC Press, Boca Raton, FL. 2005. 

[2] (a) F. Arnaud-Neu,S. Fuangswasdi, A. Notti, S. Pappalardo and M. F. Parisi, Angew Chem., 

Int. Ed. 1998, 37, 112–114; (b) D. Garozzo, F. H. Kohnke, P. Malvagna, A. Notti, S. Occhipinti, 

S. Pappalardo, M. F. Parisi and I. Pisagatti, Tetrahedron Lett., 2002, 43, 7663–7667. 

[3] For preliminary results, see: D. Garozzo, G. Gattuso, F. H. Kohnke, A. Notti, S. Pappalardo, 

M. F. Parisi and I. Pisagatti, A. J. P. White and D. J. Williams, Org. Lett., 2003, 5, 4025–4028.

Chiral chemosensors for enantiomeric recognition of aspartate 

Ana M. Costero a , Manuel Colera a , Pablo Gaviña a , Margarita Parra a , Miklós Kubinyi b , Krisztina 

Pál b , Mihály Kállay b 

a. Department of Organic Chemistry. Universidad de Valencia. Valencia. Spain. b Department of 

Physical Chemistry, University of Technology and Economics. Budapest. Hungary 

Over the last years, the development of chemosensors capable of recognizing anionic species 

have aroused great interest.[1] However, enantioselective recognition and sensing of 

biologically relevant molecules remains a major challenge for host-guest chemists.[2] Although 

several receptors have been developed for chiral dicarboxylates[3] less examples of 

enantioselective chemosensors have been described.[4] In our efforts to develop fluorescent 

chemosensors for dicarboxylates, now we would like to report the preparation of the 

cyclohexane based chiral ligands (+)-1, and (-)-1 and their utility in selective recognition of 

aspartate (2) versus glutamate (3) anions and what is more interesting the enantiomeric sensing 

of L-aspartate versus D-aspartate (Chart1). 

The relative configuration of the 

stereocentres in (+)-1 and (-)-1 was perfectly 

established by NMR techniques and the 

absolute configurations were determined 

from the CD spectra with help of the exciton 

chirality rule.[5] 

In the complexation experiments in DMSO 

the reactions with L-aspartate (L-2), D- 

EtOOC 

NHCS NHR 

NHCS NHR 

aspartate (D-2), L-glutamate (L-3) and D-glutamate (D-3), all as their tetramethylammonium 

(TMA) salts were studied. The stoichometries and equilibrium constants were determined by 

fitting of the UV spectra of equilbrium mixtures. The fluorescence spectrum of (-)-1 substantially 

changes upon the addition of D-2. The band of the pure ligand shifts from 410 nm to longer 

wavelengths and a new band emerge at 495 nm. The latter feature does not appear when L-2 is 

added to the solution. As can be expected, the opposite behaviour can be observed with ligand 

(+)-1. The appearance of the new band may be related to the fomation of an excimer species. 

[1] L. Fabbrizzi, M. Licchelli and G. Labaioli, Coord. Chem. Rev. 2000, 205, 85-108. (b) K. 

Nikura and E.V. Anslyn, J. Am. Chem. Soc. 1998, 120, 8533-8534. (c) P. Anzenbacher, Jr., 

K. Jursíková and J.L. Sessler. J. Am. Chem. Soc. 2000, 122, 9350-9351. 

[2] C.S. Wilcox, Chem. Soc. Rev. 1993, 22, 383-395. 

[3] See for example. (a) A. Ragusa, S. Rossi, J.M. Hayes, M. Stein and J.D. Kilburn, Chem. Eur. 

J. 2005, 11, 5674-5688. (b) S.Rossi, G.M. Kyne, D.L. Turner, N.J. Wells, and J.D. Kilburn, 

Angew. Chem., Int. Ed. 2002, 41, 4233-4236. (c) C.-S. Lee, P.-F. Teng, W.-L. Wong, H.-L. 

Kwong and A.S.C. Chan, Tetrahedron 2005, 61, 7924-7930. 

[4] (a) A.J. Folmer, L. Frantz; M. Vincent and E.V. Anslyn, J. Am. Chem. Soc. 2005, 127, 7986- 

7987. (b) K. Tsubaki, D. Tanima, M. Nuruzzaman, T. Kusumoto, K. Fuji and T. Kawabata, J. 

Org. Chem. 2005, 70, 4609-4616.(c) S. Pagliari, R. Corradini, G. Galaverna, S. Sforza, A. 

Dossena, M. Montalti,L. Prodi, N. Zaccheroni and R.Marchelli, Chem.Eur.J. 2004, 10, 2749- 

2758. (d) W.-L.Wong, K.-H. Huang, P.-F.Teng, C.-S.; Lee, and H.-L. Kwong, Chem. 

Commun. 2004, 384-385. 

[5] N. Berova, N. Nakanishi, in Circular dichroism: principles and applications, Ed. N. Berova, N. 

Nakanishi and R. W. Woody, Wiley-VCH, New York, 2000, 2nd edn., pp. 337-382. 

EtOOC 

EtOOC 

EtOOC 

(+)-1 

(-)-1 

NHCSNHR 

NHCSNHR 

R= 

Chart 1 

- O2C 

- O2C 

H 

H 

NH2 

CO2 - 

(R)-2 L-aspartate 

CO 2 - 

H2N H 

- 

O 2C 

(S)-2 D-aspartate 

NH2 

CO 2 - 

(R)-3 L-glutamate 

PSB 35 

Residual and exploitable fluorescence in micellar self-assembled ON-OFF 

sensors for Copper(II) 

Piersandro Pallavicini, Carlo Mangano, Luca Pasotti and Stefano Patroni 


PSB 36 

ON-OFF fluorescent sensors are said to display full emission (ON state) in the absence of the 

target species, while the emission is nihil (OFF state) when the target species is added. 

However, this is often an oversimplified view. As a matter of fact, when all the receptors 

available in the sensing medium are binding the species to be sensed (e.g. in large excess of 

the target), the read fluorescence may be not zero. Calling I0 the full fluorescence of the system 

(ON state) and IRES the residual fluorescence intensity in the presence of excess target species, 

IRES may be as high as 5-20% of I0. Moreover, in the conditions in which the receptor can 

effectively interact with the target species, the emission of the fluorophore could be not full even 

before that the target species is added (e.g. when the receptor is an amino ligand and the 

working pH is basic). Accordingly, it should be remembered that the ON state displays an 

“exploitable” fluorescence intensity, IEXP, that could be lower than I0. When the sensing system 

is a micellar self-assembly of the Receptor and of the Fluorophore, IRES and IEXP may depend on 

many factors such as R and F shape, R lipophilicity, reciprocal positioning of R and S inside 

micelles, acid/base properties of R, redox properties of its complex with the target.[1] In this 

work we have examined IEXP and IRES for a series of micellar sensors for Cu 2+ , made of pyrene 

(F) plus a R featuring the same amino-amido binding site and different lipophilizing groups. 

IRES is found to depend on the R lipophilicity, that may be quantitatively evaluated by measuring 

the difference between the protonation constants of a model ligand not included in micelle 

(L0H2) and the protonation constants of the micellized lipophilic receptors. 

[1] a) Y. Díaz-Fernandez, A. Perez-Gramatges, S. Rodríguez-Calvo, C. Mangano and P. 

Pallavicini, Chem. Phys. Lett., 2004, 398, 245; b) Y. Diaz-Fernandez, F. Foti, C. Mangano, P. 

Pallavicini, S. Patroni, A. Perez-Gramatges and S. Rodriguez-Calvo, Chem. Eur. J., 2006, 12, 

921-930

PSB 37 

New Anthracene-based cyclophane: complexation of organic cations and 

formation of Diels-Alder adducts. 

Bernardo Masci a , Sara Pasquale a 

a Dipartimento di Chimica, Università di Roma La Sapienza, Piazzale Aldo Moro 5, 00185 

Roma, Italy 

Cyclophane 1 and analogues have been found to strongly bind quaternary ammonium ions and 

alkylviologen cations. Complex formation has been investigated through both 1 H NMR and UVvis 

techniques in CDCl3 or CDCl3- CD3CN solution, moreover the crystal structure has been 

obtained of the pseudo-rotaxane complex 2, featuring a propylviologen axle. Work is in progress 

to introduce bulky end groups as stoppers to obtain the analogous locked systems. The 

presence of the two anthracene units has been exploited to obtain Diels Alder adducts in which 

the shape of the cavity is strongly modified. For instance, both mono- and diadduct formation 

has been observed in the presence or fullerene C60, the anthracene units undergoing reaction in 

9,10-positions. A more extensive investigation has been carried out in the presence of 

tetracyanoethylene that gives a fast reversible reaction at room temperature. In the latter case a 

quantitative analysis of the formation of monoadduct 3 and diadduct 4 has been performed, 

such high values as 3·10 6 L·mol -1 being observed in CDCl3-CD3CN 1:1. The above Diels-Alder 

equilibrium is strongly affected by added alkylviologen guests, that selectively bind 1 rather than 

the adducts. 

t-Bu 

O 

OR 

O 

O 

RO 

1 

t-Bu 

O 

NC 

NC 

NC 

NC 

O 

t-Bu 

t-Bu 

O 

O 

OR 

OR 

RO 

O 

NC O 

NC 

RO 

O 

NC 

O 

t-Bu 

NC 

23 

34 

2 

CN 

CN 

CN 

CN 

O 

t-Bu 

Lariat-type polyamide receptors for anion binding 

Marcin Pawlak a , Adam Sobczuk a , Jarosaw Kalisiak a , Janusz Jurczak a,b 

a 



b 

Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland 

Anion receptors represent quite new field of supramolecular chemistry 1 . Their design and 

synthesis is more demanding task comparing to receptors for cations, due to larger size, variety 

of shapes and lower charge density of anions. One of the ways to solve these problems is a 

design of the tweezer-like receptors which are flexible enough to adjust their structure to the 

guests of various sizes and shapes. A large number of anions receptors were reported so far, 

and most of them has positively charged group as binding sites (i.e. ammonium, pyrydinium 

groups or metal ions). As neutral binding sites hydrogen-bond donors (i.e. amide, thioamides, 

ureas, pyrroles) are employed. 

An interesting application of anion receptors is a preparation of optical sensors, especially those 

able to give visible response in the presence of anions 2 . 

Simple and efficient way of synthesis of macrocyclic, lariat-type polyamide receptors will be 

presented. Structures of studied compounds are presented on Fig.1. Various groups were 

incorporated to these structures (both in intraanular arm and into the macrocyclic ring) in order 

to investigate their influence on anion binding properties. The magnitude of receptor–anion 

interactions were evaluated by 1 H NMR titrations in DMSO, using three typical anions – Cl - , 

PhCOO - , and H2PO4 - in tetrabutylammonium salts form. Moreover, crystal structures of both the 

receptors and their complexes with anions were obtained. 

Nitro group introduced into the intraannular arm, besides amplification of binding strength, also 

acts as a strong chromophore. Due to this fact compounds bearing nitro group reveal a 

colorimetric response in the presence of anions, changing from colorless to different hues of 

yellow. 

O 

N 

O 

O H 

N X 

H 

O H 

N 

O 

N 

H 

H 

N 

O 

Y 

O 

1. X = Ph, C6H4 p-NO2, CH3 

Y = CH, N 

Fig.1. General structures of compounds studied in this work: 1. receptors with amide 

intraannular arm, 2. receptors with O-benzyl intraannular arm. 

[1] F.P. Schmidtchen, M. Berger, Chem. Rev., 1997, 97, 1609-1646 

[2] K. Choi, A. D. Hamilton, Coord. Chem. Rev., 2003, 240, 101-110 

O 

O 

O 

O 

O 

N 

H 

X 

H 

N 

N 

H 

O 

N 

H 

N 

O 

2. X = Ph, C6F5, C6H4 p-NO2 

PSB 38

Amplification of a Molecular Solomon Knot 

PSB 39 

Cari D.Pentecost, Nicholas Tangchaivang, Kelly S. Chichak, Andrea J. Peters, Stuart J. Cantrill 

and J. Fraser Stoddart 

California NanoSystems Institute and Department of Chemistry and Biochemistry, University of 

California Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095, USA 

(cari@chem.ucla.edu) 

The four-noded, two-component link known as the Solomon Knot (SK) has been said to contain 

all of the wisdom of King Solomon. For several centuries, many cultures have adopted this 

emblem to represent knowledge. SKs can be found in many different settings from adorning the 

crowns of African kings to being incorporated into the architecture of university libraries. With 

the advent of new synthetic methodologies that are advancing under the umbrella of templatedirected 

synthesis, chemists are beginning more and more to appreciate the subtleties of 

topologically interesting structures, and have consequently pursued the synthesis of their 

molecular analogues. For example, the complete molecular construction of the Borromean ring 

(BR) topology and its derivatives has been achieved successfully from 18 individual 

components under strict dynamic covalent, coordinative and supramolecular control. In a 

similar fashion, we have recently obtained the SK molecular topology from 12 individual 

components, resulting from mixing Cu(II) and Zn(II) metal templates in a 1:1 ratio, leading to the 

formation of the SKs in preference to the BRs. This finding suggests that, in these dynamic 

mechanically interlocked systems, there is present, under the appropriate conditions, a dynamic 

combinatorial library, from which it is possible, during a crystallization process that is kinetically 

controlled, to amplify (Box) one of the members of the library. 

[1] (a) Chichak, K. S.; Cantrill, S. J.; Pease, A. R.; Chiu, S.-H.; Cave, G. W. V.; Atwood, J. L.; 

Stoddart, J. F. Science 2004, 304, 1308–1312. (b) Cantrill, S. J.; Chichak, K. S.; Peters, 

A. J.; Stoddart, J. F. Acc. Chem. Res. 2005, 38, 1–9.. 

[2] Pentecost, C.D.; Peters, A. J.; Chichak, K. S.; Cave, G. W. V.; Cantrill, S.J.; Stoddart, J. 

F. Angew. Chem. 2006, 45, 4099–4104. 

[3] Pentecost, C.D.; Chichak, K. S.; Peters, A. J.; Cave, G. W. V.; Cantrill, S.J.; Stoddart, J. 

F. Angew. Chem. 2007, 46, 218–222 

Self-Assembled Resorcinarene Monolayers on Gold 

Jade Pettersen a , Mauro Mocerino a , Mark Ogden a , Andrew Ross b , Peter Eadington b 

a Nanochemistry Research Institute, Curtin University of Technology, Perth, Australia. 

b CSIRO Petroleum, Australian Resources Research Centre, Perth, Australia. 

PSB 40 

Self Assembled Monolayers (SAM's) are highly ordered structures formed by the spontaneous 

adsorption of a compound onto a suitable substrate. A variety of sulfur species are known to 

adsorb onto gold, for example physisorbed monolayers are formed in the presence of dialkyl 

sulfides, while chemisorbed monolayers are formed from disulfides, thiols and thioacetates. 1 

Monolayers of simple sulfur functionalised resorcinarenes have been reported by a variety of 

groups and have been used for applications as diverse as coating gold nanoparticles 2 to 

selective sensing devices 3 . Resorcinarenes are typically used as receptors, and are capable of 

complexing with a wide range of guest molecules. 4 Their bowl-like shape and eight hydroxyl 

groups on the upper rim make them an ideal scaffold on which to build more complex 

structures. 

Our goal is to prepare surfaces composed of various fuctionalised resorcinarenes for 

applications in sensing. The work presented will include the synthesis of a variety of 

resorcinarenes as well as recent work involving their use in the formation of self-assembled 

monolayers. 

[1] J. Love, L. Estroff, J. Kriebel, R. Nuzzo, G. Whitesides, Chem. Rev., 2005, 105,1103-1169. 

[2] B. Kim, R. Balasubramanian, W. Perez-Segarra, A. Wei, B. Decker and J. Mattay, Supramol. 

Chem., 2005, 17,173-180. 

[3] J. Faull, and V. Gupta, Thin Solid Films, 2003, 440, 129-137. 

[4] P. Timmerman, W. Verboom, and D. Reinhoudt, Tetrahedron,1996, 52, 2663-2704.

PSB 41 

1,3,5-Tris(2-aminophenyl)benzene: a novel platform for anion receptors. 

Piotr Pitek 

Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, 

Fax: +48-22-8225996; E-mail: ppiatek@chem.uw.edu.pl 

The design, synthesis and application of 1,3,5-Tris(2’-aminophenyl)benzene (1) as a novel, 

rigid, aromatic platform for molecular receptors is presented. This molecular scaffold was 

efficiently prepared via Suzuki-Miyaura cross-coupling reaction of 2-aminophenylboronic acid 

with 1,3,5-triiodobenzene in the presence of Ba(OH)2, Pd(OAc)2 and (2biphenyl)dicyclohexylphosphine. 

1 Alternatively, triamine 1 can be prepared via one-pot 

borylation of 2-bromoaniline and cross-coupling of the resulting boronate ester with 1,3,5triiodobenzene. 

NH 2 

B(OH) 2 

+ 

I 

I 

I 

Pd[P(Ph 3)] 4 

Ba(OH) 2 

Dioxane 

Cy 2P 

1,3,5-Tris(2’-aminophenyl)benzene 1 was used as a molecular platform for the preparation of a 

simple, acyclic, amide-functionalized tripodal receptor 2. The solid-state structure of receptor 2 

reveals that it adopts two arms “up” one “down” (partial cone) conformation. The interaction of 

receptor 2 with various anions was investigated in acetonitril-d6 solution. Those studies have 

shown that 2 display significant affinity for acetate and chloride anions (Ka=2410 and 1540 

respectively). Weak binding interactions were seen for other anions including H2PO4 - and Br - . 

Computation studies suggest that the lowest energy conformation for 2-Cl complex is cone 

conformation which is stabilized by three hydrogen bonding interactions. 

O 

n Pr 

NH 

2 

n Pr 

HN 

HN 

n Pr 

O 

O 

Cl - 

[1] P. Pitek, N. Somiany, Synlett, 2005, 2027-2030. 

O 

n Pr 

NH 

NH 2 

1 

Cl - 

H 2N 

H 2N 

nPr nPr O 

HN O 

HN 

PSB 42 

Ds-oligonucleotide-peptide conjugates featuring peptides from the leucine 

zipper region of Fos as switchable receptors for the oncoprotein Jun. 

Cecilia Portela a , Fernando Albericio b , Ramón Eritja c , Luis Castedo a and José Luis Mascareñas a . 

a Departamento de Química Orgánica y Unidad Asociada al CSIC, Universidade de Santiago 

de Compostela, Campus Sur, 15782 Santiago de Compostela, Spain. 

b Institut de Recerca Biomèdica de Barcelona, Parc Científic de Barcelona, Josep Samitier 1-5, 

E-08028 Barcelona, Spain. 

c Institut de Biologia Molecular de Barcelona, CID-CSIC, Jordi Girona 18-26, E-08034 

Barcelona, Spain. 

The nuclear oncoproteins Fos and Jun are members of the well known familiy of transcription 

factors that bind specific DNA sequences by means of a bZIP motif [1]. These proteins are 

overexpressed in a variety of cancers and proliferative diseases and therefore there is a great 

interest in antagonizing their activity [2]. 

Our studies are focused on the construction of ds-oligonucleotide-peptide conjugates that can 

selectively target the oncoprotein Jun, owing to the presence of a bivalent binding surface 

provided by the peptide and the oligonucleotide (see Figure). 

We herein decribe the synthesis of covalent conjugates between ds-DNA and a 35-aminoacid 

peptidic region of the hydrophobic leucine region of c-Fos and demonstrate that these synthetic 

ds-DNA peptide hybrids exhibit better c-Jun sequestrating properties than either the 

oligonucleotide or the peptide as isolated entities. The recognition strategy allows for switching 

the Jun-trapping capability of the constructs by using appropriately designed ssDNAs. 

[1] Glover, J. N. M.; Harrison, S. C. Nature 1995, 373, 257. 

[2] Angel, P-; Karin, M. Biochimica et Biophysica Acta 1991, 1072, 129.

Crown Ether Functionalized Texaphyrins: Approaches to Improved 

Biolocalization Properties. 

Jonathan L. Sessler a , Andreas Hirsch b , Darren Magda c , Christian Preihs a,b 

a University of Texas at Austin, 1 University Station A5300, Austin, TX 78712 

b University of Erlangen-Nuremberg, Institute of Organic Chemistry II, Henkestrasse 42, 91054 

Erlangen, Germany 

c Pharmacyclics, Inc., 995 East Arques Avenue, Sunnyvale, California, 94085. 

Irrespective of the mode of drug administration, drugs principally have to pass through cell 

membranes to become active in vivo. Therefore, a wide range of functional groups have been 

explored in an effort to improve the uptake properties of known or experimental pharmaceutical 

agents. One such functional group that has attracted attention is the crown ether. Crown 

ethers offer the opportunity to vary the overall polarity, and hence potentially improve the 

biolocalization properties of a putative active agent through coordination of alkali ions and 

tertiary amines. [1], [2] In this presentation the synthesis of motexafin gadolinium (MGd; Xcytrin ® ) 

analogues containing 18-crown-6 moieties will be described. MGd has recently completed 

Phase III clinical testing as an agent for treating brain metastases from non-small cell lung 

cancer (NSCLC) in conjunction with whole brain radiation therapy and is currently in Phase II 

clinical trials as a single agent for the treatment of recurrent NSCLC and this is providing an 

incentive to make and study analogues whose cellular uptake could be modulated via, e.g., 

changes in external conditions. Within the context of this broad conceptual goal the crown ether 

functionalized texaphyrin monomer and dimer shown below were prepared. Their syntheses, 

as well as those of related analogues, will be summarized in this presentation, as will be 

preliminary analyses of their in vitro anticancer activity. 

AcO 

AcO 

OH 

N 

N Gd 

OH 

N 

N 

N 

O 

O 

O 

K + 

O 

Figure 1: Crown-ether functionalized texaphyrins (see also [3]) 

O 

O 

[1] Borrel, M. N.; Fiallo, M.; Veress, I.; Garnier-Suillerot, A.; Biochem. Pharmacol. 1995, 50, 

2069-2076. 

[2] Garnier-Suillerot, A.; Marbeuf-Gueye, C.; Salerno, M.; Loetchu-Tinat, C.; Fokt, I.; Krawczyk, 

M.; Kowalczyk, T.; Priebe, W.; Curr. Med. Chem. 2001, 8, 51-64. 

[3] Sessler, J. L.; Mody, T. D.; Ramasamy, R.; Sherry, A. D. New. J. Chem. 1992, 16, 541-544. 

N 

OH 

OH 

N 

Gd 

N 

N 

N 

OAc 

OAc 

O 

O 

O 

K + 

O 

O 

O 

AcO 

AcO 

N 

N 

N 

Gd 

N 

HO 

HO 

N 

PSB 43 

PSB 44 

Double-threading of two strings through a ring: use of an octahedral metal 

as template 

Fabien Durola, Alexander I. Prikhod’ko (Oleksandr Prykhodko), Jean-Pierre Sauvage 

Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université Louis Pasteur- 

CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 STRASBOURG-CEDEX, France 

Investigation of intermediate [3]pseudorotaxane complexes is an essential step towards metalion 

assisted syntheses of novel mechanically interlocked molecular systems. The 

[3]pseudorotaxane complexes were obtained employing the recently reported biisoquinoline 

chelate (dabiiq) [1,2] , the biisoquinoline-based macrocycle (mb-41) [3] and iron(II)- or cobalt(II)- 

hexa-aqua ions. Following oxidation of the cobalt(II) complex led to the stable diamagnetic 

cobalt(III)-[3]pseudorotaxane. Formation of the heteroleptic species [Fe(dabiiq)2mb-41] 2+ and 

[Co(dabiiq)2mb-41] 3+ was evidenced by means of mass-spectrometry. Both cobalt(III)- and 

iron(II)-[3]pseudorotaxanes were characterised in solution by means of NMR-techniques and 

compared to the corresponding homoleptic complexes [M(dabiiq)3] n+ (M = Fe 2+ or Co 3+ ) and 

related mixed-ligand complexes such as [Fe(bipy)2mb-41] 2+ (bipy = 2,2’-bipyridine). - 

Stacking between aromatic fragments and hindered rotation of the aromatic rings as well as 

flexibility of the oxodiethylene chains belonging to the macrocycle clearly evidence the doublethreaded 

structure of the complexes. 

[1] F. Durola, J.-P. Sauvage and O. S. Wenger, Chem. Comm., 2006, 171-173 

[2] F. Durola, D. Hanss, P. Roesel, J.-P. Sauvage and O. S. Wenger, Eur. J. Org. Chem., 2007, 

125–135 

[3] F. Durola, J.-P. Sauvage and O. S. Wenger, Helv. Chim. Acta, in press.

Simple Isophthalamide Derivatives As Transmembrane Cl - PSB 45 

Transporters 

Paul V. Santacroce, † Jeffery T. Davis, † Mark E. Light, ‡ Philip A. Gale, ‡ José Carlos Iglesias- 

Sánchez, § Pilar Prados, § Roberto Quesada § 

† Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, 

USA, ‡ School of Chemistry, University of Southampton, Southampton, SO17 1BJ, United 

Kingdom, and § Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049 

Madrid, Spain 

The control of ion transport across membranes is a key function in living cells. Chloride, the 

most abundant anion in physiological solutions, is usually transported by a variety of different 

anion transport proteins buried into the membranes, being the largest family of these the ClC 

proteins. Recently, numerous diseases have been associated with malfunction of anion 

channels, notably the cystic fibrosis, the most extended genetic disease among Caucasians. 

Development of molecules or synthetic systems capable of alternative transport might have 

therapeutic potential if a disease is due to malfunction of natural anion channels. Moreover, 

transport is expected to modify the concentration gradients across cell membranes, thus 

potentially inducing physiological effects. 1 

We have synthesized a family of isophthalamide derivatives and studied their anion binding 

properties in solution and their chloride transport activity in model EYPC liposomes. 2 The 

presence of intramolecular hydrogen bonds in 4,6-dihydroxy-isophthalamides stabilizing a synsyn 

conformation of the amide groups resulted in an enhanced anion affinity and a remarkable 

transport activity. Noteworthy, this activity can be modulated as function of the pH. A detailed 

account of this work will be presented within this communication. 

[Cl - ] / mM 

30 

25 

20 

15 

10 

5 

0 

0 50 100 150 200 250 

Time /sec 

pH = 6.4 

pH = 7.8 

pH = 7.4 

pH = 8.0 

pH = 9.1 

Figure 1. Left: Representation of a 4,6-dihydroxy-N,N`-butylisophthalamide receptor 

transporting chloride anion through the lipidic membrane. Right: transport activity displayed by 

this compound as function of the pH. 

[1] For a recent review on synthetic anion transporters see: A. P. Davis, D. N. Sheppard, and B. 

D. Smith, Chem. Soc. Rev. 2007, 36, 348-357. 

[2] P. V. Santacroce, J. T. Davis, M. E. Light, P. A. Gale, J. C. Iglesias-Sánchez, P. Prados, and 

R. Quesada, J. Am. Chem. Soc. 2007; 129, 1886-1887. 

PSB 46 

Diphosphonate-macrocycle Conjugates – Probe Complexes for a Sorption 

Investigation 

T. Vitha, V. Kubíek, I. eho, P. Hermann, Z. I. Kolar, H. T. Wolterbeek, J. A. Peters, I. Lukeš 

Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, 

Albertov 6, 12843, Prague, Czech Republic 

Geminal diphosphonates are strongly adsorbed on surfaces of many inorganic oxides and 

salts.[1,2] Their strong sorption on the surface of hydroxyapatite (HA) – a main inorganic 

component of bones predeterminates their most important application – treatment of diseases 

connected with disorder of calcium metabolism (osteoporosis, Paget disease and others). 

We have synthesized and studied three ligands, combining a diphosphonic acid group with a 

DOTA-core – BPAMD [3], BPAPD and BPPED. Presence of a DOTA core makes these 

compounds extremely suitable for radiochemical studies as radiolabeling proceeds via 

complexation. Radiolabeled Tb(III) complexes of the ligands were used for study of an 

interaction between bisphosphonate acid group and HA surface. 

Tb(III)-BPAPD complex has also been used as a probe for a study of the interaction between 

HA and a group of other diphosphonates via competitive sorption. To describe the competition 

of two diphosphonates during sorption, a physicochemical model based on the Langmuir and on 

the Langmuir–Freundlich adsorption isotherm was evaluated and successfully applied. 

HOOC 

N N 

O 

N 

PO3H2 PO3H2 HOOC 

N N 

O 

N 

PO3H2 PO3H2 HOOC 

N N 

O OH 

P PO3H2 PO3H2 HOOC 

N N 

COOH HOOC 

N N 

COOH 

HOOC 

N N 

COOH 

BPAMD BPAPD BPPED 

[1] H. Fleisch, Bisphosphonates in Bone Disease, 4th ed., Academic Press London, 2000 

[2] R. L. Hilderbrand, The Role of Phosphonates in Living Systems, CRC Press, 1983 

[3] V. Kubíek, J. Rudovský, J. Kotek, P. Hermann, L. Vander Elst, R. N. Muller, Z. I. Kolar, H. 

T. Wolterbeek, J. A. Peters, I. Lukeš, J. Am. Chem. Soc., 2005, 127, 16477–16485

PSB 47 

Dynamic Combinatorial Chemistry Applied to the Synthesis of Cyclopeptidic 

Receptors for Anion Recognition in Aqueous Solutions 

Zaida Rodriguez-Docampo, a Carsten Reyheller, b Stefan Kubik b and Sijbren Otto a 

a, Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, UK. 

b, Fachbereich Chemie-Organische Chemie, Technische Universität Kaiserslautern, Erwin- 

Schrödinger Strae, D-67663, Germany. 

e-mail: zr212@cam.ac.uk 

Dynamic combinatorial chemistry has proven to be a powerful tool in the design of complex 

molecular receptors [1]. The application of disulfide exchange dynamic combinatorial chemistry 

to modified cyclopeptides of the efficient receptor 1 [2] has led to the isolation of a new series of 

receptors for anions in aqueous mixtures [3]. Structural and thermodynamic data of the binding 

properties of the receptor 2c has demonstrated that the hydrophobic interactions within the 

receptor reinforce the ligand complexation [4]. Taking advantage of this special feature of the 

system and introducing more covalent linkages between the two cyclopeptide rings to get more 

preorganised receptors, an enhancement of anion coordination is expected. With this purpose, 

cyclopeptide 3 has been synthesised and screened with several spacers and anions. Some 

preliminary promising results have been obtained. 

The challenge of this project is not only to synthesise new efficient and selective receptors for 

anions but also make them more soluble in water to make the recognition processes compatible 

with biological systems. 

O N O 

N 

NH 

HN 

N 

O 

O 

N 

N 

O N N 

H 

O 

1 

N 

O 

N 

HN 

O 

O 

H 

N 

N 

O 

N 

O 

NH 

N 

N 

O 

X 

2a, X= 

2b, X= 

2c, X= 

N 

HN 

O 

O 

N 

N 

S S 

OH 

S S 

S S 

N 

H 

O 

N 

O 

N 

O 

NH 

N 

O 

O 

HN 

O 

N 

N 

N 

O 

N 

N 

H 

O 

N 

S 

NH 

N 

S 

O 

O 

3 

O 

HN 

O 

S 

N 

S 

N 

O 

H 

N 

N 

O 

N 

O 

NH 

N 

N 

O 

[1] For a recent review see: PT. Corbett, J. Leclaire, L. Vial, KR. West, JKM. Sanders, 

S. Otto. Chem Rev. 2006, 106, 3652-3711. 

[2] S. Kubik, R. Goddard, R. Kirchner, D. Nolting, J. Seidel. Angew. Chem. Int. Ed. 2001, 40, 

2648-2651. 

[3] S. Otto, S. Kubik. J. Am. Chem. Soc. 2003, 125, 7804-7805. 

[4] Z. Rodríguez-Docampo, S.I. Pascu, S. Kubik, S. Otto. J. Am. Chem. Soc. 2006, 128, 11206- 

11210. 

A [2]-Rotaxane from a Nickel Active-Metal Template 

Pauline Fitzsimmonds, Stephen. M. Goldup, Nicholas. D. Gowans, David. A. Leigh and Vicki E. 

Ronaldson. 

School of Chemistry, University of Edinburgh, the King’s Buildings, West Mains Road, 

Edinburgh, EH9 3JJ. (v.e.ronaldson@sms.ed.ac.uk) 

Recently we have developed a strategy for the synthesis of rotaxanes in which the metal plays 

a dual function: (i) acting as a template for entwining or threading the precursors; and (ii) 

catalysing covalent bond formation between the reactants through the cavity of the macrocycle 

to form a rotaxane [1]. 

Following a literature precedent for the Ni(II)-mediated homocoupling of acetylenes [2], we have 

adapted this methodology to produce a nickel ‘active-metal template’ rotaxane synthesis. 

(Scheme 1). 

Scheme 1. A Ni(II)-mediated homocoupling to give a [2]-rotaxane. 

PSB 48 

The reaction gives high yields (up to 72%) with a 2:1 ratio of stopper to metal-macrocyclic 

complex, making it highly atom efficient. In addition, Ni(II) reagents are cheap, relatively air 

stable and easy to remove following reaction. The reaction has been shown to be tolerant to 

both propargylic ethers and aryl alkynes, proving its versatile nature and the potential for 

extension to heterocouplings, which we plan to investigate as the next step. 

[1] V. Aucagne, K. D. Hänni, D. A. Leigh, P. J. Lusby and D. B. Walker, J. Am. Chem. Soc., 

2006, 128, 2186-2187. 

[2] E. H. Smith and J. Whittall, Organometallics, 1994, 13, 5169-5172.

PSB 49 

On Sokolov’s approach to a Molecular Knot using Ring Closing Metathesis 

Pirmin Rösel, a Christopher Smith, a Catherine E. Housecroft, a Edwin C. Constable a 

a Department of Chemistry, Spitalstrasse 51, 4056 Basel, Switzerland 

We all meet knots in our daily lives and most of us are fascinated with their unique topology. 

More importantly, knots are also found in proteins and DNA and hence play an important role in 

nature [1]. 

An early approach towards a molecular knot is Sokolov’s application of an octahedral 

tris(chelate) template [2]. 

We synthesised the homoleptic iron(II)-complex 1 which has terminal alkene functionalities. 

NMR spectroscopic and ESI-MS measurements confirm the successful trifold intramolecular 

Ring Closing Metathesis. Our current efforts are concentrated on the separation and 

characterisation of 3 and its isomers. 

[1] Molecular Catenanes and Knots; Sauvage, J.-P., Dietrich-Buchecker C. Eds.; Wiley: New 

York, 1999 and ref. herein. 

[2] V. I. Sokolov, Russ. Chem. Rev. 1973, 42, 452. 

New route for the C-functionalisation of macrocyclic polyamines 

Yoann Rousselin, Franck Denat, Frédéric Boschetti, Roger Guilard 

Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB - UMR CNRS 5260) 

9, avenue Alain Savary, BP 47870, 21078 DIJON - FRANCE 

Cyclic tetraamines have received considerable attention owing to their coordination properties 

towards various metal cations. The increasing need of finely tuned macrocycles requires the 

development of new synthetic tools for the preparation of such ligands. The research in this field 

has been focused on the synthesis of bifunctional chelating agents (BFCs or BCAs) based on a 

cyclic amine containing two kinds of functional groups, one for the coordination of the guest, 

another one for the anchoring of the macrocycle onto a solid support or an antibody. The 

attachment of one functional group on the carbon skeleton is particularly advantageous since 

the four secondary amines are available for further functionalisation with chelating arms. 

Recently, we have proposed a very convenient route for the synthesis of a wide range of Cfunctionalised 

macrocycles using bisaminal intermediates. 1,2 However, this approach still implies 

the use of a biselectrophilic reagent containing the desired functional group on a carbon atom. 

Here we would like to present a new method of C-functionalisation of linear polyamines 

proceeding through the use of chloroacetaldehyde and benzotriazole (Bt) to help in the 

cyclization reaction. The displacement of the benzotriazole group by various nucleophiles gives 

access to new C-functionalised cyclens and [13]aneN4. 

N 

N 

H 

R 

Me 

R = H, Me 

n = 0, 1 

N 

N 

H 

chloroacetaldehyde 

benzotriazole 

N 

N 

R 

n = 0, 1 

N 

N 

Me 

Bt 

Nucleophilic agent 

N 

N 

R 

n = 0, 1 

N 

N 

Me 

Nu 

acidic condition 

[1] F. Boschetti, F. Denat, R. Guilard, H. Ledon, H. Chollet and J.L. Babouhot WO 03/029228. 

[2] F. Boschetti, F. Denat, E. Espinosa, J.-M. Lagrange and R. Guilard, Chem. Commun., 2004, 

588-589. 

NH 

NH 

n = 0, 1 

HN 

HN 

Nu 

PSB 50

Preparation and Properties of Rotaxanes Formed by Dimethyl-β - 

cyclodextrin and Oligo(thiophene)s with β-Cyclodextrin Stoppers 

Kazuya Sakamoto, Yoshinori Takashima, Hiroyasu Yamaguchi, Akira Harada 

Department of Macromolecular Science, Graduate School of Science, Osaka University, 1-1, 

Machikaneyama-chou, Toyonaka, Osaka 560-0043, Japan 

Email: harada@chem.sci.osaka-u.ac.jp 

Polythiophenes and oligothiophenes have 

attracted widespread interest due to their 

applications as single-molecule electronics 

devices and light-emitting diodes. Recently, 

conjugated poly(rotaxane)s, in which the 

conjugated polymer backbone is covered at 

the molecular level by wrapping macrocyclic 

molecules have been studied as insulated 

molecular wires by many research groups. 

We also reported the formation and crystal 

structure of the β-cyclodextrin (β- 

CD)−bithiophene inclusion complex and 

polymerization of the corresponding inclusion 

complexes in a selective way to give pseudopoly-(rotaxane)s. 

1 

Herein, we have prepared 2,6-di-O-methylβ-CD 

(DM-β-CD)−oligothiophene based 

[2]rotaxanes (2T-[2]rotaxane, 3T-[2]rotaxane) 

and [3]rotaxanes (4T-[3]rotaxane, 6T- 

[3]rotaxane) shown in Figure 1 and investigate 

their photophysical properties. The 

fluorescence maximum wavelength of 

rotaxane shifted to a longer wavelength with 

an increase in the conjugation length. The 

fluorescence intensity of rotaxane in aqueous 

media was higher than that of dumbbell 

shaped molecules (without DM-β-CD on axis). 

The increase in the fluorescence intensities of 

rotaxane is caused by the suppression of 

intermolecular interaction, indicative of the 

effect of insulated oligothiophene with DM-β- 

CD. The inclusion ratio of rotaxanes 

influenced their quantum yields in aqueous 

solutions. 

PSB 51 

Figure 1. Chemical structures of DM-β-CDoligothiophene 

rotaxanes with β-CD stoppers. 

Figure 2. Fluorescence spectra of 2T- 

[2]rotaxane (a), 2T-dumbbell (b), 3T-[2]rotaxane 

(c), 3T-dumbbell (d), 4T-[3]rotaxane (e), and 6T- 

[3]rotaxane (f), in H2O, 15µM, λex=378 nm (2T), 

407 nm (3T), 438 nm (4T), 449 nm (6T). 

[1] (a) Takashima, Y.; Oizumi, Y.; Sakamoto, K.; Miyauchi, M.; Kamitori, S.; Harada, A. 

Macromolecules 2004, 37, 3962-3964. (b) Takashima, Y.; Sakamoto, K.; Oizumi, Y.; 

Yamaguchi, H.; Kamitori, S.; Harada, A. J. Inclusion Phenom. Macrocycl. Chem. 2006, 56, 45- 

53. 

[2] Sakamoto, K.; Takashima, Y.; Yamaguchi, H.; Harada, A. J. Org. Chem. 2007, 72, 459-465. 

PSB 52 

Host-Guest Chemistry of Tetramethoxy Resorcinarene Crowns: Bis-Crown-5 

vs. Tribenzo-Bis-Crown-6 

Kirsi Salorinne and Maija Nissinen 

Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, 40014 

JYU, Finland 

Calixcrowns 1 are a widely studied class of compounds due to their abilities to complex cations 

and act as receptors or ionophores, in which both the properties arising from the crown ether 

unit and the calixarene skeleton contribute to the host-guest chemistry of these compounds. We 

wanted to further explore this family of compounds and introduced resorcinarene as the 

platform. As opposed to calixarene, the phenolic hydroxyl groups are situated on the upper rim 

of resorcinarene, which enables the crown ether bridges to form on the open end of the cavity 

and, therefore, makes the resorcinarene bowl available to take part in guest binding. We chose 

tetramethoxy resorcinarene 2 as the platform because it provides two sites for crown ether 

bridging creating two crown “pockets” for guest inclusion. 

The selectivity toward guest binding is determined by the functionality at the crown ether unit, 

which prompted us to design two different resorcinarene bis-crown ethers: Bis-crown-5 3 (BC5) 

and tribenzo-bis-crown-6 (TBBC6) (see figure below). The complexation properties toward 

alkali metal cations (K + , Rb + and Cs + ) were studied by means of 1 H NMR spectroscopic titration, 

picrate extraction and crystallographic methods. 

O 

MeO 

MeO 

O 

R R 

R 

R 

O 

OMe 

OMe 

O 

BC5 = 

TBBC6 = 

O O O O O 

O 

O 

O O 

O O 

Figure. Schematic presentation of tetramethoxy resorcinarene bis-crown ethers BC5 and 

TBBC6 (R=C2H5). 

[1] (a) R. Ungaro, In Calicarenes in Action; L. Mandolini, R. Ungaro, Eds.; Imperial College 

Press: London, England, 2000. (b) K.R. Sharma and Y.K. Agrawal, Rev. Anal. Chem. 2004, 23, 

133-158. (c) C. Alfiere, E. Dradi, A. Pochini, R. Ungaro and G.D. Andreetti, J. Chem. Soc.. 

Chem. Commun. 1983, 1075-1077. 

[2] M.J. McIldowie, M. Mocerino, B.W. Skelton and A.H. White, Org. Lett. 2000, 2, 3869-3871. 

[3] K. Salorinne and M. Nissinen, Org. Lett. 2006, 8, 5473-5476.

PSB 53 

New chromogenic sensors using hybrid organic-inorganic nanomaterials 

Elena Aznar a , Pilar Calero a , Carmen. Coll a , Maria Dolores Marcos a , Ramón Martínez-Máñez a , 

Félix Sancenón a , Juan Soto a , Pedro Amorós b , Jose Manuel Lloris c , Celia Silvestre c 

a) Instituto de Química Molecular Aplicada (IQMA), Universidad Politécnica de Valencia, 

Camino de Vera s/n, 46022, Valencia, Spain 

b) Institut de Ciència dels Materials (ICMUV), Universitat de Vàlencia, 46071, Vàlencia, Spain. 

c) Instituto Tecnológico de la Construcción (AIDICO), Avenida Benjamín Franklin 17, 46980, 

Paterna (Valencia), Spain. 

The blending of supramolecular chemistry with material science is in recent times leading to the 

preparation of hybrid organic-inorganic materials that opens new and exciting possibilities of 

applications in the field of molecular sensing. Some advanced examples have recently been 

reported based on the use of biomimetic concepts and gated supramolecular chemistry in 

nanomaterials. [1] Some examples developed in our research group were based on the 

formation of nanometer-sized binding pockets by anchoring suitable binding sites to the surface 

of preorganised solids in order to create sensing ensembles for the chromo-fluorogenic sensing 

of target species. Also recently we have reported for the first time the design of a colorimetric 

probe by using nanoscopic gate-like scaffoldings. [2,3] Inspired by these findings we report 

herein some novel hetero-supramolecular sensing systems based on nanoscopic scaffoldings 

for the selective and sensitive colorimetric signalling in water of borate and fatty acids. 

Borate sensing is based on the use of molecular nanoscopic gate-like ensembles as advanced 

chromo-fluorogenic sensory materials. The concept involves the development of molecular 

gate-like systems (on a MCM41 mesoporous support containing a polyalcohol anchored to the 

pore outlets) that is selectively closed in the presence of borate. Borate coordination inhibits the 

delivery of a dye (Ru(bipy)3 2+ ) in the inner pores of the mesoporous scaffolding therefore 

signalling its presence. Also inhibition of dye delivery and colorimetric recognition has been 

achieved using a polarity-controlled gate-like structure on mesoporous materials for the 

signalling of fatty acids in aqueous environments. 

A carboxylate sensing system in water has also been prepared by the grafting of 

spirobenzopyrane derivatives as signalling subunit and ureas and thioureas as binding site into 

silica nanoparticles (20 nm of diameter). The coordination of long-chain carboxylates with the 

urea/thiourea binding sites leads to the formation of a highly hydrophobic monolayer that 

stabilized the neutral form of the spirobenzopyran and induced a colour change from violet 

(cationic form of the spirobenzopyran) to light pink (neutral form of the spirobenzopyran). 

[1] A. B. Descalzo, R. Martínez-Máñez, F. Sancenón, K. Hoffman, K. Rurack, Angew. Chem. 

Int. Ed., 2006, 45, 5924-5948. 

[2] See for instance: M. Comes, G. Rodríguez-López, M. D. Marcos, R. Martínez-Máñez, F. 

Sancenón, J. Soto, L. A. Villaescusa, P. Amorós, D. Beltrán, Angew. Chem. Int. Ed., 2005, 44, 

2918-2922. A.B. Descalzo, K. Rurack, H. Weibhoff, R. Martínez-Máñez, M.D. Marcos, P. 

Amorós, K. Hoffmann, J. Soto, J. Am. Chem. Soc., 2005, 127, 184-200 

[3] R. Casasús, E. Aznar, M. D. Marcos, R. Martínez-Máñez, F. Sancenón, J. Soto, P. Amorós, 

Angew. Chem. Int. Ed., 2006, 45, 6661-6664. 

PSB 54 

Computational Studies on the Cooperative AND Ion-Pair recognition by 

Heteroditopic Calix[4] diquinone Receptors. 

Sérgio Santos a , Michael D. Lankshear b , Paul D. Beer b and Vítor Félix a 

a 

Departamento Química, CICECO, Universidade de Aveiro, 3810-193 Aveiro, Portugal. 

b 

Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks 

Road, Oxford, OX1 3QR, U.K. 

A computational study on the recognition of MX alkali 

halide ion-pairs (M = Li + , Na + , K + , Rb + , Cs + and NH4 + and 

X=Cl - , Br - and I - ) by five novel heteroditopic 

calix[4]diquinone receptors (see right) is hereby 

reported. 1 These synthetic receptors allow cooperative 

binding to the associated ion-pairs, revealing an 

unprecedented AND recognition phenomena, in which 

the receptors display no affinity towards the free ions, but 

bind strongly the ion-pairs. A first insight into the binding 

interaction was obtained through gas-phase 

conformational analyses of both free and complexed 

receptors, and conventional solution molecular dynamics. 

Succinctly results showed that all receptors have enough 

flexibility to accommodate different sized ion-pairs; however larger macrocycles prefer larger 

ion-pairs. Subsequently, the relative binding free energies (G) were obtained by means of 

thermodynamic integration calculations. Generally, the theoretical G values are in excellent 

agreement with those derived from the experimental binding constants, thus validating our 

calculations. The insertion mechanism of the ion-pairs into the receptors was investigated by 

means of Potentials of Mean Force. It was shown that the contact ion-pair interaction occurs 

through a cone conformation of the calix entity of the receptor, so as to allow - stacking 

interactions between one 

diquinone unit and the 

isophthalamide fragment, which 

is adopted after folding both 

diquinone rings from a 1,3 

alternate into a cone 

MX 

conformation (see left). In this 

binding arrangement, the anion 

and cation binding sites are 

arranged in close proximity 

allowing the AND gate 

recognition process. The 

enhanced affinity revealed by -NO2 containing receptors 2 and 4, relative to corresponding 1 

and 3, investigated by DFT NBO calculations, was attributed to the delocalization of the charge 

distribution due to the presence of that additional electron withdrawing group, leading to an 

increased acidity of the hydrogens of the amide clefts. 

[1] Lankshear, M. D.; Cowley, A. R.; Beer, P. D., Chem. Commun. 2006, 612-614. 

Acknowledgements: Sérgio M. Santos thanks FCT – Fundação para a Ciência e Técnologia – 

for the financial support under the PhD scholarship SFRH/BD/29596/2006.

Molecular inclusion of organometallic sandwich complexes within hybrid 

cavitand-resorcin[4]arene receptors 

María Ángeles Sarmentero, a Guzmán Gil, a Pablo Ballester a,b . 

a Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 

Tarragona, Spain. b ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain. 

The confinement of guests within molecular vessels modifies their chemical behaviour. While 

included, guests can undergo reactions with significant rate enhancement and improved product 

selectivity.[1] On the other hand, the inclusion of redox-active guests, generally tends to slow 

down the kinetics of heterogeneous electron transfer reactions.[2] The complete encapsulation 

of cobaltocenium cations in non polar solvents has been achieved, mainly through cation- 

interactions, using non-covalent dimeric and hexameric capsules [3]. 

In this communication we describe the efficiency of simple and neutral hybrid cavitandresorcin[4]arene 

hosts for the molecular inclusion of positively charge organometallic sandwich 

complexes. The complexation process has been studied by 1 H-NMR and cyclic voltammetry 

techniques in organic solvents. 

The obtained results point out that the aromatic cavities present in the vase conformation of 

these receptors are electronically rich and capable of including organometallic sandwich cations 

by offering CH- and - interactions. Furthermore, the receptors show a remarkable size and 

charge selectivity in the molecular inclusion of the redox active guests. 

R 2 HN 

R 2 HN 

H 4 

H 3 

O 

H 9 

O 

H1 

H 5 

Co 

R 2 HN 

H7 

NHR 2 

O O 

H10 R 1 

H2 R 1 

R 1 H6 R 1 =CH2CH3 

R 1 

H8 OH HO 

Ru 

O 

H 9 

O 

R 2 =H; 

R 2 =COCH2CH3; 

NHR 2 

NHR 2 

PSB 55 

[1] a) D. Fiedler, D. H. Leung, R. G. Bergman and K. N. Raymond, Acc. Chem. Res., 2005, 38, 

349-358, b) M. Fujita, M. Tominaga, A. Hori and B. Therrien, Acc. Chem. Res., 2005, 38, 

369-378. 

[2] C. M. Cardona, S. Mendoza and A. E. Kaifer, Chem. Soc. Rev., 2000, 29, 37-42. 

[3] a) D. Ajami, M. P. Schramm, A. Volonterio and J. Rebek, Jr., Angew. Chem. Int. Ed., 2007, 

46, 242-244. b) I. Philip and A. E. Kaifer, J. Org. Chem., 2005, 70, 1558-1564. 

PSB 56 

Subcomponent Exchanges in Self-Assembled Metallo-Organic Structures 

David Schultz, Jonathan R. Nitschke 

Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 

Geneva 4, Switzerland 

Using the principles of dynamic self-assembly we can build structures that are held together by 

two kinds of reversible bonds, covalent (C=N) and coordinative (NM) bonds, giving the 

possibility for dynamic sorting and substitution to occur. 

Selectivity imposed by metal ions was used to simplify dynamic combinatorial libraries of ligand 

subcomponents. We have shown that two different copper(I) complexes may self-assemble 

quantitatively from a common pool of subcomponents in each other’s presence.[1] 

Simultaneous templating involving the cooperative action of Cu I and Fe II allowed us to simplify 

an even more complex mixture of compounds.[2] 

Substitution of ligand subcomponents in such metallo-organic complexes is ruled by several 

factors that can be used to quantitatively and selectively transform one structure into another. 

The difference in pKA between the protonated amines was found to drive substitution by 

favoring the displacement of the protonated form of the weaker acid and the incorporation of the 

deprotonated form of the stronger acid.[4] 

Another way to drive subcomponent substitution is provided by the substituent electronic 

effects. We have shown the existence of a linear free energy relationship connecting the 

electron-donating character of an anilines’ para-substituent, as measured by the Hammett para 

parameter, to that aniline’s ability to compete with unsubstituted aniline to form imines.[3] 

These results allowed us to design the three-step transformation of a series of copper 

containing structures shown below. Electronic effects combined with the chelate effect allowed 

each step to proceed in predictably high yield. One interest of this experiment is that the 

topology of the product is changed at each step. 

O 

N 

N Cu 

N 

N 

+ 

O 

NH 2 

N N 

Cu 

N N 

+ 

NMe 2 

NMe 2 

O O 

NH2 N N 

Cu 

N N 

+ 

N 

N Cu 

N 

N 

+ 

99.5% 

NH2 97% 

H2N NH2 93% 

NMe2 N 

N Cu 

N 

N 

+ 

[1] David Schultz and Jonathan R. Nitschke, Proc. Natl. Acad. Sci. USA 2005, 102, 11191- 

11195 

[2] David Schultz and Jonathan R. Nitschke, Angew. Chem. Int. Ed. 2006, 45, 2453-2456 

[3] David Schultz and Jonathan R. Nitschke, J. Am. Chem. Soc. 2006, 128, 9887-9892 

[4] David Schultz and Jonathan R. Nitschke, Chem. Eur. J. 2007, in press. 

O 

O

PSB 57 

Removal of heavy metal ions from waste waters by molecular recognition 

technology 

Giuseppe Arena a , Elisa Longo a , Carmelo Sgarlata a , Richard A. Bartsch b , Dongmei Zhang b and 

Yanfei Yang b 

a 

Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, 95125 Catania, Italy 

b 

Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, 79409-1061, 

USA 

Selective transport of metal ions through polymeric inclusion membranes (PIM), containing 

macrocyclic receptors, is an environmentally friendly and cost-effective technology for the 

removal of metal ions and pollutants from waste waters [1]. In this work, some calix[4]arene 

receptors, blocked in the cone conformation and functionalized with two N-(X)sulfonyl 

carboxamide groups on the lower rim, are proposed as carriers to be incorporated into PIMs. 

Preliminary studies of the complexing properties for related ligands, based on solvent extraction 

experiments, indicated a high complexation efficiency towards some heavy metal cations, such 

as Pb 2+ , Cd 2+ and Hg 2+ [2]. To obtain a better understanding of the complexing features of these 

systems, we have carried out a thermodynamic investigation by means of UV-Vis 

spectrophotometric titrations in acetonitrile. The data analysis, performed by a multivariate and 

multiwavelength treatment of the data, has allowed us to determine the complex species formed 

in solution, as well as their stability constants. The carriers with the best efficiency and 

selectivity have been incorporated into PIMs and employed as tools for the removal of target 

ions from an aqueous source phase into an aqueous receiving phase. Experiments have been 

conducted for i. solutions containing single cations species (to measure the transport efficiency 

of the incorporated ligands towards each metal ion) and ii. mixtures of metals ions (to evaluate 

the selectivity of the carriers towards the target ions). The UV-Vis and transport experiments 

were carried out with and without ionic strength adjustment to probe its effects on the 

complexing properties and transport efficiency of the investigated systems. 

Me 

O 

O O 

R R 

O 

Me 

1 

2 

R 

CH2C(O)NHSO2Ph CH 2C(O)NHSO 2C 6H 4-4-NO 2 

[1] G. Arena, A. Contino, A. Magrì, D. Sciotto and J. D. Lamb, Supramol. Chem., 1998, 10, 5- 

15. 

[2] G. G. Talanova, H. S. Hwang, V. S. Talanov and R. A. Bartsch, Chem. Commun., 1998, 419- 

420; G. G. Talanova, H. S. Hwang, V. S. Talanov and R. A. Bartsch, Chem. Commun., 1998, 

1329-1330. 

PSB 58 

Synthesis, metal ion complexation and polymric membrane ion-selective 

electrode studies of some novel calix[4]arene-crown macrocycles 

M. Shamsipur a , M. Taghdiri b , M. K. Rofouei b , S. Sahari a , K. Alizadeh a , Z. Asfari c , M. Leroy c 

a Department of Chemistry, Razi University, Kermanshah, Iran 

b Department of Chemistry, Tarbiat Moallem University, Tehran, Iran 

c Laboratoire de Chimie Analytique, UMR 7178 ULP/CNRS/IN 2P3 (LC4) ECPM, 25 rue 

Becquerel, F-67087, Strasburg Cedex, France 

Five novel calix[4]arene-crown macrocycles L1-L5 (Scheme 1) were successfully synthesized 

and fully characterized [1]. The complexation of these ligands with several alkali, alkaline earth 

and transition metal ions in acetonitrile solution was investigated using conductometric, 

spectrophotometric, 1 H-NMR and 133 Cs-NMR methods. Depending on the nature and size of 

metal ions used and structural properties of the calix[4]arene-crown macrocycles, different 

metal-to-ligand stoichiometries of 1:1, 2:1 and 3:2 were confirmed in solution. The stability 

constants of the resulting complexes were evaluated from computer fitting of the corresponding 

conductance, absorbance or chemical shift versus mole ratio data. 

To obtain more information about the conformational changes of the calix[4]arene-crowns upon 

complexation with some metal ions, the molecular structures of free ligands and their metal ion 

complexes were built with the Hyperchem program version 7.0 [2]. The structure of free ligands 

were optimized using the 6-31G* basic set at the restricted Hartree-Fock (RHF) level of theory. 

The optimized structures of ligands were then used to find out the initial structure of their metal 

ion complexes. Finally, the structures of the resulting complexes were optimized using the 

Lan12mb basis set at the RHF level of theory, using the Gaussian 98 program. Sample results 

are shown in Scheme 2. 

Based on the selectivity results obtained from complexation studies, some of the ligands were 

used as suitable ionophores for the preparation of PVC-membrane ion-selective electrodes for 

the corresponding metal ion-ligand systems. An interesting example is a highly selective and 

sensitive potentiometric sensor with a limit of detection of 1.0 10 -6 M for barium ion based on 

ligand L2. The details of the results obtained on the complexation and polymeric membrane ionselective 

electrode studies of the ligands L1-L5 will be discussed in this seminar. 

L1 L2 L3 L4 L5 

Scheme 1. Structures of ligands L1-L5 

Scheme 2. Optimized structures of free L2 and its Ba 2+ 

complex 

[1] Z. Asfari, P. Thuery, M. Nierlich, J. Vicens, Tetrahedron Lett., 1999, 40, 499-502. 

[2] M. Shamsipur, M. Hosseini, K. Alizadeh, M. F. Mousavi, A. Garau, V. Lippolis, A. Yari, Anal. 

Chem., 2005, 77, 276-283.

PSB 59 

Supramolecular mixed complexes of the crown-containing ditopic receptors 

with organic acids and metal cation. 

O.A. Fedorova, E.Yu. Chernikova, Yu.V. Fedorov, E.N. Gulakova, 

M.M. Mashura, N.E. Shepel' and M.V. Alfimov 

a Photochemistry Center of Russian Academy of Sciences, Novatorov str., 7a, Moscow, 117421, 

Russia. E-mail: fedorova@photonics.ru 

Compared to the large number of chromo/fluororeceptors for cations and anions, the 

development of artificial receptors for organic acids is quite limited in spite of their importance 

for biochemical analysis. In designing of the receptors which able to form multicomponent 

molecular assemblies with ammonium cations, carboxylic and amino acids we used crowncontaining 

hetarylphenylethenes possessing two binding centers of different nature. The main 

interactions involved in its recognition are hydrogen bonding, metal cation binding and steric 

complementary. In this work multicomponent molecular assemblies of crown-containing 15crown-5-ether 

4-styrylpyridine (1) with potassium cations, phthalic and isophthalic acids in 

MeCN were investigated by UV-VIS spectroscopy, ESI-mass, NMR and X-Ray analysis. 

K + 

H 

O O 

O 

O 

O 

O O 

O 

O 

O 

O 

O- 

+ N 

H + N 

K + 

O 

O 

O 

O 

N + 

O 

H O 

O 

MeO 

H O 

MeO 

OH 

O 

O 

OH 

OH 

O 

N 

N 

N 

O 

O 

O 

O 

O 

O 

O 

O 

K 

O 

O 

O 

O 

O 

O 

O 

+ 

K + 

Hydrogen and coordination bonds as well as complementary of reacting molecules play the 

important role in the assembly formation. The crown ether moiety prefers to bind with alkaline 

and alkaline-earth metal cations, forming the 'sandwich' complex between 1 and large metal 

cations like K + or Ba 2+ , resulting in hypsochromic shift of long wavelength absorption band of 1. 

In the presence of phthalic acid the protonation of 1 was observed in MeCN solution 

accompanying by bathochromic shift of long wavelength absorption band in UV-vis spectrum. 

The addition of K + to acid complex results in the formation of the mixed sandwich complex. In 

case of isophthalic acid a more complicated complex containing two isophthalic acids, three 

ligands and three K + was found. In this complex isophthalic acid interacts with pyridine residue 

by hydrogen bond formation, crown ether fragments are connected to each other by potassium 

cations. 

Acknowledgment. The study was supported by CRDF (Grant RUC2-2656-MO-05), INTAS 

(Grant 03-51-4696), RFBR (Projects Nos. 05-03-32268 and 06-03-32899). 

PSB 60 

New Series of 18-Membered Aza-oxa-thia and Coumarin Pendent Armed 

Macrocyclic Systems, Synthesis and Applications 

Abbas Shockravi * , Hasan Valizadeh, Hamideh Hoseini and Zahra Taheri 

Tarbiat Moallem University, 49-Mofatteh Ave. Faculty of Chemistry, Post Code 15416, Tehran, 

Iran. Abbas_Shockravi@yahoo.co.uk; Shockravi@tmu.ac.ir 

In the course of the search for new prospective Aza-oxa-thia macrocyclic compounds we 

found that the reaction of different diamines and diacid chlorides/diesters leads to 12- to 20- 

membered (i.e. 1,2) macrocycles and 24- to 40-membered due to dimerization processes [1,2]. 

Conductometry studies of macrocycle (1) and NMR studies of the stiochiomertry and stabilities 

of macrocycle (2) with Ba +2 , Sr +2 , Hg +2 , K + , Ag + and Tl + ions in binary 50% acetonitrilenitrobenzene 

mixture at 300 K proved that macrocycle (1) acts as Ag + sensor and the stabilities 

of the resulting 1:1 complexes vary in the order Ba 2+ > Sr 2+ > Hg 2+ ,… with macrocycle (2). 

Studies on the macrocycle (1) and its sulfoxide derivative revealed that they were biologically 

active and cytotoxic via oxidative response triggering as studied by V79 cell line [3]. Syntheses 

of several chromogenic macrocycles derived from (1) involve the fluorescence species such as 

coumarin subunit attached to nitrogen atom (3, 4). The chemosensor activities of these novel 

coumarin lariat ether macrocycles are under study in our research laboratory and the results will 

be presented in the meeting. 

N 

H 

O NH 

HN 

O 

O 

S 

O 

(1) 

O 

H 

N 

O 

O 

S 

O 

NH HN 

O O 

O 

(2) 

R=a-c 

H 

N 

O NH 

HN 

O 

O O 

O O O 

Br 

O 

O 

O 

O 

(a) (b) (c) 

O 

S 

R 

N 

O 

(3) 

H 

N 

O NH 

HN 

O 

[1]. A. Shockravi, S. Bavili T, E. Rostami, A. Yousefi, A. Dejurian and R. Tohidi, J. Inclusion 

Phenom. Macrocyclic Chem., 2004, 49, 163-166. 

[2]. A. Shockravi and S. Bavili T, J. Inclusion Phenom. Macrocyclic Chem., 2005, 52, 223-227. 

[3]. M. Mashhadi Akbar Boojar and A. Shockravi, Bioorganic and Medicinal Chemistry., 2007, 

18, 3337-3344. 

O 

R 

N 

S 

O 

(4)

PSB 61 

Molecular Recognition of Electron-Deficient Guests Molecules by Podand 

Diazacoronands 

Adam Sobczuk a , Marcin Pawlak a , Jarosaw Kalisiak a , Janusz Jurczak a,b 

a Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland 

b Department of Chemistry, Warsaw University, Poland 

Molecular recognitions, the keystone of supramolecular chemistry, 1 depends on a variety of 

noncovalent interaction. Among them an arene-arene interaction play a fundamental role in the 

selective complexation of –neutral guests. The interaction between simple arenes compromise 

–acid/base (charge-transfer), van der Walls (dispersive), and polar electrostatic (coulombic) 

components. 2 The understanding of electron transfer processes is essential for future progress 

in many diverse fields of science, spinning from biological enzymes 3 via organic synthesis 4 to 

optoelectronic devices. 5 

In this communication we would like to present the synthesis and complexation study of Obenzylated 

diazacoronands of type 1. 

Ar = 

N 

O 

H 

Ar 

O 

O 

O 

O 

H 

N 

1 

N 

O O 

R = H, OMe, N(Me) 2 

O 

O 

Cl Cl 

, , , 

O O 

The above-mentioned electron-rich macrocyclic donor compounds with electron-poor acceptor 

like nitroarenes, forming charge-transfer complexes. Their formation was confirmed by X-ray 

analysis and UV-vis spectroscopy as well as NMR. 

[1] J.-M. Lehn, Angew. Chem., Int. Ed. 1990, 29, 1304. 

[2] C. A. Hunter, K. R. Lawson, C. J. Urch, J. Chem. Soc., Perkin Trans., 2001, 2, 651. 

[3] C. A. Hunter, J. Mol. Biol. 1993, 230, 1025. 

[4] J. F. Stoddart, D. J. Williams, J. Org. Chem. 1997, 62, 26. 

[5] P. Günter, C. Bosshar , V. Gramlich, Adv. Mater. 1998, 10, 777. 

R 

An electrochemical sensor for anions based on a tris-imidazolium cage and 

on the Co III /Co II PSB 62 

redox change 

Cristina Spadini a , Valeria Amendola a , Massimo Boiocchi b , Benoît Colasson c , Luigi Fabbrizzi a , 

Maria-Jesús Rodriguez Douton a 

a Dipartimento di Chimica Generale, Università di Pavia, 27100 Pavia, Italy 

b Centro Grandi Strumenti, Laboratorio di Cristallografia, Università di Pavia, 27100 Pavia, Italy 

c LCBPT, Université PARIS V, 75270 Paris Cedex 06, France 

Transition metals can be used to direct the assembly of concave receptors, suitable for anion 

inclusion. A recent example refers to the system illustrated by the structural formula a, in which 

a low-spin Fe II centre induces the formation of a defined cavity, which offers H-bonds from the 

CH fragments of three imidazolium subunits. Inclusion of halides (e.g. Br ) and pseudohalides 

(e.g. N3 ) has been documented through X-ray and spectroscopic studies [1]. 

The architectural metal centre can play an additional role in signalling anion inclusion, through 

changes of its photophysical (e.g. Ru II ) or electrochemical properties. In this latter perspective, 

the Co II complex of the tris-imidazolium-bipyridine (L) ligand has been investigated. Figure b 

shows the crystal structure of the [Co II (L)]Cl(PF6)4 . H2O . 2MeCN complex salt. Quite surprisingly, 

a water molecule is included within the tris-imidazolium cavity, while the chloride ion stays 

outside of the cage, and, being placed between symmetrically related [Co II (L)H2O] 5+ 

complexes, favours the formation of molecular chains that extends along the a axis in the 

crystal. In any case, in a water/MeCN mixture (1:4, v/v), halide and pseudohalides anion are 

incorporated into receptor’s cavity through equilibria characterised by unusually high logK 

values. The oxidation behaviour of the [Co II (L)] 5+ complex both in pure and in aqueous MeCN, in 

presence of a variety of anions, has been investigated through cyclic voltammetry and 

differential pulse voltammetry (DPV) studies. Figure c shows the DPV profiles obtained on 

titration with chloride of a MeCN solution of [Co II (L)] 5+ (0.1 M [Bu4N]ClO4). On anion addition, the 

potential of the Co III /Co II couple becomes distinctly less positive, which reflects the higher affinity 

of the anion towards the Co III containing receptor (E = 120 mV for Cl , which corresponds to 

logK = 2.0; E = 90 mV and logK = 1.5 for Br ). The redox active [Fe II (L)] 5+ complex cannot 

be used as an electrochemical sensor because of the too positive value of the Fe III /Fe II 

potential, which exceeds that associated to the X2/X couple (X = halogen). 

[1] V. Amendola, M. Boiocchi, B. Colasson, L. Fabbrizzi, M-J. Rodriguez Douton, F. Ugozzoli, 

Angew. Chem., Int. Ed., 2006, 45, 6920-6924.

pH-Responsive Molecular Shuttles Containing Palladium 

James D. Crowley, David A. Leigh, Paul J. Lusby, Roy T. McBurney, Laure-Emmanuelle Perret- 

Aebi, Christiane Petzold and Mark D. Symes 


Edinburgh, EH9 3JJ, United Kingdom (m.d.symes@sms.ed.ac.uk) 

Following the synthesis of Pd(II)-containing rotaxanes [1] and catenanes [2] , we report the 

synthesis of two Pd(II)-based molecular shuttles, in which the position of a macrocycle in a 

[2]rotaxane can be controlled with high precision by altering the pH of the environment. A 

macrocycle with a tridentate carboxamide binding motif shows an equilibrium distribution in 

favour of a substituted dimethylaminopyridine (DMAP) station over a substituted pyridine 

station in a ratio of 9:1 at neutral pH in deuterated DMF. Under acidic conditions, this 

equilibrium shifts so that the macrocycle prefers the pyridine over DMAP in a 9:1 ratio 

(Scheme 1). 

O 

O 

DMAP Station Pyridine Station 

O 

N 

O 

N 

N PdN 

N 

O O 

N 

N + 

H X- O 

N 

-H + 1 equiv. H + 

N 

O 

N PdN 

O 

N 

O 

Scheme 1: A Pd(II)-based pH shuttle 

Subtle alteration of the structure of the macrocycle allows improved discrimination for DMAP 

over pyridine in the neutral form and pyridine over DMAP in the protonated form. Furthermore, 

the reaction time is greatly reduced and milder conditions (room temperature as opposed to 

110 °C) are found sufficient to bring about the shuttling. 

[1] A.-M. Fuller, D. A. Leigh, P. J. Lusby, I. D. H. Oswald, S. Parsons and D. B. Walker, 

Angew. Chem. Int. Ed., 2004, 43, 3914-3918. 

[2] A.-M. L. Fuller, D. A. Leigh, P. J. Lusby, A. M. Z. Slawin and D. B. Walker, J. Am. Chem. 

Soc, 2005, 127, 12612-12619. 

O 

O 

PSB 63 

Contraction of Supramolecular Double-Threaded Dimer Formed by α- 

Cyclodextrin with Long Alkyl Chain 

Yoshinori Takashima, Shouichi Tsukagoshi, Atsuhisa Miyawaki, Hiroyasu Yamaguchi, and Akira 

Harada* 


Toyonaka, Osaka 560-0043, Japan; e-mail: takasima@chem.sci.osaka-u.ac.jp 

PSB 64 

Molecular motors and machines in 

biological systems, such as dynein, 

flagellar, myosin and kinesin, have highlyprecise 

structures and achieve controlled 

movements by external stimuli. Recently, 

the subject of nanoscale artificial 

molecular muscles and motors has 

attracted much interest from researchers. 

We previously reported that 6cinnamamide-α-CD 

and 6aminocinnamate-α-CD 

formed a doublethreaded 

dimer, however, substituent 

groups on α-CDs are too short to mimic 

the contraction and extension of skeletal 

muscle. 6 Scheme 

In this paper, we have prepared 

a modified 6-aminocinnamamide-α-CD 

and investigated the formation of the double-threaded dimer. We discuss the conformational 

change of the double-threaded dimer by increased solvent polarity. 

To estimate the size of the double-threaded dimer 3 in DMSO-d6 and H2O/DMSO-d6 

(1:1), the pulse field gradient spin-echo (PFGSE) NMR technique was used and the diffusion 

coefficients (D) and hydrodynamic radii (RH) of the supramolecular complexes were determined. 

The apparent RH of the double-threaded dimer 3 in DMSO-d6 and H2O/DMSO-d6 (1:1) showed 

1.63 nm and 2.08 nm in diluted solution (5 mM), respectively. The change of length of the 

double threaded dimer (3) is estimated to be about 0.66 nm calculated by the molecular 

modeling. These results are conconsistent with the hydrodynamic radii, and indicate that 

double-threaded dimer 3 forms the complex with larger size or the stretched state in 

H2O/DMSO-d6. 

We are currently expanding these studies to the synthesis of supramolecular polymers 

based on double threaded dimer units. 

[1] Tsukagoshi, S.; Miyawaki, A.; Takashima, Y.; Yamaguchi, H.; Harada, A. 

Org. Lett. 2007, 6, 1053-1059.

PSB 65 

Switching of Self to non-Self Supramolecular Structures by Isomerization 

Yoshinori Takashima, Naoki Tomimasu, Hiroyasu Yamaguchi and Akira Harada* 


Toyonaka, Osaka 560-0043, Japan; e-mail: takasima@chem.sci.osaka-u.ac.jp 

In recent years, supramolecular chemistry 

has been expanding to supramolecular 

polymer chemistry. More recently, 

construction of sophisticated 

supramolecular polymeric structures has 

been reported, such as columnar, helices, 

and rotaxane polymers. Previously, we 

reported alternating supramolecular 

polymers of α-CD derivative and β-CD 

derivatives. Here we report new 

supramolecular structures formed by 2-(O)cinnamoyl 

α-CD (2-CiO-α-CD) and 3-(O)cinnamoyl 

α-CD (3-CiO-α-CD), and 

switching of supramolecular structures by 

isomerization. 

We have obtained a single crystal of 

2-CiO-α-CD suitable for X-ray 

crystallographic analysis. The X-ray 

crystallographic analysis showed formation 

of a cyclic dimer. However, although the 

PFG NMR spectra of 2-CiO-α-CD show a 

definite diffusion coefficient (D) over 10 

mM, that of 3-CiO-α-CD shows that 

diffusion coefficient decreases 

monotonously with its concentrations. 

These results indicate that although 2-CiOα-CD 

formed a cyclic dimer, 3-CiO-α-CD 

formed weak supramolecular oligomers in 

aqueous solutions. 

Figure 1. Schematic illustration of the formation of 

supramolecular complexes using CiO-α-CDs. 

Although 2-CiO-α-CD and 3-CiO-α-CD did not isomerize at high concentrations, each 

isomer was found to isomerize in dilute aqueous solutions to give a 1:1 mixture. Interestingly, 

the mixture of 2-CiO-α-CD and 3-CiO-α-CD forms an alternative supramolecular complex, and 

not self-supramolecular complex. 

2-CiO-α-CD and 3-CiO-α-CD organized by itself to give a supramolecular cyclic dimer 

and a weak supramolecular oligomer, respectively, at high concentrations. In contrast, at low 

concentrations, CiO-α-CD isomerizes to its isomer to give stable alternating supramolecular 

polymers. These results are interesting because each isomer switches from self recognition to 

non-self recognition by isomerization. We are now studying the mechanism in detail. 

Sulfides peroxide oxidation in the presence of crown ethers 

A.V.Anisimov, A.V.Tarakanova, Pham Vinh Thai, A.A.Seleznev, N.S.Kulikov 

Moscow State University, Department of Chemistry, 119992, Moscow, RUSSIA 

E-mail: anis@petrol.chem.msu.ru 

Sulfides oxidation is very important route for purification of hydrocarbon raw materials and 

oil fractions from sulfur compounds. Among the different catalysts proposed in literature for this 

process transition metal peroxocomplexes are the most frequently studied. There are many 

difficulties to carry out benzothiophene derivatives oxidation in the presence of homogeneous 

and heterogeneous conditions. In the present work, we dedicated particular attention to crown 

ethers as possible catalysts of peroxide oxidation of alkyl aryl sulfides and and 

benzothiophenes. As model reaction oxidation of methylphenylsulfide and benzothiophene was 

selected at 20-40 O C temperature by hydrogen peroxide. In most cases oxidation of 

methylphenyl sulfide proceed with the formation of the mixture of corresponding sulfoxide and 

sulfone. The kinetic studies of the process showed that sulfide oxidation is two step reaction. 

The first step is the formation of sulfoxide and the second one their oxidation to sulfone. The 

practically quantitative yield of methylphenyl sulfone was obtained by 40 O C when reaction 

proceeded for 4 hrs. The only product of benzothiophene oxidation was corresponding sulfone. 

The highest yield of benzothiophene sulfone (80%) was achieved at 40 o C by reaction time 

about 6 hrs. The structure of crown ethers complexes with sulfides and hydrogen peroxide and 

oxidation products were confirmed by NMR spestroscopy, and mass-spectromertry.. 

We thank RFBR to financial support, grant N 06-03-32367. 

PSB 66

PSB 67 

Cooperative Complexation of -Cyclodextrin with Micelle-like Aggregates 

Formed from Amphiphilic Polyanions 

Daisuke Taura, Akihito Hashidzume, and Akira Harada 


Toyonaka, Osaka 560-0043, Japan 

Molecular recognition in biological 

systems often exhibits high selectivity to 

form precisely controlled supramolecular 

structures, which express various 

functions necessary for maintaining living 

activities. We have been aware of the 

importance of macromolecular chains in 

the biological molecular recognition for 

the past decade, and thus studying the 

interaction of cyclodextrins (CDs) with 

hydrophobic side chains attached to 

water soluble polymers (WSPs). The 

previous studies focused on the 

interaction of CDs with WSPs modified 

with a small amount of hydrophobes, whereas this study focuses on the interaction of CDs with 

WSPs bearing a number of hydrophobes to investigate the effect of competition with 

self-association of hydrophobes. In this study, we employed alternating copolymers of sodium 

maleate and dodecyl vinyl ether with different molecular weights (pC12MAn, Figure 1). 

Steady state fluorescence and sedimentation equilibrium measurements confirmed that 

pC12MAn formed micelle-like aggregates in aqueous media. The interaction of -, -, and -CDs 

with pC12MAn was investigated by several NMR techniques. These spectra indicated that only 

-CD interacted significantly with dodecyl (C12) groups in pC12MAn. Then, the complexation 

equilibrium between -CD with pC12MAn was explored by 1 H NMR spectra measured in the 

presence of varying concentrations of -CD. These spectra exhibit resonance bands due to free 

and complexed C12 groups separately at intermediate -CD concentrations, indicating slow 

exchange between the free and complexed states comparing with the NMR time scale. Using the 

concentrations of free and complexed C12 groups, the concentrations of free and complexed 

-CD (CCD,f and CCD,c, respectively) were calculated. Values of CCD,c were plotted against CCD,f to 

prepare binding isotherms. The binding isotherms exhibit sigmoidal curves, indicative of 

cooperative complexation of -CD with pC12MAn. Figure 1 shows a conceptual illustration for the 

cooperative complexation of -CD with pC12MAn. The binding isotherms were analyzed using a 

model based on one dimensional lattice model although it may not be a proper model. The 

analysis indicated that -CD interacted more cooperatively with pC12MAn of a higher molecular 

weight. 

Dissociation Kinetics of Tl + , Pb 2+ , Cd 2+ , and Bi 3+ Cryptates 

Gary. L. N. Smith, Olajumoke O. Oluwu, Baige Bian, Richard W. Taylor 

Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, 

Norman, OK 73019, USA 

Cryptands form stable complexes with heavy metal ions such as Tl + , Pb 2+ , Cd 2+ , and Bi 3+ . 

Structural factors that affect the complexation selectivity include: i) cavity size, ii) type of donor 

atoms (O, N, S), and iii) backbone substituents (benzo, cyclohexano). We have studied the 

dissociation kinetics for the compounds shown below to examine the role of these structural 

factors. In the presence of excess strong acid the observed rate constant, kobs, shows several 

types of [H + ] dependence. For most cryptates studied, a linear dependence on [H + ] is observed 

(kobs = kd + kH [H + ]), where kd and kH are the rate constants for the acid-independent and aciddependent 

pathways, respectively. However, the dissociation of Tl(2.2.2) + shows saturation 

type behavior (kobs = (kd + kH [H + ])/(1 + k’[H + ]). For complexes with polyaza-cryptands such as 

Pb(2N.2.2) 2+ and Bi(2N.2N.2N) 3+ pathways indicating higher-order [H + ] dependence are observed 

(kobs = (kd + kH1 [H + ] + kH2[H + ] 2 ). The role of various structural factors on the dissociation 

kinetics and the detailed mechanisms consistent with [H + ] dependence of kobs are discussed. 

O 

N O O N 

O O 

N O O N 

a 

a = 1; 2.2.1 

a = 2; 2.2.2 

a = 3; 3.2.2 

R 

O O 

O O 

R 

R = C 6H 4 ; 2 B.2 B.2 

R = C 6H 10 ; 2 C.2 C.2 

X X 

N O O N 

O O 

X = O; 2.2.2 

X = S; 2 S.2.2 

X = N; 2 N.2.2 

NH HN 

H 

N N N 

H N 

NH HN 

2 N.2 N.2 N 

O O 

N O O N 

O O 

An2.2.2 

N N 

N O O N 

O O 

2.2.2 BIPY 

PSB 68

Investigation of -cyclodextrin binding affinity to some purine alkaloids. 

Irina Terekhova 

Institute of Solution Chemistry of Russian Academy of Sciences, 1 Akademicheskaya str., 

Ivanovo 153045, Russia, E-mail: ivt@isc-ras.ru 

PSB 69 

Cyclodextrins (cyclooligosaccharides) are a family of macrocyclic receptors, which are able to 

form inclusion complexes with a wide variety of organic compounds. Physical-chemical and 

biological properties of guest molecules included into cyclodextrin cavity during the complex 

formation can be significantly modified. An inclusion complexation phenomena of cyclodextrins 

determines their numerous practical applications. Primarily, cyclodextrins are used as 

solubilizing and stabilizing agents in cosmetic, food and pharmaceutical industries, as well as 

drug carriers. Therefore, the aim of present work was to reveal the capability of native and 

substituted -cyclodextrins to form inclusion complexes with caffeine and theophylline in 

aqueous solution. These alkyl substituted xanthines referred to the class of purine alkaloids are 

the substances of biological and pharmaceutical importance. 

Interactions of - and hydroxypropyl--cyclodextrins with caffeine and theophylline in water at 

298.15 K were studied by calorimetry, 1 H NMR and solubility methods. Systems with complex 

formation and weak interactions were characterized by the thermodynamic parameters of 

complexation (K, cG, cH and cS) and enthalpic virial coefficients (hxy), respectively. 

The obtained results demonstrate that: 

- -Cyclodextrins display low binding affinity to caffeine and theophylline. 

- Structure of purine alkaloids influences the thermodynamics of interaction and binding 

affinity of cyclodextrins. In comparison with theophylline, caffeine forms more stable 

complexes with -cyclodextrin. 

- Complex formation of -cyclodextrin with caffeine is enthalpy-entropy driven, whereas its 

binding with theophylline is only entropically favourable. However, the entropy 

contribution in the free energy is dominant in both cases. 

- Partial substitution of OH-groups surrounding the -cyclodextrin molecule by 

hydroxypropyl-groups results in weakness of binding. Probably, hydroxypropyl 

substituents may be too bulky hindering complexation of hydroxypropyl--cyclodextrin 

with caffeine and theophylline. 

- Insignificant enhancement of aqueous solubility of purine alkaloids under study in the 

presence -cyclodextrin was observed. 

This work was supported by the Russian Foundation for Basic Research (grant no. 06-03- 

96313) and by the Russian Science Support Foundation. 

Ditopic dithiophosphoramides and acylthiourea ligands as metal salt 

extractants 

Jy Chartres, Shalima Shawuti, Peter A. Tasker * , Christine C. Tong 

University of Edinburgh, School of Chemistry, Joseph Black Building, West Mains Road, 

Edinburgh, Scotland EH9 3JJ email: ctong@staffmail.ed.ac.uk 

Ditopic ligands are those that have binding sites for a cation and anion in a single covalent 

molecule and are effective ligands for transferring metal salts from aqueous to water-immiscible 

phases. [1-2] As such, ditopic ligands provide an effective strategy for isolating metal value from 

mining leachates and provide access to more environmentally friendly metal recovery 

processes. 

Metal salts are extracted from the aqueous phase into the organic phase using a ditopic ligand. 

The metal cation and anion can then be stripped into aqueous solution by adjusting the pH. 

Separate cation and anion stripping is effected by the differences in pKa of the cation and anion 

binding sites (Fig. 1). This paper reports the synthesis and characterization of 1 and 2 as well as 

their efficacy as ditopic metal salt extractants, thereby elaborating on the existing successful 

(but limited) motifs for ditopic extractants for base metals. [3-4] 

AH 

AH 

ligand salt 

+2NH3 

-[NH4]2X 

HB + 

X 2- 

HB + 

+H2X 

-MX 

AH B 

AH B 

free ligand 

A - 

M 2+ 

A - 

+ MX 

metal-salt 

complex 

HB + 

X 2- 

HB + 

HB + 

AH 

Y 

AH 

2- 

HB + 

ligand salt 

1 2 

[1] L. A. J. Chrisstoffels, F. de Jong, D. N. Reinhoudt, Chem. Euro. Journal 2000, 6, 1376. 

[2] R. A. Coxall, L. F. Lindoy, H. A. Miller, A. Parkin, S. Parsons, P. A. Tasker, D. J. White, 

Dalton Trans. 2003, 55. 

[3] N. Akkus, J. C. Campbell, J. Davidson, D. K. Henderson, H. A. Miller, A. Parkin, S. Parsons, 

P. G. Plieger, R. M. Swart, P. A. Tasker, L. C. West, Dalton Trans. 2003, 1932. 

[4] S. G. Galbraith, P. G. Plieger, P. A. Tasker, Chem. Comm. 2002, 2662. 

+H2Y 

+2NH3 

-[NH4]2Y 

+2NH3 

-[NH4]2X 

+H2X 

+2H2Y 

-MY 

A - 

M 2+ 

A - 

metal-only 

complex 

+MY 

-[NH4Y] 

Fig. 1 Schematic diagram of pH controlled loading and stripping of ditopic ligands 

coordinated to metal salts. The uncoordinated salts are in the aqueous phase. For our 

interests, M = Cu 2+ , Ni 2+ , Zn 2+ and Co 2+ and X = SO4 2- . 

N 

S 

S 

P P 

N 

H 

t-Bu t-Bu 

t-Bu 

O S 

NH 

N 

N 

B 

B 

PSB 70

PSB 71 

Synthesis and preliminary molecular recognition studies of novel protonionizable 

crown ethers containing a diarylphosphinic acid moiety 

Péter Huszthy a,b , Tünde Tóth b , György Székely a , Viktor Farkas c , Miklós Hollósi c 

a Department of Organic Chemistry and Technology, Budapest University of Technology and 

Economics, H-1111 Budapest, Szent Gellért tér 4, Hungary 

b Research Group for Alkaloid Chemistry of Hungarian Academy of Sciences, H-1111 

Budapest, Szent Gellért tér 4, Hungary 

c Department of Organic Chemistry, Eötvös Lóránd University, H-1117 Budapest, Pázmány 

Péter sétány I/A, Hungary 

Proton-ionizable crown ethers having a pH switching mechanism have attracted the attantion of 

many researchers, because at pH values higher than their pKa, they are mostly ionized to ligand 

anions, which increase the cation-ligand complex stability with enhancement of selectivity, and 

avoid the need for a counter anion is in transport through various membrane systems or in 

solvent extraction [1, 2]. 

R 

* O O 

O 

P 

OH 

O O 

O 

R = H, alkyl group 

Figure 

* 

R 

Starting from commercially available and 

relatively cheap starting materials novel 

enantiopure proton-ionizable crown ethers 

(Figure, R=alkyl) and their achiral parent 

compound (Figure, R=H) containing the 

diarylphosphinic moiety were synthetized by 

multistep reactions. 

The molecular recognition studies on these 

novel proton-ionizable ligands including 

enantioselective complexation with the 

enantiomers of chiral primary amines using CD 

spectroscopy are in progress. 

Financial support of the National Scientific Research Fund of Hungary (OTKA: K 62654) is 

greatfully acknowledged. 

[1] C. W. McDaniel, J. S. Bradshaw and R. M. Izatt, Heterocycles, 1990, 30, 665-706. 

[2] R. A. Bartsch, ACS Sympos. Series, 1999, 716, 146-155. (Chem. Abstr. 1999, 130, 201386.) 

Cyclen based dimers as tridimentional receptors for polyphosphate 

recognition. 

Raphaël Tripier, Stephanie Develay, Michel Le Baccon, Guy Serratrice and Henri Handel 

PSB 72 

UMR CNRS 6521, “Chimie, Electrochimie Moléculaire et Analytique”, Université de Bretagne 

Occidentale, C. S. 93837, 6 avenue Victor Le Gorgeu, 29238 Brest Cedex 3, France. Tel: 33 2 

98017927; Fax: 33 2 98017001; E-Mail: Raphael.tripier@univ-brest.fr 

There is a growing interest in the molecular recognition of anionic species because of their 

potential applications in environmental, industrial and health-related areas. Phosphate type 

anions are ubiquitous as well in human activity effluents as in biological structures. 

Polyprotonated macrocycles behave as efficient receptors for polycharged anions in aqueous 

solutions; they strongly associate to nucleotides via electrostatic interactions between the 

cationic binding sites (ammonium groups) of the receptor and the negatively charged 

polyphosphate chain. 

We recently reported a facile synthesis of 

cyclen based dimers (bis-macrocycles and 

macrotricycles) using the efficient bisaminal 

tool that allowed us to get 

tetraazacycloalkanes dimers in high 

overall yields. These ligands which include 

eight amino groups and rigid phenyl or 

pyridinyl spacer(s) are potentially good 

receptors for inorganic anions or 

nucleotides. 

The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions 

and these tridimentional ligands possessing ortho-, meta-, para-xylenyl or 2,6-pyridinyl linkers 

was investigated by potentiometric measurements and NMR spectroscopy. 1 Each ligand gave in 

aqueous solution protonated species that further formed ternary complexes after binding with 

anions; the structure of these complexes were analyzed as a result of hydrogen bond formation 

and coulombic attraction between the organic host and the inorganic guest. 

The results unambiguously showed the importance of the protonation degree, the rigidity of the 

ligand and underlined, especially for the triphosphate species, the contribution of the nitrogen 

atom of the pyridinyl spacer as supplementary anchoring point in acidic medium. The 

equilibrium constants found for all the detected species will be reported and the selectivity will 

be discussed. 

[1] S. Develay, R. Tripier, M. Le Baccon , V. Patinec, G. Serratrice, H. Handel, Dalton Trans. 

2005, 3016; S. Develay, R. Tripier, M. Le Baccon , V. Patinec, G. Serratrice, H. Handel, 

Dalton Trans. 2006, 3418; S. Develay, R. Tripier, N. Bernier, M. Le Baccon, V. Patinec, G. 

Serratrice, H. Handel, Dalton Trans. 2007, 1038-1046.

Novel ditopic probes for different metal cation recognition 

Elena Tulyakova a , Olga Fedorova b , Yuri Fedorov b , Gediminas Jonusauskas c , Alexander 

Anisimov a 

a Chemistry Department, M. V. Lomonosov Moscow State University, 119992, Moscow, Russia 

b Photochemistry Center of Russian Academia of Sciences, 119421 Moscow, Russia 

CPMOH – UMR CNRS 5798, Bordeaux University I, 33405 Talence, France 

Design of new probes for cooperative recognition of hard and transition metal cations along with 

alkaline earth metals is topic of current importance in medicine and environmental monitoring. 

The aim of present work is investigation a bifunctional molecules combined two different 

receptor residues which show such a multifold signal expression in the presence or absence of 

one or two different types of metal cations. New ion-selective receptors with two ionophoric 

centers had been obtained due to the ability of benzocrown ether moiety to bind alkali, alkaline, 

earth metal cations and the affinity of phenylazathiacrown ether to heavy metal cations. The 

response of compounds is useful both in absorption and emission spectroscopy: the strong 

wavelength shifts observed in the presence of cations make the dyes suitable for dual 

wavelength analysis in self-calibrating measurements. The interaction strength between ligands 

and cations was measured. Due to simple model of complex formation the reliable correlation 

between the concentration of metal cations in solution and value of optical response of dyes 1-4 

can be obtained. So compounds can be considered as probe designed with the purpose to 

measure cation concentration in different kind of cationic analysis. 

R 1 = 

R 1 

O 

O 

1 : 2 : R1 N R2 N 

R2 - CH3 - 

ClO 

ClO4 CH 4 

3 

O 

O 

O 

= Mg 

R2 = 

2+ , Ba2+ , Ca2+ = Hg2+ , Cu2+ , Ag + 

S O 

N 

S O 

3 : R1 N (CH2) 3 N R2 4 : R1 N (CH2) 3 N S 

- ClO4 - ClO4 - ClO - R2 4 ClO4 

PSB 73 

Acknowledgements. Generous financial support from the Russian Science Support Foundation, 

grant supporting for talented students, PhD students and young scientists of M.V. Lomonosov 

Moscow State University and RFBR (05-03-32268, 06-03-32899) are gratefully acknowledged. 

Preparation of new octa(alkoxy) pyrazinoporphyrazines 

Rabia Zeynep Uslu Kobak, Ahmet Gül 


Fax:(+90) 212 285 63 86, e-mail: uslur@itu.edu.tr 

Substituted azaphthalocyanines(AzaPc’s) are generally more soluble than the corresponding 

phthalocyanines (Pc’s) and may, therefore, be more applicable in various areas of technology 

and especially in photodynamic therapy. A limited number of substituted AzaPc’s have been 

reported in the literature, where alkyl groups, carboxylic acids or esters are mentioned as 

substituents. For instance, AzaPc’s , substituted with carboxylic acids, were prepared as 

potential activators for photodynamic cancer therapy[1]. 

Presently we report the synthesis of a new alkoxy substituted pyrazine dicarbonitrile and its 

cyclotetramerisation to AzaPc. The metal complexes were synthesized by template 

cyclotetramerisation of the pyrazinedicarbonitrile in the presence of the appropriate metal salts. 

The new ligand and AzaPc’s were characterized by UV-Vis, IR, 1 H-NMR and mass spectra[2,3]. 

O 2N 

O 2N 

O 

O 

O 2N 

O 2N NO 2 

N 

N 

N 

N 

N 

O O 

N N 

N 

O 

N 

M 

N 

N 

O 

N 

N 

N 

M=Zn,Co,Cu 

References 

[1] Morkved H.E., Ossletten H., Ksojen H., Acta Chemica Scandinavica , 1999, 53, 1117-1121. 

[2] Uslu R.Z., Gül A., C.R. Acad. Sci. Paris. Serie IIC/Chimie , 2000 ,643-648. 

[3] Nazlı A.,Gonca E., Gül A., Journal of Porphyrins and Phthalocyanines,2006,10, 996-1002. 

N 

N 

NO 2 

O 

O 

NO2 

NO 2 

PSB 74

Design, synthesis and study of the first “excimer helicates” 

Miguel Vázquez, a M. Eugenio Vázquez, b Clara Gómez-Reino, b Maurizio Licchelli, c Manuel R. 

Bermejo a 

a Departamento de Química Inorgánica, Facultad de Química, Universidad de Santiago de 

Compostela, 15782 Santiago de Compostela, Spain 

b Departamento de Química Orgánica, Facultad de Química, Universidad de Santiago de 

Compostela, 15782 Santiago de Compostela, Spain 

c Dipartimento di Chimica Generale, Università di Pavia, 27100 Pavia, Italy 

There has been an increased interest in the study of metallic helicates since the discovery of 

their DNA binding properties, but the nature and details of such interaction are still poorly 

understood.[1] Therefore, it is of great importance the development of new analytical tools for 

studying their assembly and recognition properties with DNA. Excimers are particularly useful 

for the development of sensors, since their emission is sensitive to changes in the molecular 

geometry and environment. This property has been extensively exploited to monitor numerous 

biologically relevant recognition processes and, in our opinion, is remarkably suited to the study 

of helicates and their interactions.[2] 

Herein we present the first two examples of “excimer helicates”, using the bis-naphtalene 

tetraamine L1 as ligand. We have found that the interaction of either M II (Zn II or Cd II ) with ligand 

L1 follows 2:2 stoichiometry, with a three dimensional arrangement that brings the naphtalene 

fluorophores face-to-face on each end of the ligand, promoting the formation of intramolecular 

excimer species that can be applied to monitor the self-assembly process. 

We strongly believe that that this new family of supramolecular architectures opens new 

important perspectives for studying the interactions of helicates with DNA. 

E.T. 

H 

N 

H 

N 

base 

H 2 

N 

H 2 

N 

acid 

L 1 

H 

N 

H2 

N 

H 4L 1 4+ 

290 nm 290 nm 475 nm 

E.T. 

H N 

290 nm 

H 2 

N 

NH NH 

HN NH HN NH 

2 M HN NH 

II II M MII 

310 - 360 nm 

[M 2(L 1) 2] 4+ 

PSB 75 

[1] M. J. Hannon, Chem. Soc. Rev., 2007, 36, 280. 

[2] C. Guarnaccia, B. Raman, S. Zahariev, A. Simoncsits, S. Pongo, Nucleic Acids Res. 2004, 

32, 4992 

Synthesis and characterisation of a liquid-crystalline 2catenane and its 

copper(I) complex 

Etienne D. Baranoff a , Julie Voignier b , Takuma Yasuda a , Valérie Heitz b , Jean-Pierre Sauvage b , 

Takashi Kato a 

a Department of Chemistry and Biotechnology School of Engineering, University of Tokyo, 

Hongo, Bunkyo-ku, Tokyo 113-8656, Japan 

b Laboratoire de Chimie Organo-Minérale, Institut de Chimie de Strasbourg, Université Louis 

Pasteur, 4 rue Blaise Pascal 67070 Strasbourg Cedex, France 

The combination of 2catenanes and liquid crystals (LC), which are mobile and ordered 

condensed states, is a new promising approach towards practical devices and molecular 

machines. Indeed 2catenanes could control self-assembled behaviour of LC molecules, 

whereas the LC molecular order of these mobile systems will provide them with an organized 

dynamic environment. Free 2catenane 1 was obtained by double esterification of 3 with 4 

mediated by EDC in 75% yield. Subsequent reaction of 1 with copper(I) led quantitatively to 2. 

As expected, formation of layered self-assembled structures of smectic LC phases induced by 

the incorporation of forklike dendrons 4 1 

into the 2catenane 3 2 was observed. The LC 

2catenane 1 and its copper(I) complex 2 form organized structures in their bulk state over 

wide temperature ranges. 3 

3 4 

free [2]catenane 1 

Copper(I) [2]catenane 2 

PSB 76 

[1] K. Kishimoto, M. Yoshio, T. Mukai, M. Yoshizawa, H. Ohno, T. Kato, J. Am. Chem. Soc., 

2003, 3196-3197 

2 for related compounds see: J.-L. Weidmann, J.-M. Kern, J.-P. Sauvage, D. Muscat, S. 

Mullins, W. Köhler, C. Rosenauer, H. J. Räder, K. Martin, Y. Geerts, Chem. Eur. J., 1999, 5, 

1841-1851 

3 E.D. Baranoff, J. Voignier, T. Yasuda, V. Heitz, J.-P. Sauvage, T. Kato, Angew. Chem. Int. 

Ed., 2007, in press.

PSB 77 

Synthesis, supramolecular architecture and redox properties of cobalt and 

iron(II) macrocyclic and macrobicyclic bis- and tris-dioximates with 2,6-ditert-butylphenol 

pendants 

Yan Z. Voloshin , Dmitrii B. Shpakovsky b , Elena R. Milaeva b , Tatyana V. Magdesieva b , 

Alexander S. Belov a 

 


E-mail: voloshin@ineos.ac.ru 

b 

Moscow State Lomonosov University, 119992 Moscow, Russia 

The synthesis of coordination compounds with redox-active organic ligands, which are capable 

to form stable radical pendants, will be presented. 

– e, – H 

HO O 

+ 

. 

M M 

The novel cobalt and iron(II) macrocyclic bis-dioximates (the derivatives of ligand 1) and 

macrobicyclic tris-dioximates 2 - 4 with 2,6-di-tert-butylphenol substituents were obtained. 

HO 

OH 

N 

N 

OH 

O 

N 

N 

O 

O 

F 

B 

O 

N 

Fe 2+ 

N 

N N 

O 

O 

B 

F 

H 

HO 

S 

HO 

S B 

O O 

N 

N 

M 2+ 

S S N N N S 

S N 

O 

O 

O 

O 

OH 

HO 

S B 

OH HO 

S 

1 2 HO 3 HO 4 

O 

N 

S 

OH 

HO 

S 

HO 

S B 

O O 

N 

N 

Fe 2+ 

O 

N 

N N 

O 

O 

B 

M 2+ = Fe 2+ , Co 2+ 

From one up to six hindered phenol pendants were incorporated in the cage molecules by the 

nucleophilic substitution of the initial reactive chloride clathrochelate precursors with 

thiophenolate anion: 

N 

Fe 

N 

2+ 

B 

O O O 

N 

N N 

O 

O 

B O 

N H 

F 

Cl 

F 

OH 

S 

. 

The pathways and the products of clathrochelates redox transformations in solutions have been 

studied using ESR, UV-vis spectroscopy and CVA. The oxidation of phenol-containing 

clathrochelates in toluene leads to the formation of stable phenoxyl species. 

This work was supported by RFBR ( 05-03-33184, 05-03-32869, 06-03-90903, 06-03-32626 

and 07-03-00765). 

2 

S 

S 

OH 

OH 

PSB 78 

First synthesis of clathrochelate iron(II) oximehydrazonate with a differ 

orientation of the functionalizing substituentes relative to the capping 

1,3,5-triazacyclohexane ring 

Yan Z. Voloshin , Sergei Y. Erdyakov b , Mikhail E. Gurskii b , Irina G. Makarenko a , 

Ekaterina G. Lebed a , Yurii N. Bubnov a 

 


e-mail: voloshin@ineos.ac.ru 

b 

N. D. Zelinsky Institute of Organic Chemistry, RAS, 119991 Moscow, Russia 

e-mail: bor@ioc.ac.ru 

The H + -ion-catalyzed condensation of the boron-, tin-, antimony- and germanium-containing 

semiclathrochelates with an excess of triethyl ortoformate (TOF) results in the formation of the 

single clathrochelate product for each of these precursors [1-4]. In case of boron-containing 

compounds, the complexes obtained have syn,syn,syn-orientation of the ethoxy groups and 

semiclathrochelate fragment relative to the 1,3,5-triazacyclohexane ring, whereas the tin-, 

antimony- and germanium-containing clathrochelates molecules have an anti, anti, anticonfiguration. 

The macrocyclization of o-carboranyldiboron-capped iron(II) oximehydrazonate 

semiclathrochelate with an excess of TOF (Scheme) unexpectedly gives the single 

clathrochelate complex with mixed syn, syn, anti-orientation of ethoxy substituents (see X-ray 

structure) and with the detachment of one of the two boronate fragments. The unusual antiorientation 

of one of the three ethoxy substitutents may be explained by the steric hindered 

caused by the second boronate group on the first step of macrocyclization reaction. 

H B 

Fe 2+ 

OH 

N 

NH2 NH2 

N N 

2+ 

Fe 

N N 

N (H3CO) 2B 

NH2 N 

N 

O O O 

B 

C 

NH 2 

B(OCH 3) 2 

+ 

C 

H + 

TOF 

CH 3CN 

B H 

C 

B(OCH3) 2 

H B 

CH 3CN 

H C2H5O C2H5O N N 

H 

N N 

2+ 

Fe 

H 

OC2H5 N 

N 

N N N 

O 

O 

B 

O 

Scheme 

This work was supported by RFBR ( 05-03-33184, 06-03-90903, 06-03-32626, 07-03-00765 

and 05-03-33268). 

[1] Y.Z.Voloshin, O. A.Varzatskii et al., Inorg.Chem.Commun., 1998, 1, 328-331 

[2] Y.Z.Voloshin, A.I.Stash et al., Inorg.Chim.Acta, 1999, 284, 180-190 

[3] Y.Z.Voloshin, O. A. Varzatskii et al., Inorg.Chim.Acta, 2000, 299, 104-111 

[4] Y.Z.Voloshin, O.A. Varzatskii et al., Inorg. Chim. Acta, 2004, 357, 3187-3204 

C 

+ 

H H 

H

Azomacrocyclic derivatives of pyrrole as chromoiononophores and 

fluoroionophores 

Ewa Wagner-Wysiecka, Elbieta Luboch, and Tomasz Rzymowski 

Chemical Faculty, Gdansk University of Technology, Narutowicza St 11/12, 80-952 Gdask, 

Poland 

Crown ethers incorporating an azo group as a part of macrocycle are interesting metal 

complexing agents showing properties typical for azo metallochromic reagents [1]. Recently, we 

described series of chromogenic crown ethers bearing simultaneously heterocyclic residue of 

pyrrole [2] or imidazole [3] as a part of macrocycle. This work presents synthesis and properties 

of novel pyrrole containing chromogenic crown ethers (Fig. 1) and studies of metal ion 

complexation. The complexation was investigated with the use of UV-Vis and fluorescence 

spectroscopy. 

O 

O 

O 

O 

N 

N 

H 

N N N 

O 

O O 

O 

N N 

H 

N N N 

O 

O 

O 

O 

N 

N 

H 

N N N 

Fig.1 Investigated azomacrocyclic derivatives of pyrrole 

N O O 

S 

S 

O 

O 

N 

O 

N 

N 

H 

N N N 

O 

S 

O 

N 

O 

N 

N 

H 

N N N 

Complexation of alkali, alkaline earth and heavy metal cations (Pb 2+ , Co 2+ , Ni 2+ , Zn 2+ ) was 

studied in different organic and water containing solvent systems. 

[1]. For example see review: E. Luboch, R. Bilewicz, M. Kowalczyk, E. Wagner-Wysiecka, J.F. 

Biernat, Azo Macrocyclic Compounds. In G. W. Gokel , Ed.,Advances in Supramolecular 

Chemistry; Cerberus: South Miami, USA, 2003, vol.9, p.72. 

[2]. E. Luboch, E.Wagner-Wysiecka, M.Fainerman-Melnikova, L.F.Lindoy, J. F Biernat, 

Supramol. Chem. 2006, 18, 593-601. 

[3]. E.Wagner-Wysiecka, M. Jamrógiewicz, J. F. Biernat, Tetrahedron, 2007, 63, 4414-4421. 

Financial support from the Polish State Committee for Scientific Research, Grant no. 

3TO9A15127 is kindly acknowledged. 

PSB 79 

PSB 80 

Cation and anion binding studies of a large N,O-donor macrocycle:Single 

ion extraction and synergistic enhancement 

Marco Wenzel 1,2 , Kerstin Gloe 1 , Karsten Gloe 1 , Gert Bernhard 2 , Jack K. Clegg 3 , Xue-K. Ji 3 , 

Leonard F. Lindoy 3 

1 Department of Inorganic Chemistry, TU Dresden,01062 Dresden, Germany 

2 Institute of Radiochemistry, Research Centre Dresden-Rossendorf, 01314 Dresden, Germany 

3 School of Chemistry, University of Sydney, NSW, 2006, Australia 

Mixed N,O-donor macrocycles have been shown to result in interesting complexation properties 

towards both cations and anions (the latter on protonation of the macrocycle's nitrogen 

functions).[1-3] 

In the present study the phase transfer properties of 1 toward selected transition metal ions and 

anions have been evaluated by liquid-liquid extraction studies under different pH conditions. 

The order of increasing extraction follows the Irving-Williams series Co(II) < Ni(II) < Cu(II) > 

Zn(II), while the anion extraction is contolled by the Hofmeister series. 

A synergistic enhancement of metal extraction was obtained on exploiting a dual host strategy 

[4] in which the tripodal thiourea host 2 was incorporated in the system. In this case atypical 

anti-Hofmeister behaviour was obtained in which significant metal extraction of chloride or 

sulfate was observed from solution. 

N 

O 

O 

NH 

NH 

HN 

HN 

O 

O 

N 

S 

NH 

S 

NH 

1 2 

[1] N.A. Bailey, D. E. Fenton, S.J. Kitchen, T.H. Lilley, M.G. Williams, P.A. Tasker, A.J. Leong 

and L.F. Lindoy, J. Chem. Soc. Dalton Trans., 1991, 627-637. 

[2] H. Adams, N.A. Bailey, D.E. Fenton, I.G. Ford, S.J. Kitchen, M.G. Williams, P.A. Tasker, A.J. 

Leong and L.F. Lindoy, J. Chem. Soc. Dalton Trans., 1991,1665-1674. 

[3] L. Tušek-Boži, š, Polyhedron 24, 2005, 97–111. 

[4] K. Kavallieratos, R.A. Sachleben, G.J. Van Berkel and B.A. Moyer, Chem. Commun., 2000, 

187-188. 

N 

NH 

NH 

HN 

NH 

S

PSB 81 

Tripodal polyamines as anion receptors: Extraction and structural studies 

Marco Wenzel 1,2 , Bianca Antonioli 1 , Kerstin Gloe 1 , Karsten Gloe 1 , Maria G. Sanchez 1 , Gert 

Bernhard 2 , David J. Bray 3 , Jack K. Clegg 3 , Leonard F. Lindoy 3 

1 Department of Chemistry, TU Dresden,01062 Dresden, Germany 

2 Institute of Radiochemistry, Research Centre Dresden-Rossendorf, 01314 Dresden, Germany 

3 School of Chemistry, University of Sydney, NSW 2006, Australia 

Tripodal polyamines based on the tris(2-aminoethyl)amine (tren) platform are useful complexing 

agents for cations or anions depending on the pH of the solution.[1,2] The binding properties of 

such compounds can be tuned by the addition of aromatic binding groups to the molecule. 

A series of different substituted tren (1-4) derivatives were synthesised and characterised. Here 

we present some recent solvent extraction and liquid membrane transport results that show a 

gradation in anion binding behaviour along I - , Cl - , Br - , CrO4 2- , SO4 2- and PO4 3- . Finally, structural 

aspects of the anion complexes formed will be discussed, with the X-ray structure of the 

bromide complex of ligand 3 being presented. 

R 

1 

2 

3 

4 

NH 

R = 

R = 

R = 

R = 

N 

NH 

NH 

R 

R 

OCH 3 

OC 10H 21 

X-ray structure of [H33][Br3]·Br - 

[1] A.G. Blackman, Polyhedron, 2005, 24, 1-39 

[2] K. Wichmann, B. Antonioli, T. Söhnel, M. Wenzel, K. Gloe, K. Gloe, J.R. Price, L. F. Lindoy, 

A.J. Blake, M. Schröder, Coord. Chem. Rev., 2006, 250, 2987-3003 

Carbohydrate Dynamic Combinatorial Libraries for Quadruplex DNA 

Recognition 

Jean-Luc Wietor, Anthony Bugaut, Katja Jantos, Shankar Balasubramanian, Jeremy K. M. 

Sanders 

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW. 

E-mail: jlw48@cam.ac.uk 

A Dynamic Combinatorial Library (DCL) [1] made from small building blocks can change its 

composition upon introduction of a template molecule, with increases in the concentration of 

successful template-binding library members. Disulfides, obtained from the oxidation of thiols, 

are often used to provide a stable yet exchangeable bond between building blocks. 

We use this concept to probe the affinity of carbohydrates to quadruplex-DNA [2], a biomolecule 

that plays central roles in cell ageing processes, expression of oncogenes and cancer. The 

selective binding of quadruplex DNA over duplex DNA or of one particular quadruplex 

conformation or sequence remains a major goal in this area. 

We present a system based on a quadruplex-binding macrocycle [3], several simple 

carbohydrate building blocks and glutathione, a thiol-containing tripeptide which acts as a 

disulfide exchange mediator. Upon addition of the quadruplex template, we observed an 

increase of macrocycle-carbohydrate species at the expense of other library members (Figure 

1). 

O 

Quadruplex 

O 

O 

G 

G Template 

G 

G 

O 

Building blocks: 

O 

O 

DCL 

G 

O 

G 

O 

Amplification 

carbohydrate macrocycle G glutathione 

Figure 1: Schematic of a DCL and amplification of successful quadruplex binders. 

This system allowed us (a) to demonstrate the specific attractive interactions between 

quadruplex DNA and neutral carbohydrates and (b) to probe effects of carbohydrate size and 

anomeric isomerism on binding strength. 

[1] 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 

[2] S. Burge, G. N. Parkinson, P. Hazel, A. K. Todd and S. Neidle, Nucleic Acids Res., 2006, 34, 

5402-5415 

[3] K. Jantos, R. Rodriguez, S. Ladame, P. S. Shirude and S. Balasubramanian, J. Am. Chem. 

Soc., 2006, 128, 13662-13663 

O 

G 

G 

PSB 82

Synthesis of Functional Aromatic Oligoamides 

Fred Campbell, Jeff Plante, Barbora Malkova and Andrew Wilson 

 

 

School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, United Kingdom 

Astbury Centre for Structural Molecular Biology, University of Leeds, Woodhouse Lane, Leeds 

LS2 9JT, United kingdom 

The design and synthesis of oligomers that adopt well defined conformations [1-3] is a key goal in 

developing functional supramolecular architectures that mimic those found in nature. Currently, 

methods to synthesise abiotic oligomers with different sequences of monomers are lacking. 

In this presentation we will discuss our initial studies on the synthesis of O and N-alkylated 

O 

NH2 O 

R3 

O 

NH 

NH 

O R2 

O-alkylated 

trimers 

O R1 

O 

HN 

O 

N 

R 3 

N 

N-alkylated 

macrocycles 

CO2H CO2H Figure 1. Trimeric N and O alkylated aromatic oligoamide scaffolds 

R 2 

N-alkylated 

trimers 

aromatic oligoamides 

derived from paminobenzoic 

acid (Figure 

1). We will highlight the 

subtle role that the 

conformation of secondary 

and tertiary amides can 

play in adopting helical or 

extended conformations 

and the role of hydrogenbonding 

in promoting 

extended structures. We 

will also discuss how short 

foldamers can be used to 

access macrocycles with a 

regiospecific arrangement 

of functional groups. 

Finally the potential for these architectures to act as inhibitors of protein-protein interactions [3] 

will be discussed. 

[1]S.H.Gellman,Acc. Chem. Res. 1998, 31, 178-180. 

[2] I. Huc, Eur. J. Org. Chem. 2004, 17-29. 

[3] Z.-T. Li, J.-L. Hou, and H.-P. Yi, Chem. Asian. J., 2006, 1, 766-778. 

[3]H.YinandA.D.Hamilton,Angew. Chem.Int. Ed. 2005, 44, 4130-4163. 

R 1 

R 3 

O 

N 

N 

O 

R 1 

N 

O 

R 2 

PSB 83 

Hexafunctionalized Borromeates 

Claire R Yates, Diego Benítez and J Fraser Stoddart 

California NanoSystems Institute and Department of Chemistry and Biochemistry, 

University of California Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095, USA 

(cryates@chem.ucla.edu) 

The molecular construction of the Borromean Ring (BR) topology has been achieved[1] 

successfully from 18 individual components under dynamic control that characterizes not only 

the noncovalent, but also the coordinative and covalent bonds formed in the molecules. 

Stabilized by a combination of 12 - stacking interactions and 30 dative bonds, six tridentate 

and six bidentate ligands are spatially organized around six Zn(II) ions, such that they react 

preferentially to form molecular BRs in ‘one reaction’ via the formation of 12 imine bonds. 

This molecular BR topology provides a unique symmetrical, nanoscale three-dimensional 

scaffold onto which unique features can be embedded at will. The significance of this research 

is to introduce a further level of sophistication structure-wise into the metal containing BRs via 

the construction (Box) of hexasubstituted borromeates.[2] Two orthogonal approaches have 

been investigated, namely Pre-Assembly Modification – which involves the incorporation of the 

desired functionality on the incipient tridentate ligand, followed by subsequent assembly of the 

rings via metal template-directed synthesis, and Post-Assembly Modification – which first of all 

involves the synthesis of Borromeates with pendant reactive groups attached to the incipient 

tridentate ligand prior to assembly, then modification of the periphery via the introduction of a 

new functional group. Herein, we show the efficient convergent formation of both hexaolefinic 

and hexa-p-tolylpentenyloxy Borromeates. For comparison, in post-assembly terms, efforts 

were made to incorporate six styrenic substrates to a pre-assembled olefin-modified 

Borromeate core employing olefin cross metathesis (OXM).[3] The results conclude that the 

making of hexasubstituted Borromeates divergently, is still an open challenge, as demonstrated 

by the application of ruthenium-catalyzed OXM to a pre-assembled hexaolefinic Borromeate 

core. 

Cross 

Metathesis 

BOX 

Self 

Assembly 

[1] a) K. S. Chichak, S. J. Cantrill, A. R. Pease, S. -H. Chiu, G. W. V. Cave, J. L. Atwood, J. F. 

Stoddart, Science, 2004, 304, 1308–1312; b) S. J. Cantrill, K. S. Chichak, A. J. Peters, J. F. 

Stoddart, Acc. Chem. Res., 2005, 38, 1–9. 

[2] C. R. Yates, D. Benítez, S. I. Khan, J. F. Stoddart, Submitted. 

[3] a) R. H. Grubbs, Tetrahedron, 2004, 60, 7117–7140; b) A. K. Chatterjee, T. -L. Choi, D. P. 

Sanders, R. H. Grubbs, J. Am. Chem. Soc., 2003, 125, 1136011370. 

+ 

PSB 84

PSB 85 

Templated Synthesis of Large Macrocyles by Ring-Closing Metathesis 

Yeni, Markus Albrecht 

Institut für Organische Chemie der RWTH Aachen, Landoltweg 1, D-52056 Aachen, Germany 

yeni@oc.rwth-aachen.de 

The synthesis of large macrocyclic molecules is still considered as a challenge. [1] 

Recently, we developed an efficient way to synthesize such macrocycles, which contain 

intraanular functional groups (figure 1). 

NH 2 

O 

O 

O 

O 

H 2N 

Figure 1: Macrocyles with intraanular nitrogen functional groups. 

The synthetic strategy we applied is shown in scheme 1. We chose an organic molecule as a 

template to facilitate the cyclization by ring-closing metathesis. The reaction between the 

template and the compound induced a labile covalent bond in the precursor of the macrocycle 

and after the cyclization we can easily remove the template by breaking the covalent bond, 

which is connecting the template to the macrocycles. 

Scheme 1: Synthetic strategy to prepare funtionalized macrocycles. 

[1] D. H. Camacho, E. V. Salo, Z. Guan, Org. Lett., 2004, 6, 865-868 

O 

R NH2 H2N R 

O 

(CH 2) 20 

(CH 2) 20 

R = H, t-Bu 

O 

O 

Application of benzopyrroles in the construction of anion receptors 

Tomasz Zieliski, a Pawe Dydio a,b and Janusz Jurczak a,b 

a 



b 

Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland 

PSB 86 

Coordination chemistry of anions is one of the most active fields of supramolecular chemistry.[1] 

In this research area, construction of neutral receptors that bind anions by hydrogen bonds has 

been a subject of extensive exploration. In contrast to other hydrogen bond donor groups, 

pyrrole moiety does not contain a built-in hydrogen bond acceptor, thus a risk of unfavorable 

intramolecular bonds is diminished. Benzopyrroles preserve this advantageous feature, and in 

addition they have interesting spectroscopic properties. They are also more acidic, and as a 

result, they can interact with anions more strongly. These aspects make benzopyrroles an 

attractive skeleton for construction of anion receptors.[2] We would like to present our studies of 

ligands containing indole, carbazole or dipyrrolonaphthalene subunits. 

We used indole-7-amine as an alternative to aniline for the preparation of amide-based ligands. 

The replacement of aniline with indolamine can enhance anion binding for more than five times, 

due to the presence of indole NHs as additional binding sites. Versatility of indoleamines as 

synthons was demonstrated by the preparation of indolyl analogues of dipyrrolomethane-based 

ligands. 

Advantages of benzopyrroles as rigid skeletons for construction of anions receptors are 

illustrated undoubtedly by bisamides derived from 1,8-diaminocarbazole. It turned out that these 

simple acyclic receptors, equipped with just three anchoring points, bind anions strongly even in 

the very competitive media, and that they are much better receptors than their pyrrole 

analogues. 

Further enrichment of ligands with additional binding sites does not necessary increase affinity 

towards anions, as for example, derivatives of dipyrrolonaphthalene bind anions only 

moderately. However, due to the presence of naphthalene chromophore, the 

dipyrrolonaphthalene-based receptors can act as optical sensors for anions. We observed 

remarkable fluorescence enhancement upon complexation of dihydrogenphosphate. 

By comprehensive structural analysis of our model ligands, we were able to resolve the 

relationship between their structure and binding properties. 

[1] J. L. Sessler, P. A. Gale, W. S. Cho, Anion Receptor Chemistry, The Royal Society of 

Chemistry, Cambridge, 2006. 

[2] M. J. Chmielewski, M. Charon, J. Jurczak, Org. Lett. 2004, 6, 3501-3504; P. Pitek, V. M. 

Lynch, J. L. Sessler, J. Am. Chem. Soc. 2004, 126, 16073-16076; D. Curiel, A. Cowley, P. D. 

Beer, Chem. Commun. 2005, 236-238; X. M. He, S. Z. Hu, K. Liu, Y. Guo, J. Xu, S. J. Shao, 

Org. Lett. 2006, 8, 333-336.

N,N-bis(2-aminoethyl)-2,2-bipyridine-3,3-dicarboxamide: A Novel 

Fluorescent Chemosensor For Divalent Nickel and Copper 

Rati Kanta Bera, B. K. Kanungo and Minati Baral* 

Department of Chemistry, Sant Longowal Institute of Engineering & Technology, Longowal, 

Punjab-148106, India 

PSB 87 

A novel bipyridyl based fluorescent system, N,N-bis(2-aminoethyl)-2,2-bipyridine-3,3dicarboxamide 

(BABD) for sensing divalent nickel and copper has been synthesized and 

characterized through elemental analyses and spectral (UV-VIS, IR, 1 H NMR and 13 C NMR) 

data. The lowest energy molecular geometry of BABD was obtained through empirical and 

quantum mechanical method. Theoretical UV–VIS, IR and 1 H NMR spectral data were 

calculated from the energy-minimized structure (Fig. 1) by applying semi-empirical ZINDO, PM3 

and TNDO/2 method, respectively and were compared with the experimental data. The 

fluorescence behavior of this system has been studied in the absence and in the presence of 

the salt of several transition metal ions. On excitation at 289 nm the system gives a maximum 

emission band at ~379 nm and two shoulders at 410 and 442 nm. It was observed that BABD is 

highly specific and selective towards divalent nickel and copper and gives sensitive response of 

fluorescence enhancement in aqueous solution. The emitting behavior of the BABD over the pH 

range 2 to 11 was investigated through a spectrofluorimetric titration experiment. 

Fig 1. Energy minimized structure of BABD 

The fluorescence band of BABD at ~379 nm showed dramatic enhancement with increase in pH 

whereas in low pH (

PSB 89 

Direct C-C coupling of 1,2,4-Triazin-5(2H)-ones with Benzoannelated Crown 

Ethers in the Synthesis of Amino Acid's Receptors. 

Nadezhda A. Itsikson , Mikhail I. Kodess , Anatoly I. Matern b , Yuri Yu. Morzherin b Oleg N. 

Chupakhin a 

a I. Postovsky Institute of Organic Synthesis of RAS, S.Kovalevskaya/Akademicheskaya, 22/20, 

620219, Ekaterinburg, 

b Urals State Technical University, Chemical Technology Faculty, Mira, 28, 620002, 

Ekaterinburg, Russia 

Molecular recognition of bipolar organic molecules such as amino acids is a rapidly growing 

area of research due to their potential application as sensors for monitoring of biological 

systems and as selective extractants. 

A convenient method for one-step modification of hetarenes by different macrocyclic compound 

based on the methodology of nucleophilic addition to unsubstituted carbon atom in azines has 

been elaborated.1-3 

For example reaction of benzocrown ether 1 with 3-Ph-1,2,4-triazin-5(2H)-one 2 results in the 

coupling of two different complexating centres in the one molecule, so can be effectively applied 

for design of heteroditopic receptors. 

The complexating properties of obtained compounds toward amino acids have been studied by 

used various methods. The results of extraction of amino acids by obtained compounds are 

shown in the figure 

3 

This work was financially supported by the grants Russian Foundation of Basic Researches 05- 

03-32094, 05-03-32085. 

[1] V.N. Charushin, O.N. Chupakhin. Pure and Applied Chem., 2004, 9, 1621. 

[2] G.L. Rusinov, D.G. Beresnev, N.A. Itsikson, and O.N. Chupakhin, Heterocycles, 2001, 2349. 

[3] D.G. Beresnev, N. A. Itsikson, O.N. Chupakhin, V.N. Charushin, M.I. Kodess, A.I. Butakov, 

G.L. Rusinov, Yu.Yu. Morzherin, A.I. Konovalov, and I.S. Antipin, J.Org.Chem., 2006; 71, 21, 

8272. 

PSB 90 

Synthesis, Spectroscopic, Potentiometric Studies and Molecular Modeling 

of a New Biomemitic Siderophore Analogue 

Suban K. Sahoo, Minati Baral and B. K. Kanungo 

Department of Chemistry, Sant Longowal Institute of Engineering & Technology, Longowal 

148106, India 

Siderophores are low molecular weight molecules produced by bacteria and fungi for iron 

uptake, which contain either hydroxamate or catechol binding units and the complexes have six 

oxygens in an octahedral sphere about the Fe(III). Among all siderophores, the catechol based 

enterobactin is known to form very strong chelate with highest formation constant and its 

efficiency as Fe(III) ion scavenger and carrier has stimulated the synthesis of many analogues 

containing three catechol units in tripod with respect to their use in iron overload treatment and 

to elucidate biological process [1]. Keeping these facts in view, two novel enterobactin 

analogues: cis,cis-1,3,5-tris[(2,3-dihydroxybenzylidene)aminomethyl]cyclohexane (L 1 ) and 

cis,cis-1,3,5-tris[(2,3-dihydroxybenzyl amine) aminomethyl]cyclohexane (L 2 ) (Figure 1) 

containing one catechol unit in each arm of a tripodal amine, cis,cis-1,3,5tris(aminomethyl)cyclohexane 

have been investigated as a chelators for iron(III) through pH 

potentiometric and spectrophotometric methods in an aqueous medium of 0.1N ionic strength 

and 298 K. 

HO 

OH 

N 

H 

H 

N 

OH 

OH 

N 

HO 

HO 

OH H 

N 

NH 

OH 

OH 

N 

H 

HO 

L HO 

H H 

H 

H 

1 L2 HO 

N 

O 

OH 

N 

Fe 

O 

HO 

N 

O 

HO 

N 

H 

O 

O 

N 

H 

O 

Fe 

O 

N 

H 

O 

O 

FeL1 FeL2 Figure 1. L 1 , L 2 , FeL 1 and FeL 2 . 

Both the ligands form monomeric complexes of the types FeLH3, FeLH2, FeLH and FeL. Ligand 

L 2 (log KML = 27.1) forms stable complex as compared to L 1 (log KML = 20.4). The step-wise 

formation of complexes was explained through the results obtained from potentiometric titration 

and spectrophotometric measurements, and using molecular modeling calculations. Ligand L 1 

showed the potential to coordinate iron(III) through imine nitrogens and catecholic oxygens at 

ortho to form a tris(iminophenolate) type complex whereas L 2 formed a tris(catecholate) type 

complex (Figure 1). Molecular modeling calculations suggested that, ligand L 1 undergoes ringflipping 

from most stable equatorial conformation to axial conformation during complexation 

whereas no such conformational changes were depicted in L 2 . 

[1] J. Neilands, J. Biol. Chem., 1997, 270, 26723.

Synthesis of new Calixarenic Dendron 

Mouna Mahouachi a,b, Rym Abidi, b ,* Jacques Vicens a ,* and Yang Kim, c ,* 

PSB 91 

a 



b 


c 

Department of Chemistry and Advanced Materials, Kosin University, Yeongdo-gu, Busan, 606- 

702 Korea 

The term "dendrimer" comes from two words, dendrite and polymer, the first evoking the 

ramified structure of the molecules, the second the repetition of the same motive. Those 

dendrimers are giant hyperbranched molecules made up of multi-functionnalized central cores, 

branches, internal cavities resulting from the ramifications and end groups. While the dendrons 

are derivatives of dendritic molecules, which, in addition to the surface functionality, cores are 

also functionalized. These nanomaterial have potential applications in different fields (catalyses, 

pharmacy, biochemistry, molecular recognition, environment, optics…). Indeed their tree-like 

structure, allowing to the dendrimers an internal cavities close to the cores, as well as the 

functions located on the surface, makes them suitable as complexing agent for small molecules 

or metals. We have been interested in a new family of dendrimers supporting N–multidentate 

cores and calixarenes, macrocycles with three-dimensional cavities, as branches Within this 

framework six new dendrimers of first generation were synthesized. 

Cation Binding Properties by Ligands Deriving from Calix[4]crown-5- 

azacrown-5 

Mouna Mahouachi a,b , Rym Abidi, b ,* Jong Seung Kim, c ,*and Jacques Vicens a ,* 

PSB 92 

a 



b 


c 


The biphasic extraction and the complexation behavior of monoazacrown-dipropoxy or 

monoazacrown- monoethercrown calix[4]arene were assessed by UV spectrophotometry and 

1 H NMR titration experiments. 

Our principal objective was to observe the amine proton substitution effect on the chelating and 

exractant properties, and to compare azacrown cavities behavior in presence of dipropoxy and 

ethercrown. 

Evidence of ML, ML2 and M2L complex formation with alkali metal ions in acetonitrile was 

obtained.

PSB 93 

The study of cytotoxicity effect and status of oxidative stress of two novel 

synthesized tri-aza macrocyclic diamides as studied in the WI38 cell lines 

Massod Mashhadi Akbar Boojar, a Abbas Shockravi, b 

a Corresponding and author address: Dr. Massod M. A. Boojar, Department of Biology, 

Faculty of Sciences, Tarbiat Moallem University, No: 49, Mofateh Avenue, 

P.O.Box:15614. Tehran. Iran. 

Tel & Fax: + 9821-88848940 E-mail: aboojar@yahoo.com 

b Dr. Abbas Shockravi, Faculty of Chemistry, Tarbiat Moallem University, No: 49, 

Mofateh Avenue, P.O.Box: 15614. Tehran. Iran. 

Two tri-aza macrocycles as diamide derivatives of macrocyclic compounds, posses a 

hydrophilic cavity surrounded by hydrophobic ring, which enable them to diffuse cell membrane 

and interfere with different living systems. In this study, we comparatively evaluated cytotoxicity 

effects of tri-aza dibenzo sulfoxide (TSD) and dibenzo sulfide (TTS) macrocyclic diamides in a 

range of doses (0.25 to 8 mM) and the role of oxidative stress in WI38 cells culture. 

We assessed the effects of these substances on ROS level, cellular viability, apoptosis events, 

activity of antioxidant enzymes including; superoxide dismutase (SOD), glutathione peroxidase 

(GPX), catalase (CAT), and on some macromolecules oxidative damages end-products; 

malondialdehyde (MDA), dityrosine and 8-Hydroxy-deoxyguanosine (8-OH-dG) that were 

assessed by spectrometry and HPLC methods. Both compounds revealed cytotoxicity effects 

on cell culture particularly at doses >1 mM after 24 h incubation. They decreased cellular 

viability and significantly promoted ROS generation, increased enzyme activities and enhanced 

oxidative damages in which TSD was more effective. Treatment of cells with each compound 

alone increased significantly the percent of apoptotic events at 2 and then 4 mM. Co-treatment 

with alpha-tocopherol (á-TCP) drastically reduced these events. Cells exposure with mixture of 

30 µM alpha–tocopherol and 8 mM of each compound exerted significant decrease on the 

levels of ROS, enzyme activities and oxidative damage biomarkers. 

As conclusion, our study documented the oxidative radicals forming ability of the studied 

compounds and further strengthened the documentation of their cytotoxicity effects through 

lipids, proteins and DNA oxidation damages. 

Key words: Tri-aza macrocyclic diamides; WI38 cells; Cytotoxicity; Antioxidant enzymes; 

Malondialdehyde; Dityrosine; 8-OH-dG; á–tocopherol. 

Gurbanov, K. G.; Paperno, S. A.; Bogomaz, S. A. Acta Physiol. Pharmacol. Bulg. 

1992, 18,27. 

Shockravi, A.; Bavili, T. S. Journal of Inclusion Phenomena Macrocyclic Chem. 

2005, 52, 223. 

Pederson, C. J. Sci. 1988, 241, 156. 

Mcphee, M. M.; Kerwin, S. M. Bioorg. Med. Chem. 2001, 9, 2809. 

Carolina, M.; Massimo, F.; Venera, C. Neuroscience letters 2002, 329, 21. 

PSB 94 

Synthesis of photocromic crown containing benzo- and naphtopyranes 

Sergey V. Paramonov a , Olga A. Fedorova a , Valerii P. Perevalov a , Vladimir Lokshine b , 

André Samat b 

a 

Mendeleev University of Chemustry and Technology of Russia, 9, Miusskaya sqr., Moscow, 

Russia 125047, e-mail: par.serg@rambler.ru 

b 

Université de la Méditerranée, Faculté des Sciences de Luminy, UMR 6114, Case 901, 

Cedex 9, Marseille, France 13288 

One of the interesting approaches to modify the photochromic compounds able to change color 

under light irradiation is to introduce an ionophoric moiety (e.g. crown ether) into the molecule. 

Due to such a structure the systems involved are able to reveal considerable changes in 

spectral and kinetic properties when coordinating with metal ions. These properties are very 

important in modern technologies of creating mass storage devices and molecular electronics. 

Mn+ hv 

Photochromic 

transformation 

Photochrome 

Crownether 

Complexation 

This work represents syntesis and investigations of novel benzo- and naphthopyranes 

containing 18-crown-6 and 15-crown-5-ethers. Due to the molecule structure it is suggested that 

complexation and phototransformation processes will influence to each other considerably. Key 

reaction of these schemes is the obtaining of chromene structure from crown containing phenol 

or naphthol. Two methods were applied: using 1,1-diphenylpropargyl alcohol and - 

phenylcinnaroic aldehyde as main reagents. 

OH 

Ph 

Ph 

Ph 

Ph 

OH 

CH 

O 

O Ph 

It was showed that all compounds synthesized reveal photochromic properties and they depend 

on the crown ether moiety position in the molecule. The results of investigations of the influence 

of complexation process on the phototransformation of some substances involved are also 

given. 

Acknowledgment. All investigations were carried out under support by grant RFFI (No. 05-03- 

32268) and exchange program CNRS-RAS. 

Ph

PSB 95 

Photoresponsive Malachite Green Derivative and Photoinduced Vesicle 

Fusion 

Ryoko M. Uda a , Keiichi Kimura b 

a Department of Chemical Engineering, Nara National College of Technology, Yata 22, Yamatokoriyama, 

Nara 639-1080, Japan 

b Department of Applied Chemistry, Faculty of Systems Engineering, Wakayama University, 

Sakae-dani 930, Wakayama 640-8510, Japan 

Amphiphiles contain hydrophilic and hydrophobic moieties and spontaneously form assemblies 

in aqueous media. Control of molecular assembling can be achieved by shifting the balance of 

hydrophobicity and hydrophilicity. Amphiphiles containing a photochromic moiety can undergo 

conformational and electronic changes upon photoirradiation, offering an attractive modulation 

of assemblies. We have designed a Malachite Green derivative carrying a long alkyl chain (Fig. 

1). The Malachite Green derivative, when ionized photochemically, exhibits hydrophilicity by its 

triphenylmethyl cation and hydrophobicity by its long alkyl chain. Consequently, the long-alkylchain 

Malachite Green generates an amphiphilicity on the lipophilic compound by 

photoirradiation. The photogenerated electrical charge on the head group is expected to provide 

assemblies with a drastic effect. Actually, we have observed significant changes induced by the 

long-alkyl-chain Malachite Green in the critical micelle concentration and the solubility of oily 

substance into micelle solution 1,2 . 

O 

H3C CH3 N 

Here we present the photoinduced structural change in vesicles containing the long-alkyl-chain 

Malachite Green derivative. The Malachite Green derivative is embedded in the vesicle bilayer 

consisting of cationic and anionic surfactants. Photoirradiation on the Malachite Green 

derivative destabilizes the vesicle bilayer, resulting vesicle fusion (Fig. 2). We discuss the 

photoinduced vesicle fusion by fluorescence analysis and transmission electron microscopy. 

[1] R. M. Uda, M. Oue, K. Kimura, Chem. Lett., 2004, 33, 586-587. 

[2] R. M. Uda, K. Kimura, Bull. Chem. Soc. Jpn., 2005, 78, 1862-1867. 

C CN 

N 

H3C CH3 

UV 

Heat 

Hydrophobic group 

Hydrophiric group 

H3C N CH3 O C+ 

+ CN - 

N CH3 H3C Figure 1. Photo-generated amphiphilicity on the long-alkyl-chain Malachite Green derivative. 

Malachite Green derivative 

UV 

Generated amphiphilicity 

Bilayer destabilization Vesicle fusion 

Figure 2. Conceptual represetion of photoinduced bilayer destabilization and subsequent vesicle fusion 

Stable terbium probes highly luminescent in aqueous solutions : 

macrocyclic ligands derived from N,C-pyrazolylpyridine 

Isabelle Nasso, C. Galaup, B. Mestre, C. Picard 

Laboratoire de Synthèse et Physicochimie de Molécules d’Intérêt Biologique, CNRS UMR 5068, 

Université Paul Sabatier, 31062 Toulouse cedex 09, France 

Some organic ligands can act as light collectors (antenna) transferring intra-molecularly the 

excitation energy to the lanthanide ion (emitter), yielding highly luminescent lanthanide 

complexes. [1] Eu(III) systems working in aqueous solutions are widely used for time-resolved 

measurements in high throughput assays (clinical diagnostic assays or drug development) or 

fluorescence microscopy. [2] 

Recently, we reported the efficient sensitization of Tb(III) ion by an open chain polyaminocarboxylate 

ligand based on the N,C-pyrazolylpyridine chromophore as antenna (compound 

1). [3] Here we present the synthesis of new macrocyclic ligands based on this chromophoric unit 

(compounds 2-4), and the luminescence properties of the corresponding Tb(III) complexes. 

1 

N 

N 

N 

N 

HO2C CO2H HO2C 2 

HO 2C 

N 

N 

N 

N 

N 

N 

CO 2H 

N 

CO 2H 

CO 2H 

R 

N 

N 

N 

HO 2C 

N 

N 

3, R = H 

N 

N 

4, R = COOH 

CO 2H 

CO 2H 

PSB 96 

These complexes are highly luminescent in aqueous solution: the decays of the Tb( 5 D4) 

luminescence are long lived ( 1.70 ms) and high quantum yield ( 40 %) were obtained 

following excitation of the -* state of the pyrazolylpyridine unit. The photophysical properties 

of these complexes will be discussed with regard of the mechanism of the ligand-to-metal 

energy transfer process and will be compared with those derived from 2,2’-bipyridine 

analogues. Their kinetic stability in aqueous solutions will also be reported. 

[1] P. G. Sammes and G. Yahogliou, Nat. Prod. Rep., 1996, 13, 1-28. 

[2] I. Hemmila and V. Laitala, J. Fluorescence, 2005, 15, 529-542. 

[3] C. Picard, N. Geum, I. Nasso, B. Mestre, P. Tisnès, S. Laurent, L. Vander Elst, Bioorg. Med. 

Chem. Lett., 2006, 16, 5309-5312.

PSB 97 

Development of innovative sol-gel coatings for solid phase microextraction 

based on quinoxaline-bridged cavitands 

Paolo Betti a , Federica Bianchi b , Franco Bisceglie b , Enrico Dalcanale a , Monica Mattarozzi b 

a Dipartimento di Chimica Organica ed Industriale, Università di Parma, Viale G.P. Usberti 17/A, 


b Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università 

di Parma, Viale G.P. Usberti 17/A, 43100 Parma, Italy 

A problem of paramount importance in the field of analytical chemistry is related to the 

development of innovative materials to be used as new devices both in the separation field and 

for sample preparation techniques, thus enhancing the selectivity as well as the overall 

performances of the system under investigation with regard to target analytes or specific 

classes of compounds. In particular, the use of innovative materials, capable of highly selective 

interactions with the analytes (avoiding co-extraction of interferents from the matrix), turns out 

particularly interesting in all those cases in which commercially available materials do not allow 

an adequate extraction of the compounds under investigation. As far solid phase 

microextraction (SPME) is concerned, the major challenge is to improve the capabilities of this 

technique by developing novel coatings characterised by high thermal, chemical and pH 

stability. New technologies are required in order to obtain chemically bonded materials onto the 

silica surface. Sol-gel technology [1] has been recently proposed as innovative alternative to the 

commonly utilized grafting procedures owing to its capabilities of producing a great variety of 

inorganic networks from silicon or metal alkoxide monomer precursors under mild conditions. 

In this study, cavitands are proposed as supramolecular receptors in order to develop materials 

characterized by high selectivity for the sampling of toxic compounds [2]. Owing to the 

capabilities of providing specific interactions with target analytes, quinoxaline-based cavitands 

have been properly tuned up and introduced in a sol-gel process, thus producing highly stable 

and selective materials to be used as trapping devices for volatile organic compounds. 

[1] O. Lev, Anal. Chem, 1995, 67, 22A–30A 

[2] F:Bianchi, R. Pinalli, F. Ugozzoli, S. Spera, M. Careri, E. Dalcanale, New J. Chem., 2003, 

27, 502–509

Aguilar A. PSA 84 

Akkaya E.U. PSA 6 

Akkaya E.U. PSA 33 

Albericio F. PSB 42 

Alberti G. PSA 38 

Albrecht M. PSB 85 

Alessio E. IL 3 

Alessio E. PSA 27 

Alfimov M.V. PSA 89 

Alfimov M.V. PSB 59 

Alfonso I. PSA 1 

Aliev A.E. PSA 65 

Allen M.C. PSA 34 

Allouche L. OP 14 

Ambard C. PSA 75 

Ambrosi G. PSB 88 

Amendola V. PSA 13 

Amendola V. PSB 17 

Amendola V. PSB 62 

Amirov R. PSA 87 

Amorós P. PSB 53 

Amorós P. PSB 5 

Anisimov A. V. PSB 73 

Anisimov A. V. PSA 96 

Anisimov A. V. PSB 66 

Antipin I. PSA 87 

Antonioli B. PSB 81 

Anzenbacher Jr. P. OP 13 

Aprahamian I. PSB 27 

Arduini A. PSA 2 

Arduini M. OP 5 

Arduini M. PSA 9 

Arena G. PSA 3 

Arena G. PSB 57 

Arnal-Herault C. OP 2 

Arnaud-Neu F. PSA 75 

Arnaud-Neu F. PSA 76 

Arnaud-Neu F. PSB 10 

Arslanoglu Y. PSA 4 

Arslanoglu Y. PSA 5 

Ascenso J.R. PSB 4 

Atilgan S. PSA 6 

Aznar E. PSB 5 

Aznar E. PSB 53 

Bakirci H. PSA 73 

Bakirci H. OP 4 

Bala K. PSA 65 

Balasubramanian S. PSB 82 

Baldini L. PSA 7 

Ballester P. PSA 27 

Ballester P. PSA 59 

Ballester P. PSB 55 

Baltariu C. PSB 19 

Baral M. PSB 87 

Baral M. PSB 90 

Baranoff E.D. PSB 76 

Baratoiu R.D. PSB 20 

Barboiu M. OP 2 

Barkey N. PSA 8 

Bartsch R.A. PSB 57 

Battanolli G. PSA 9 

Battistini G. PSA 17 

Baù L. PSA 9 

Bazylak G. PSA 10 

Bazzicalupi C. PSA 19 

Becher J. PSB 22 

Beer P.D. PL 5 

Beer P.D. PSB 54 

Index of authors 

Belda R. PSA 11 

Belenguer A. PSA 12 

Belov A.S. PSB 77 

Ben Othman A. PSA 51 

Ben Othman A. PSA 52 

Bencini A. PSA 19 

Benítez D. PSB 84 

Bera R.K. PSB 87 

Bergamaschi G. PSA 13 

Bergin E. PSA 14 

Bergman R.G. OP 18 

Bermejo M.B. PSB 75 

Bernardinelli G. PSA 78 

Bernhard G. PSB 80 

Bernhard G. PSB 81 

Berryman O. PSA 15 

Berryman O. PSA 16 

Betti P. PSA 17 

Betti P. PSB 97 

Beves J.E. PSA 18 

Bian B. PSB 68 

Bianchi A. PSA 19 

Bianchi F. PSB 97 

Bibal B. PSA 20 

Bibal B. PSA 60 

Biesuz R. PSA 38 

Bisceglie F. PSB 97 

Biver T. PSA 19 

Blasco S. PSA 11 

Bobylyova A.A. PSA 96 

Bocheńska M. PSA 21 

Boev N.V. PSA 85 

Boggioni A. PSA 19 

Böhmer V. PSA 76 

Boiocchi M. PSB 3 



Bolte M. PSA 76 

Bonacchi S. PSA 19 

Bond A.D. PSA 82 

Bonomi R. PSA 22 

Borzsonyi G. PSA 23 

Boschetti F. OP 9 

Boschetti F. PSB 50 

Bowman-James K. PL 3 

Bowman-James K. PSA 83 

Bray D.J. PSB 81 

Brisset H. PSA 96 

Brooker S. OP 3 

Brotin T. PSA 53 

Bru M. PSA 1 

Bryantsev V.S. PSA 15 

Brzezinski B. PSB 32 

Brzezinski B. PSB 33 

Bubnov Y.N. OP 17 

Bubnov Y.N. PSB 78 

Buck D. PSA 39 

Bugaut A. PSB 82 

Burguete M.I. PSA 1 

Buschmann H.J. PSB 18 

Buschmann H.J. PSB 19 

Busi M. PSA 67 

Cacciapaglia R. PSA 42 

Cacciarini M. OP 19 

Cacciarini M. PSA 55 

Calero P. PSB 53 

Calisto V. PSA 26 

Caltagirone C. PSA 24

Campbell B. PSA 39 

Campbell F. PSB 83 

Campbell V.E. IL 5 

Cano J. PSB 5 

Cantrill S. J. PSB 39 

Cao X.-Y. PSA 25 

Carasel I.A. IL 6 

Carvalho S. PSA 26 

Casanova M. PSA 27 

Casasús R. PSB 5 

Casnati A. PSA 7 

Castedo L. PSB 42 

Celotti L. PSA 9 

Chalissery L. PSA 39 

Chartres J. PSB 70 

Chaux F. OP 9 

Chichak K.S. PSB 39 

Cho M. IL 9 

Cho Won-Seob PSB 22 

Cho Won-Seob PSA 82 

Cho Won-Seob PSA 84 

Chupakhin O.N. PSB 89 

Chwalisz P. PSA 28 

Clegg J. K. OP 10 

Clegg J.K. PSA 29 

Clegg J.K. PSB 80 

Clegg J.K. PSB 81 

Cohen Y. PSB 34 

Colasson B. PSA 30 

Colasson B. PSB 62 

Colera M. PSB 35 

Coll C. PSB 53 

Collin J.-P. PSA 46 

Collin J.-P. OP 20 

Collins G. PSA 39 

Colucci G. PSA 31 

Comes M. PSB 5 

Compagnin C. PSA 9 

Constable E.C. PSA 18 



Constable E.C. PSB 49 

Constantinescu T. PSB 20 

Coppola C. PSA 32 

Coquière D. PSA 30 

Coskun A. PSA 33 

Costa J. PSB 7 

Costero A.M. OP 12 

Costero A.M. PSB 35 

Coumans R.G.E. IL 2 

Cragg P.J. PSA 34 

Cragg P.J. PSB 4 

Crowley J.D. PSB 63 

Cruz C. PSA 35 

Dacarro G. PSA 36 

Dacarro G. PSA 37 

Dacarro G. PSB 3 

Dacarro G. PSB 30 

D'Agostino G. PSA 38 

Dalcanale E. PSA 67 



Dalcanale E. PSB 97 

Danesi A. PSA 19 

Daschbach M. IL 6 

Davidson G.J.E. PSA 79 

Davis J.T. PSB 45 

Day A. PSA 39 

Day V.W. PSA 83 

de Blas A. PSA 48 

De Napoli L. PSA 32 

Dearden D.V. PSA 40 



Dejsupa C. PSA 40 

Delgado R. PSA 26 



Delgado R. PSB 7 

Denat F. OP 9 

Denat F. PSB 50 

Deutman A.B.C. IL 2 

Develay S. PSB 72 

Di Fabio G. PSA 32 

Di Stefano D. PSA 42 

Diacu E. PSB 19 

Diaz Fernandez Y. PSA 43 

Dichtel W. PSB 27 

Didane Y. PSA 96 

Diederich F. OP 1 

Donnio B. IL 8 

Dorkov P. PSB 13 

Drew M.G.B. PSA 35 

Drew M.M.G. PSA 26 

D'souza R.N. PSA 44 

Duong A. PSA 72 

Durola F. PSA 49 

Durola F. PSA 45 

Durola F. PSB 44 

Durot S. PSA 46 

Dutasta J.-P. PSA 53 

Dydio P. PSA 47 

Dydio P. PSB 86 

Eadington P. PSB 40 

Elemans J.A.A.W. IL 2 

Eller L.R. PSA 84 

Elliott E. IL 6 

Erdyakov S.Y. PSB 78 

Eritja R. PSB 42 

Espinosa E. PSB 11 

Esteban Gómez D. PSA 48 

Fabbrizzi L. PSA 31 

Fabbrizzi L. PSA 13 

Fabbrizzi L. PSB 17 

Fabbrizzi L. PSB 62 

Fages F. PSA 96 

Faimani G. PSA 2 

Faimani G. PSA 7 

Faiz J. PSA 49 

Fang N. PSA 41 

Fanì M. PSB 12 

Fedorov Y.V. PSB 73 

Fedorov Y.V. PSA 50 

Fedorov Y.V. PSB 59 



Fedorova O.A. PSA 50 

Fedorova O.A. PSB 73 


Fedorova O.A. PSB 94 


Fekih Ahme-Abidi R. PSA 51 

Fekih Ahme-Abidi R. PSA 52 

Fekih Ahme-Abidi R. PSB 91 



Félix V. PSA 35 

Félix V. PSB 54 



Fenniri H. PSB 1 

Fenniri H. PSA 23 

Fenniri H. PSB 25 

Fernandez Y.D. PSB 30 

Fitzsimmonds P. PSB 48 

Fogarty H.A. PSA 53 

Fonseca N. PSA 54 

Forgan R.S. OP 16

Formica M. PSB 88 

Francesconi O. PSA 55 

Francesconi O. OP 19 

Franchi P. PSB 12 

Frémond L. PSB 11 

Frey J. OP 20 

Fritsky I. O. PSB 15 

Fucassi F. PSA 34 

Fujiki M. PSA 68 

Fujita N. PSB 2 

Furlow J. PSA 40 

Fusi V. PSB 88 

Fyles T. OP 8 

Galaup C. PSB 96 

Gale P.A. PSA 24 

Gale P.A. PSB 45 

Garcia Rivera D. PSA 56 

García-España E. PSA 11 

García-España E. PSA 61 

Gardner J.S. PSA 41 

Gardner J.S. PSA 70 

Garolfi M. PSA 31 

Gasa T. PSB 27 

Gasparini G. OP 7 

Gasperov V. PSA 93 

Gattuso G. PSA 57 

Gattuso G. PSB 34 

Gaviña P. OP 12 

Gaviña P. PSB 35 

Gaviña P. PSA 11 

Gibb B. PSA 58 

Gibb C.L.D. PSA 58 

Gil G. PSB 55 

Gil Ramirez G. PSA 59 

Gil S. OP 12 

Giorgi C. PSA 19 

Giorgi L. PSB 88 

Givelet C. PSA 20 

Givelet C. PSA 60 

Glasson C.R.K. OP 10 

Gloe K. PSB 80 




Glukhareva T.V. PSB 16 

Gokel G. IL 6 

Golding P. PSA 65 

Goldup S.M. PSB 9 

Goldup S.M. PSB 48 

Gómez-Reino C. PSB 75 

Gonzalez J. PSA 61 

González J. PSA 11 

Gorbatchuk V. PSA 62 

Gottschalk T. OP 1 

Gowans N.D. PSB 48 

Graf E. OP 14 

Granzhan A. PSA 63 

Graziano C. PSA 64 

Greco E. PSA 65 

Gross D. PSA 66 

Gross D.E. PSA 84 

Gruppi F. PSA 67 

Guenet A. OP 14 

Guilard R. PSB 50 

Guilard R. OP 9 

Guilard R. PSB 11 

Gül A. PSB 74 

Gulakova E.N. PSA 89 

Gulakova E.N. PSA 50 

Gulakova E.N. PSB 59 

Guldi D.M. PSB 22 

Guliyev R. PSA 33 

Gurskii M.E. PSB 78 

Hadrava P. PSA 74 

Haidar A. A. PSA 10 

Hailes H.C. PSA 65 

Haley M.M. PSA 16 

Hamuryudan E. PSA 4 

Hamuryudan E. PSA 5 

Handel H. PSB 72 

Harada A. IL 4 

Harada A. PSB 67 

Harada A. PSA 88 








Haraguchi S. PSA 68 

Harmon C. PSA 40 

Harris K. PSA 69 

Harrison R.G. PSA 70 

Harrison R.G. PSA 41 

Harrowfield J. PSA 25 

Hashidzume A. PSB 67 

Hashimoto N. OP 6 

Haukka M. PSB 15 

Havlickovà J. PSA 71 

Hay B.P. PSA 15 

Heitz V OP 20 

Heitz V. PSB 76 

Helzy F. PSA 72 

Henderson D.K. OP 16 

Hennig A. PSA 73 

Hennig A. OP 4 

Hermann P. PSA 71 


Hermann P. PSB 46 


Herrera A.M. IL 9 

Herschbach H. PSB 10 

Hirsch A. PSB 43 

Hlinka J. PSA 74 

Hodacova J. PSA 74 

Hollósi M. PSB 71 

Hoseini H. PSB 60 

Hosseini M.W. OP 14 

Housecroft C. E. PSB 49 

Housecroft C.E. PSA 18 



Huang W.H. OP 11 

Hubscher V. PSA 75 

Hubscher V. PSA 76 

Hunter C.A. OP 3 

Huszthy P. PSA 77 

Huszthy P. PSB 71 

Hutin M. PSA 78 

Hutin M. IL 5 

Ienco A. PSA 55 

Iengo E. PSA 79 

Iengo E. IL 3 

Iengo E. PSA 27 

Iglesias-Sánchez J.C. PSB 45 

Intenza R. OP 15 

Iqbal K.S.J. PSA 34 

Isaacs L. OP 11 

Itsikson N.A. PSB 89 

Itsikson N.A. PSB 16 

Izzo I. OP 21 

Jadhav V.D. PSA 80 

Jameson G.B. OP 3 

Jantos K. PSB 82 

Jarosz M. PSA 81 

Jaun B. OP 1 

Jensen F. PSB 22

Jensen L.G. PSA 82 

Jeppesen J.O. IL 8 

Jeppesen J.O. PSA 82 

Jeppesen J.O. PSB 22 

Ji X.-K. PSB 80 

Jiménez H. PSA 11 

Jobin E. PSA 76 

Johnson C.A. PSA 16 

Johnson D.W. PSA 15 

Johnson D.W. PSA 16 

Johnson K. A. PSA 84 

Jolliffe K.A. PSA 29 

Jonusauskas G. PSB 73 

Jonusauskas G. PSA 96 

Jost P. PSA 75 

Jounauskauskas G. PSA 50 

Jurczak J. PSA 81 

Jurczak J. PSA 47 

Jurczak J. PSB 86 




Kádár M. PSA 77 

Kaden T.A. PL 1 

Kalchenko V.I. PSB 6 

Kalisiak J. PSB 38 

Kalisiak J. PSB 61 

Kállay M. PSB 35 

Kang S.O. PSA 83 

Kannupal S. PSA 58 

Kanungo B.K. PSB 90 

Kanungo B.K. PSB 87 

Kardashev S.V. PSA 96 

Karnas E. PSA 84 

Katayev E. PSA 85 

Katayev E. IL 8 

Kato T. PSB 76 

Kepert C.J. PSA 18 

Kim J.S. PSB 92 

Kim J.S. PSA 51 

Kim J.S. PSA 52 

Kim L. PSB 19 

Kim Y. PSB 91 

Kimizuka N. OP 6 

Kimura K. PSB 95 

Kodessа M.I. PSB 89 

Kolar Z. I. PSB 46 

Kolesnikov G.V. PSA 85 

Koner A.L. PSA 86 

Konovalov A. PSA 87 

Korda T.M. PSB 6 

Korendovych I.V. IL 9 

Korovin Y. PSA 87 

Kost S. PSA 87 

Kostin G.A PSB 6 

Kotek J. PSA 94 



Kraus T. OP 20 

Kropotina P.E. PSB 16 

Kuad P. PSA 88 

Kubíček V. PSA 71 

Kubíček V. PSB 46 

Kubik S. IL 12 

Kubik S. PSB 47 

Kubinyi M. PSB 35 

Kulikov N.S. PSB 66 

Kuznetsov N. PSB 8 

Kyritsakas N. OP 14 

Labazava I. PSA 89 

Lamb J.D. IL 10 

Lamb J.D. PSA 70 

Lamb J.D. PSA 41 

Lan Y. OP 3 

Lankshear M.D. PSB 54 

Le Baccon M. PSB 72 

Lebed E.G. PSB 78 

Lee J.T. PSA 84 

Lee J.W. PSA 51 

Lee J.W. PSA 52 

Lehn J.-M. PL 8 

Lehn J.-M. PSA 25 

Leigh D.A. PSB 9 


Leigh D.A. ICA 


Lena S. PSA 90 

Lesińska U. PSA 21 

Leska B. PSA 91 

Levin B. IL 6 

Lewis D. PSA 14 

Li C. PSA 68 

Li F. PSB 7 

Li R. IL 6 

Licchelli M. PSA 31 

Licchelli M. PSB 75 

Licen S. OP 21 

Light M.E. PSB 45 

Light M.E. PSA 24 

Lima L.M.P. PSA 92 

Lin T. PSA 93 

Lindoy L.F. OP 10 

Lindoy L.F. PSB 80 

Lindoy L.F. PSB 81 

Lindoy L.F. PSA 29 

Liu S. OP 11 

Liu S. PSA 12 

Llinares J. M. PSA 61 

Llinares J.M. PSA 11 

Lloris J.M. PSB 53 

Lokshine V. PSB 94 

Longo E. PSB 57 

Lubal P. PSA 94 

Luboch E. PSB 79 

Lucarini M. PSA 95 

Lucarini M. PSA 64 

Lucarini M. PSB 12 

Luis S.V. PSA 1 

Lukeš I. PSB 46 

Lukovskaya E. PSA 96 

Luong H. OP 8 

Lusby P.J. PSB 63 

Lusby P.J. PSB 9 

Lynch V.M. PSA 66 




Macedi E. PSB 88 

Madalan A. PSA 25 

Magda D. PSB 43 

Magda D.J. PSA 84 

Magdesieva T.V. PSB 77 

Mahouachi M. PSB 91 

Mahouachi M. PSB 92 

Makarenko I.G. PSB 78 

Makeiff D.A. PSB 1 

Maksimov A.L. PSA 96 

Malik S. PSB 2 

Malkova B. PSB 83 

Mancin F. PSA 22 

Mancin F. OP 5 

Mancin F. PSA 9 

Mandolini L. PSA 42 

Mangano C. PSA 43 

Mangano C. PSB 36 

Mangano C. PSB 3 

Marcos M.D. PSB 5 

Marcos M.D. PSB 53

Marcos P.M. PSB 4 

Marmois E. PSA 96 

Marrot J. PSA 30 

Martínez-Máñez R. PSB 5 

Martínez-Máñez R. PSB 53 

Mascareñas J. L. PSB 42 

Masci B. PSB 37 

Mashhadi A. Boojar M. PSB 93 

Mashukov V. PSB 6 

Mashura M.M. PSA 89 

Mashura M.M. PSA 50 

Mashura M.M. PSB 59 

Masiero S. PSA 64 

Masiero S. PSA 90 

Masiero S. PSB 31 

Massera C. PSA 2 

Matern A. I. PSB 16 

Matern A.I. PSB 89 

Mateus P. PSB 7 

Mattarozzi M. PSB 97 

Matveev E. PSB 8 

Maulucci N. OP 21 

McAllister F. OP 16 

McBurney R.T. PSB 9 

McBurney R.T. PSB 63 

Meehan G.V. OP 10 

Meisner J.S. PSA 15 

Melfi P. PSA 85 

Melfi P. IL 8 

Mellah B. PSB 10 

Meshcheryakov D. PSA 76 

Mestre B. PSB 96 

Metrangolo P. OP 15 

Metrangolo P. PSA 57 

Meyer F. OP 15 

Meyer M. PSB 11 

Mezzina E. PSA 95 

Mezzina E. PSB 12 

Michel S. PSA 76 

Micheloni M. PSB 88 

Milaeva E.R. PSB 77 

Mileo E. PSA 95 

Mitewa M. PSB 13 

Miyawaki A. PSB 14 

Miyawaki A. PSB 64 

Mizerev A.A. PSA 96 

Mobian P. PSA 46 

Mocerino M. PSB 40 

Móczár I. PSA 77 

Mognato M. PSA 9 

Moneti G. PSA 55 

Montesarchio D. PSA 32 

Moroz I. PSB 15 

Morzherin Y. PSB 16 

Morzherin Y. PSB 89 

Mosca L. PSB 17 

Mukhopadhyay P. OP 11 

Mustafina A. PSA 87 

Mutihac L. PSB 18 



Mutihac R.C. PSB 18 

Mutihac R.C. PSB 19 

Myles A. PSA 23 

Na'il Saleh PSA 86 

Nakamoto Y. PSB 26 

Nakazono K. PSB 21 

Nasso I. PSB 96 

Natalya Rusakova PSA 87 

Nativi C. PSA 55 

Nativi C. OP 19 

Nau W.M. OP 4 

Nau W.M. PSA 44 

Nau W.M. PSA 73 

Naumann C. PSA 12 

Neuburger M. PSA 69 

Neuburger M. PSA 18 

Nicolaou S. PSA 84 

Nielsen K.A. IL 8 

Nielsen K.A. PSB 22 

Nielsen K.A. PSA 82 

Nikan M. PSB 23 

Nishiyabu R. OP 6 

Nissinen M. PSB 52 

Nitschke J.R. IL 5 

Nitschke J.R. PSB 56 

Nitschke J.R. PSA 78 

Nitschke J.R. PSA 25 

No K. PSB 10 

Nolte R.J.M. IL 2 

Notti A. PSB 34 

Numata M. PSA 68 

Obrocka A.K. PSB 24 

Oderinde M. PSB 25 

Ogden M. PSB 40 

Ogoshi T. PSB 26 

Okumura Y. IL 4 

Okumura Y. PSB 29 

Olsen J.C. PSB 27 

Oluwu O.O. PSB 68 

Organo V. IL 9 

Osaki M. PSB 28 

Oshikiri T. PSB 29 

Otto S. PSA 14 

Otto S. PSB 47 

Ozdemir T. PSA 6 

Pál K. PSB 35 

Palacios M.A. OP 13 

Pallavicini P. PSB 30 

Pallavicini P. PSA 36 

Pallavicini P. PSA 43 



Pandoli O. PSB 31 

Pankiewicz R. PSB 32 

Pankiewicz R. PSB 33 

Pankiewicz R. PSA 91 

Pantcheva I.N. PSB 13 

Pantos G.D. PSA 79 

Pantos G.D. PSA 8 

Paoli P. PSB 88 

Pappalardo A. PSA 57 

Pappalardo A. PSB 34 

Pappalardo S. PSA 57 

Pappalardo S. PSB 34 

Paramonov S. PSB 94 

Parisi M.F. PSA 57 

Parisi M.R. PSB 34 

Parra M. PSB 35 

Parsons S. PSA 29 

Parsons S. OP 16 

Pasotti L. PSB 36 

Pasotti L. PSA 43 

Pasotti L. PSB 30 

Pasquale S. PSB 37 

Pasulka J. PSA 94 

Patroni S. PSB 36 

Patroni S. PSA 43 

Patroni S. PSB 30 

Pawlak M. PSB 38 

Pawlak M. PSB 61 

Pedulli G.F. PSA 95 

Pentecost C. PSB 39 

Perevalov V.P. PSB 94 

Perez-Velasco A. OP 3 

Perret-Aebi L.-E. PSB 63 

Perrin D. PSB 23 

Pesavento M. PSA 38

Peters A.J. PSB 39 

Peters A.J. PSB 46 

Petersen B.M. PSB 22 

Peterson Q.P. IL 10 

Pettersen J. PSB 40 

Petzold C. PSB 63 

Piatek P. PSB 41 

Picard C. PSB 96 

Pieraccini S. PSA 64 

Pieraccini S. PSA 90 

Pieraccini S. PSB 31 

Pikramenou Z. PSA 14 

Pilati T. OP 15 

Pilati T. PSA 57 

Pisagatti I. PSB 34 

Plante J. PSB 83 

Platas-Iglesias C. PSA 48 

Pluth M.D. OP 18 

Plutnar J. PSA 71 

Pochini A. PSA 2 

Poggi A. PSA 13 

Poggi A. PSB 17 

Portela C. PSB 42 

Prados P. PSB 45 

Prangé T. PSA 30 

Preihs C. PSB 43 

Price D.J. PSA 18 

Price J. OP 3 

Prins L. OP 7 

Prodi L. PSA 17 

Profumo A. PSA 38 

Prykhodko O. PSB 44 

Przybylski P. PSB 33 

Quesada-Pato R. PSB 45 

Ramos P.H. IL 2 

Raymond K.N. OP 18 

Raymond K.N. PSA 3 

Reddi E. PSA 9 

Rehor I. PSB 46 

Reinaud O. IL 11 

Reinaud O. PSA 30 

Resnati G. OP 15 

Resnati G. PSA 57 

Reyheller C. PSB 47 

Ribeiro-Claro P.J.A. PSA 54 

Riccardis F.D. OP 21 

Ricci P. PSA 37 

Rissanen K. PSA 61 

Rodriguez Douton M.-J. PSB 62 

Rodríguez-Blas T. PSA 48 

Rodríguez-Docampo Z. PSB 47 

Rodríguez-Muñiz G.M OP 12 

Roelens S. OP 19 

Roelens S. PSA 55 

Rofouei M. K. PSB 58 

Ronaldson V. PSB 48 

Rösel P. PSB 49 

Ross A. PSB 40 

Rossi P. PSB 88 

Rousselin Y. PSB 50 

Rousselin Y. OP 9 

Rousselin Y. PSB 30 

Rowan A. IL 2 

Rubio J. PSA 1 

Rudkevich D.M. IL 1 

Ruiz E. PSB 5 

Rybak-Akimova E. IL 9 

Rzymowski T. PSB 79 

Sahari S. PSB 59 

Sahari S. PSB 58 

Sahoo S.K. PSB 90 

Sakamoto K. PSB 51 

Sakurai K. PSA 68 

Salorinne K. PSB 52 

Saltiel J. PSA 89 

Sama A. PSB 94 

Samorì P. PSA 90 

Samorì P. PSB 31 

Sancenon F. PSB 53 

Sancenón F. PSB 5 

Sanchez M.G. PSB 81 

Sanders J.K.M PSB 82 

Sanders J.K.M. PSA 79 

Sanders J.K.M. PSA 12 

Sansone F. PSA 7 

Santacroce P.V. PSB 45 

Santos S.M.F. PSB 54 

Sarma R. IL 5 

Sarmentero M. A. PSA 59 

Sarmentero Martìn M.A. PSB 55 

Sarova G. PSB 22 

Sauvage J.-P. PSB 44 

Sauvage J.-P. PL 6 

Sauvage J.-P. PSA 45 



Sauvage J.-P. OP 20 

Sauvage J.-P. PSB 76 

Schaffner S. PSA 69 

Schaffner S. PSA 18 

Schilf W. PSB 33 

Schilter D. PSA 29 

Schilter D. OP 10 

Schmidtchen F.P. PSA 80 

Schollmeyer E. PSB 18 

Schroeder G. PSB 32 

Schroeder G. PSA 91 

Schroeder G. PSB 33 

Schultz D. PSB 56 

Schultz D. IL 5 

Scott L.M. PSA 20 

Scrimin P. OP 7 

Secchi A. PSA 2 

Secco F. PSA 19 

Segurado M.A.P. PSB 4 

Seleznev A.A. PSB 66 

Serratrice G. PSB 72 

Sessler J.L. IL 8 

Sessler J.L. PSA 66 



Sessler J.L. PSB 43 



Sessler J.L. PSB 22 

Sgarlata C. PSB 57 

Sgarlata C. PSA 3 

Shamsipur M. PSB 58 

Shaw A.M. IL 8 

Shawuti S. PSB 70 

Sheldrick W. S. PSB 13 

Shepel N. E. PSA 50 

Shepel' N.E. PSB 59 

Shepel' N.E. PSB 59 

Sherman J.C. PSB 23 

Shinkai S. PL 2 

Shinkai S. PSB 2 

Shinkai S. PSA 68 

Shivachev B. PSB 13 

Shockravi A. PSB 60 

Shockravi A. PSB 93 

Shpakovsky D.B. PSB 77 

Silvestre C. PSB 53 

Slovak S. PSB 34 

Smith C. PSB 49 

Smith G.L.N. PSB 68 

Sobczuk A. PSB 61 

Sobczuk A. PSB 38

Socoteanu R. PSB 20 

Solovieva S. PSA 87 

Soriano C. PSA 11 

Soriano C. PSA 61 

Soto J. PSB 5 

Soto J. PSB 53 

Spada G. PSA 64 

Spada G. PSA 90 

Spada G. PSB 31 

Spadini C. PSB 62 

Stancu A.D. PSB 19 

Stay D.P. PSA 15 

Steed J.W. IL 7 

Stępień M. IL 8 

Stoddart J.F. PL 4 

Stoddart J.F. PSB 27 



Střelcová Z. PSA 94 

Surin M. PSA 90 

Svobodová I. PSA 94 

Symes M. PSB 63 

Székely G. PSB 71 

Taghdiri M. PSB 58 

Taglietti A. PSA 36 

Taglietti A. PSA 37 

Taheri Z. PSB 60 

Takashima Y. PSB 64 


Takashima Y. PSA 88 




Takashima Y. IL 4 


Takata T. PSB 21 

Taktak S. IL 9 

Tananaev I.G. PSA 85 

Tangchaivang N. PSB 39 

Tarakanova A. PSB 66 

Tasker P. OP 16 

Tasker P. PSA 29 

Tasker P.A. PSB 70 

Tasker P.A. PSA 93 

Taura D. PSB 67 

Taylor R.W. PSB 68 

Tecilla P. OP 21 

Tecilla P. OP 5 

Terekhova I. PSB 69 

Terencio C. PSA 11 

Terraneo G. OP 15 

Teulade-Fichou M.P. PSA 63 

Thai P.V. PSB 66 

Tibbitts B.J. IL 10 

Tiedemann B.E.F. PSA 3 

Tikhomirov G. PSB 25 

Tock C. OP 20 

Tomimasu N. PSB 65 

Tonellato U. PSA 22 

Tonellato U. OP 5 

Tonellato U. PSA 9 

Tong C. PSB 70 

Torgov V.G. PSB 6 

Tóth K. PSA 77 

Toth T. PSB 71 

Tripier R. PSB 72 

Tsukagoshi S. PSB 64 

Tulyakova E. PSB 73 

Uda R. PSB 95 

Ugozzoli F. PSA 2 

Ungaro R. PL 7 

Ungaro R. PSA 7 

Uslu Kobak R.Z. PSB 74 

Vacca A. PSA 55 

Valizadeh H. PSB 60 

Valtancoli B. PSA 19 

Varzatskii O.A. OP 17 

Vázquez López M. PSB 75 

Vázquez M.E. PSB 75 

Veauthier J. IL 8 

Venturini M. PSA 19 

Vicens J. PSB 91 

Vicens J. PSA 51 

Vicens J. PSA 52 

Vicensa J. PSB 92 

Viktor F. PSB 71 

Villaescusa L.A. PSB 5 

Vistos J.M. PSA 61 

Vitha T. PSB 46 

Voignier J. PSB 76 

Vollmer Guy-Yves PSB 11 

Voloshin Y. OP 17 

Voloshin Y. PSB 77 

Voloshin Y. PSB 78 

Wagner-Wysiecka E. PSB 79 

Wang W. IL 6 

Wenzel M. PSB 80 

Wenzel M. PSB 81 

Werner M. Nau PSA 86 

Wessjohann L.A. PSA 56 

White F.J. PSA 29 

Wietor J.-L. PSB 82 

Wilson A.J. PSB 83 

Winter R. IL 6 

Wipff G. PSA 75 

Wolterbeek H. T. PSB 46 

Wood P.A. OP 16 

Wuest J.D. PSA 72 

Yamagishi T.aki. PSB 26 

Yamaguchi H. IL 4 

Yamaguchi H. PSB 29 

Yamaguchi H. PSA 88 






Yamnitz C. IL 6 

Yang Y. PSB 57 

Yasuda T. PSB 76 

Yates C.R. PSB 84 

Ye W. IL 9 

Yeni PSB 85 

You L. IL 6 

Zairov R. PSA 87 

Zangrando E. IL 3 

Zhang D. PSB 57 

Zhao Y. PSA 39 

Zhizhin K. PSB 8 

Zhorova R. PSB 13 

Ziach K. PSB 24 

Zielinski T. PSB 86 

Zieliński T. PSA 47 

Ziganshin M.A. PSA 62 

Zito V. PSA 3

Sponsors of ISMSC 2007 

The contribution of the sponsors in the organization of the Symposium 

is gratefully acknowledged: 

PERKIN ELMER 

RSC ChemComm 

RSC New Journal of Chemistry 

SAN PELLEGRINO 

VARIAN 

In particular, 11 out of 20 grants which allowed young scientists to 

attend the meeting were provided by: 

BRACCO (5) 

CHEMATEC (3) 

SPRINGER (2) 

RSC New Journal of Chemistry (1)

Local Wine and Food Sponsors 

SALUMERIA ANGELO DEDOMENICI 

Frazione Casanova di Destra 8 bis 

27050 Santa Margherita Staffora (PV) Italy 

Tel: 0383 551341 

a.dedomenici@tin.it 

AZIENDA AGRICOLA BISI 

fraz. Villa Marone, 70 

27040 San Damiano al Colle (PV) Italy 

Te:l 0385.75037 

info@aziendagricolabisi.it 

AZIENDA AGRICOLA ISIMBARDA 

Località Castello 

27046 Santa Giuletta (PV) Italy 

Tel: 0383 899256 fax 0383 814077 

info@tenutaisimbarda.com 

AZIENDA AGRICOLA MONTELIO 

Via Domenico Mazza, 1 

27050 Codevilla (PV) Italy 

Tel: 0383 373090 Fax: 0383 373083 

montelio.g@virgilio.it 

CANTINA DI CASTEGGIO SOC. COOP. 

via Torino, 96 

27045 Casteggio (PV) Italy 

Tel: 0383.806311 

info@cantinacasteggio.it 

CASEO 

fraz. Caseo, 9 

27040 Canevino (PV) Italy 

0385.99937 

caseo@caseo.it 

MARCHESE ADORNO 

loc. Salita Durazzo, 6 

27050 Retorbido (PV) Italy 

Tel: 0383.374404 

info@marcheseadorno-wines.it 

TORREVILLA Viticoltori Associati di Torrazza Coste e Codevilla 

via Emilia, 4 

27050 Torrazza Coste (PV) Italy 

Tel: 0383.77003 

info@torrevilla.it

ISMSC 2007 - Università degli Studi di Pavia

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