Bioinorganic Chemistry

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Series C: Mathematical and Physical Sciences - Vol. 459

Bioinorganic Chemistry An Inorganic Perspective of Life

edited by

Dimitris P. Kessissoglou Department of General and Inorganic Chemistry, Aristotle University of Thessaloniki, Thessaloniki, Greece

Springer-Science+Business Media, B.V.

Proceedings of the NATO Advanced Study Institute on Bioinorganic Chemistry. An Inorganic Perspective of Life Rhodes Island, Greece June 5-17, 1994

A C.I.P. Catalogue record for this book is available from the Library of Congress.

ISBN 978-94-010-4113-3 ISBN 978-94-011-0255-1 (eBook) DOI 10.1007/978-94-011-0255-1

Printed on acid-free paper

All Rights Reserved © 1995 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1995 Softcover reprint of the hardcover 1st edition 1995 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo­copying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

Preface

List of Contributors

List of Participants

Metalloenzymes

Methane Monooxygenase Stephen I. Lippard

TABLE OF CONTENTS

The Coordination Chernistry of Iron in Biological Transport and Storage; Iron Removal in Vivo

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Kenneth N. Raymond and Barbara L. Bryan 13

Siderophore-Mediated Iron Transport in Microbes Kenneth N. Raymond and lason R. Telford 25

On the Mechanism of Epoxidation and Hydroxylation Catalyzed by Iron Porphyrins. Evidence for Non-Intersecting Reaction Pathways lohn T. Groves and Zeev Gross 39

Self-Assembly, Catalysis and Electron Transfer with Metalloporphyrins in Phospholipid Membranes Ronald M. Kim, Gwendolyn D. Fate, lesus E. Gonzales, loydeep Lahiri, Solomon B. Ungashe and lohn T. Groves 49

Mechanistic Studies on the Binuclear Fe Enzymes Ribonucleotide Reductase and Purple Acid Phosphatase M.AS. Aquino, l.-Y. Han, 1.C. Swarts and AG. Sykes 57

Structure and Reactivity of the BIue Copper Proteins P. Kyritsis, C. Dennison and AG. Sykes 67

Copper-Zinc Superoxide Dismutase: Mechanistic and Biological Studies loan Selverstone Valentine, Lisa M. Ellerby, lanet A Graden, Clinton R. Nishida and Edith Butler Gralla 77

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NMR of Paramagnetic Molecules: A Contribution to the Understanding of Enzymatic Mechanisms Ivano Bertini and Maria Silvia Viezzoli 93

Magnetic and EPR Studies of Superoxide Dismutases (SOD): Electronic Structure of the Active Sites for the (Copper-Zinc)SOD, Its Cobalt Substituted Derivative and the Iron(III)SOD from E. Coli Irene Morgenstern-Badarau 105

Mechanism of Action of Thiamin Enzymes. Role of Metal Ions N. Hadjiliadis, K. Dodi and M. Louloudi 113

Metal-DNA Interaction

Platinum Anticancer Drugs Stephen f. Lippard 131

NMR Spectroscopic Structure Determination of Metal Ion - Oligonucleotide Complexes - The Results of Sequence-Selective Binding Studies Einar Sletten and Nils Age Fr(9ystein 141

Metal Ion-Coordinating Properties in Solution of Purine-Nucleoside 5' -Monophosphates and Some Analogues Helmut Sigel 155

Metal-Nucleobase Chemistry: Coordination, Reactivity, and Base Pairing B. Lippert 179

DNA Cleavage by Cationic Metalloporphyrins B. Meunier, G. Pratviel and f. Bernadou 201

The Role of Metal Ions in Biological Systems and Medicine f. Anastassopoulou and T. Theophanides 209

The Interaction of Heavy Metal Ions with DNA N. Katsaros 219

Thermodynarnics and Kinetics of Competing Redox Processes during DNA Cleavage: Reactivity-Based Selectivity c.-c. Cheng, Gregory A. Neyhart, Thomas W. Welch, fames G. GoU and H. Holden Thorp 237

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Modeling Active Sites

MolS Chemistry and Its Importance in Enzymatic Catalysis Dimitri Coucouvanis 247

Use of de Novo Designed Peptides for the Study of Metalloproteins and Enzymes G. Dieckmann, S. Heilman, D. McRorie, W. DeGrado and V.L. Pecoraro 275

Modeling the Chemistry and Properties of Multinuclear Manganese Enzymes Vincent L. Pecoraro, Andrew Gelasco and Michael f. Baldwin 287

Manganese-Proteins and -Enzymes and Relevant Trinuclear Synthetic Complexes Dimitris P. Kessissoglou 299

Catalytic Oxidation of Pollutants by Ligninase Models Based on Metalloporphyrins and Metallophthalocyanines B. Meunier and A. Sorokin 321

Nickel Coordination Chemistry with Oxothiolate Ligands and Its Relevance to Hydrogenase Enzymes fun-Hong Chou, Constantinos Varotsis and Mercouri G. Kanatzidis 333

Artificial Batteries with Lanthanide Porphyrins? A.G. Coutsolelos 349

Novel Transition Metal Heteropolymetalates and Derivatives: Structural Chemistry, Biological and Catalytic Relevance Bernt Krebs 359

Purple Acid Phosphatases and Catechol Oxidase and Their Model Compounds. Crystal Structure Studies of Purple Acid Phosphatase from Red Kidney Beans Bernt Krebs 371

Molybdenum-Copper Antagonism Dimitris P. Kessissoglou 385

Subject Index 401

PREFACE

During the last decade significant attention has been focused on the role of metal atoms in biology, giving rise to a very active research field of Bioinorganic Chemistry. Many crucial questions arising from the interference of metal ions in OUT life still remain unanswered. Even though very important structures of metalloenzymes as MoFeco of nitrogenase, copper or manganese superoxide dismutase or plastocyanin are known, the synthetic routes of modelling these centers are of great interest. Besides, other metalloenzymes, like the manganese center of Oxygen Evolving Complex(OEC) of PSIJ, are still in the centre of structural and spectroscopic in-depth examination. The drug-metal interaction and the metal ions antagonism are also an essential area of investigation. The understanding of the chemistry of metal ions in biological systems will be most beneficial to the scientific community because it will make possible the attack on certain difficult problems. Such problems may include biomineralization and the future production of advanced materials by micro-organisms. The NATO ASI, on which this book is based, was organised to promote interactions across these fields, to expose young researchers at an early stage of their careers to the several conceptual frameworks that currently contribute to the area.

Therefore, in June, 1994, ab out ninety scientists gathered at the Olympic Palace, on the Ixia coast near the City of Rhodes, Rhodes Island of Aegean Sea, Greece, for a two­week Advanced Study Institute dedicated to the theme of Bioinorganic Chemistry. This volume contains most of the invited lectures presented at the NATO ASI on "Bioinorganic Chemistry: An Inorganic Perspective of Life". It was decided not to 'referee' the submitted manuscripts, and therefor the entire responsibility of the content of the lectures rests with the authors.

It was my pleasure to act as the Director of the NATO ASI and I am most grateful to my esteemed colleagues on the Organising committee, Prof. Dimitri Coucouvanis, University of Michigan, USA, Prof. Mercouri Kanatzidis, Michigan State University USA, Dr. Bernard Meunier, CNRS, Toulouse, FRANCE and Prof. Athanassios Coutsolelos, University of Crete, GREECE and the invited lecturers for their enthusiastic support and valuable advice on various matters relating to the ASI. My special heartfelt thanks go to the students without whose interest and participation the ASI would not have been possible.

I sincerely thank Dr. L.V. da Cunha, Director, NATO Advanced Study Institute Programme and his Staff, who helped me throughout the various Stages of the ASI.

Of course the ASI would not have been possible without the financial aid of NATO. We are also grateful for the very important financial support and technical assistance provided by the Greek Secretariat of Research and Technology, the Greek Ministry of Industry, the Greek National Tourist Organisation, the Municipality of Thessaloniki, the Municipality of City of Rhodes, the University of Thessaloniki, the University of Crete, the Center of Solid Fuels Technology & Applications(C.S.F.T.A.), DOW Hellas and Petrola Hellas.

The local arrangements were handled with the cheerful aid of Dr. Catherine Dendrinou-Samara, Ms. Dora Malamatari and Mr. Nasos Papadopoulos. I also express my thanks to Prof. Evangelos Bakalbassis, who has handled many manuscript for this book, reformatting most of the chapters, and skilfully catching slips of the authors' word processors. I cannot fully express my appreciation for the unfailing support and understanding given to me by my wife Mary and my sons Philip and John during my Directorship of the Advanced Study Institute.

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Finally I would like to express my best thanks to Professor George Manoussakis for his presentation during the ASI dinner. It was an excellent historical review of the sciences developed in Ancient Aegean Sea, where the Rhodes Island is situated. I believe that the readers of this book will loose the roots of the scientific output of this meeting without having access to this presentation. So it would be a pleasure for me if this preface came along with the following speech of Prof. George Manoussakis.

Dimitris P. Kessissoglou

"Ladies and Gentlemen,

As you know we are in the south part of the Aegean Sea whieh was the eradle of a great eivilisation 25 eenturies ago. Several velJ' weil known philosophers were born and have developed their ideas in this area.

I will stop at those plaees which are more important to us as ehemists. I will stop to the philosopher who tried to answer most sueeessfully to the question "w hat ist h e wo r I d made of?". I will foeus partieularly on the lonian and Atomie Philosophers.

. c-..... ( Pythagoras I Samos aunu~'\)

~'Q '. ~ c;::7 f Mijet

'l~~~ f~ Q JJO· , . ''''----~ .... ~ -;{?

M:~ ,,; ~ ~ ~ '" 12oe:1

Thira'!b 60 ...

Thales Anaximander • ß olles Anaximenes i> ,

MEDITERRANEAN SEA

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The Ionian or Milesian School is represented by Thales, Anaximander and Anaximanes, all three were trom the same prosperous Ionian city of MelIitus. Their time overlapped in the earJy sixth centwy B.C.

Thales conc1uded that the world is made of w a te r . The train of thoughts which led him to this conclusion is that water exhibits itself in three forms: solid, liquid and gaseous as ice water and steam. Water is everywhere and is a component almost of everything, alive or not. He also supported the idea that Earth rests on water.

The younger fellow-citizen of Thales, Anaximander supported the idea that the world is a result of the combination of 0 p pos i t e qua 1 i ti es, of which four were primary, hot an d cold, we t an ddr y. The combination of wet and cold gives water, wet and hot air, hot and dry flIe, cold and dry earth. According to Anaximander, and opposite to the Thales suggestion that earth rest on the water, earth rests on not hing and it does not fall because it is situated just on the center of the universe and has no reason for falling in one direction or another.

air

water

The ideas of Anaximander were adopted Jater by AristotJe trom Stageira in his notation of the four basic "elements" of which the material world consisted of; they emerged trom the opposition of and contained the properties proposed by Anaximander, i.e. the combination of wet and cold gives water, wet and hot air, hot and dry flIe, cold and dry earth.

Anaximenes, another member ofthe Milesian School, claimed that the primary substance is air (a er, a rl p ). A ccording to him, the term air includes mist or fog. Air, surrounds the earth; moreover, air is possible to undergo p.avOJaT/, i.e., condensation. The name manometer is after the word p.avOJaT/. The result ofthe p.avOJaTf(condensation) is mist, water and further, solid and stones. Healsosupportedthat"air is the stuff of Jife".

Pythagoras, was bom in island Samos (550 Be), his main interest was initially mathematical. He used to say that "Things were number and the harmony of sounds and the movement or stars is a matter of mathematicaJ equations". Alsohebelievedthat "The number is in the center of matter and adjusts its properties". We know today that the atomic number, the number of protons in atomic nucleus, adjusts the chemicaJ properties ofth elements.

The Pythagorean ideas of a peacefUl and harmonie world, were rejected by Heraclitus, another famous Ionian philosopher.

Heraclitus (576-480), trom Ephessos of Asia Minor, believed that war is the father of all and there is attraction between opposites. His primary substance was fi re. According to him everything comes trom flre and ends to flre. He said that "fj re co n s ist s 0 f tin y partic1es" which he named "lfIrlrp.ara" The "flre" of Heraclitus may be regarded as corresponding to e ne r g y and in an anaJogous manner "1fI rl r p. ara" to the qua nt a of energy.

All these ideas ofthe Ionian philosophers may sound today as simply-minded, but we have to remember that untiJ their time the theories about the creation of the universe were based entireJy on purely magieal or theologicaJ explanations and the forces of nature were attributed to the actions of the anthropomorphic gods, e.g. Zeus (cJoud-gatherer, thunder-striker) and Poseidon (mover of earth, ship-wrecker).

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The atomic philosopher Dcmocritus, from Avdera of Thrace (460 Be), believed that the smallest particles of matter and therefore of substances are atoms.

The characteristics of atoms* are the following:

-solid, -hard, -indestructible, -unsplitable, -too small to be perceived by senses -c1ashing and recoiling in endless motion and -substantial identical.

Atoms differ in size and shape onlyas the difference between the letters A and N. The combination in different ways of these letters (atoms) gives the isomers compounds AN or NA. So Democritus had, in a way, predicted the phenomenon of isomerization. Democritus with his Atomic Theory tried to explain many properties of matter.

Hard-soft. Hard things are made of atoms packed c10sely together, so the absence of the possibility of compression offers resistance to the touch. Sott things are made of atoms wider apart. They contain more empty space and so are capable of compression thus offering less resistance to the touch.

Taste. Sweet things are made of smooth atoms. Bitter taste is caused by sharp atoms which make minute excoriation on the tongue.

Colour. The various positions of the atoms on the surface of objects causes the ligh~ which falls upon them, to throw back or retJect in different ways. These differences we perceive as different colours.

Volatility. The volatile substances consist of particularly small, fine and round atoms moving quickly because oftheir smallness and roundness.

Smell. Atoms of a certain size and shape, being in the surface of substance, detach from the surface and as they dritt through the air to the nase produce the sense of smell.

We believe today that the atoms of a certain size and shape, being in the surface of a substance, detach from the surface and as they dritt through the air to the nase, fill the receptors of the ends of certain nerves stimulate them and produce the sense of smell. "

• The word atoms comes from the word a:tO/Lo which means indivisible. The letter (1- preceding greek words has a steretic value corresponding generally to modem un- and the verb 1:E/LVro means to split.

LlST OF CONTRIBUTORS

STEPHEN J. LIPPARD Department of Chemistry Massachusetts Institute of Technology Cambridge, Massachusetts 02139, USA; Te1.:001-(617)-2531892; FAX:00l-(617)-2588150 El.Mail: LIPP ARD@LIPPARD.MIT.EDU

KENNETH N. RA YMOND Department of Chemistry University of California, Berkeley, CA 94720, USA; Tel:001-(510)-6427219; FAX:OO 1-(51 0)-4865283, El.Mail: RA YMOND@GARNET. BERKELEY.EDU

lOHN T. GROVES Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA; Tel: 001-(609)-2583900; FAX: 001-(609)-2586746

A.G.SYKES Department of Chemistry, University of Newcastle, Newcastle upon Tyne, NEI 7RU, UK; Tel: 0044-(91 )-222-6700; FAX:0044-91-222-6929

lOAN SEL VERS TONE VALENTINE Department of Chemistry and Biochemistry,University of California, Los Angeles, California 90024, U.S.A.; Te.:001-(310)-825-9835; FAX: 001-(310)-206-7197

IVANO BERTINI Department of Chemistry - University of Florence Via Gino Capponi 7, 50121 Florence, IT AL Y Tel.0039-(55)-2757549;FAX: 0039-(55)-2757555 El.Mail; BERTINI@IFICHIM

IRENE MORGENSTERN-BADARAU Laboratoire de Chirnie bioorganique et bioinorganiquem Institut de Chirnie Moleculaire d'Orsay, Universite PARIS-SUD-XI, 91405-0rsay, France; Tel.: (00331)69417440; FAX:(00331 )69417281

N. HADJILIADIS Laboratory of Inorganic and General Chemistry, Department of Chemistry, University of Ioannina, Ioannina 45-110, GREECE; FAX: 0030-(651)-44112; EI.Mail: NHADJIL@GRIOANUN. BITNET

EINAR SLETTEN Department ofChemistry, University ofBergen, N-5007 Bergen, NORWAY; Tel; 0047-(55)-213352;FAX:0047-(55)-329058; EI.Mail: EINAR@MVII.KJ. UIB.NO

HELMUT SIGEL University of Basel, Institute of Inorganic Chemistry, Spitalstrasse 51, CH-4056 Basel, SWITZERLAND; Tel. 0041-61-322-1557, FAX: 0041-61-322-1554 EI.Mail:SIGEL@URZ.UNIBAS.CH

BERNHART LIPPERT Department of Chemistry, University of Dortmund, D-44221 Dortmund, Germany; Tel:0049-(231 )-7553840; FAX:0049-231-755-3771 ; EI.Mail: UCH026@UNIDORZ. HRZ.UNI-DORTMUND.DE

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T. THEOPHANIDES National Technical University of Athens, Chemical Engineering Department, Radiation Chemistry and Biospectroscopy, Zografou Campus, Zografou 15780, Athens, Greece; Tel:0030-Q)-80 14979

N. KATSAROS NCSR "Demokritos" Institute of Physical Chemistry, 153 10 Aghia Paraskevi Attikis, Greece; Tel. 0030-(1)-6513111; FAX: 0030-1-6511767

H. HOLDEN THORP Department of Chemistry, University of N orth Carolina at Chapel Hill, Chapel Hill, N orth Carolina 27599-3290; Tel. (001)(919)962-0276, FAX:(OO 1 )(919)(962-2388); THORP @GIBBS.OIT.UNC.EDU

DIMITRI COUCOUV ANIS Department of Chemistry, The University of Michigan, Ann Arbor Michigan, 48109-1055 USA; Tel: 001-(313)-764-7339, FAX:001-(313)-747-4865; EI.Mail: Dimitri COUCOUV ANIS@UM.CC. UMICH.EDU

VINCENT L. PECORARO Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 USA; Tel:001-(313)-7631519;FAX: 001-(313)-7474865; E1.Mail: USERLB4D@UM.CC. UMICH.EDU

B. MEUNlER Directeur de Recherche, Centre National de la Recharche Scientifique, Laboratoire de Chimie de Co ordination du CNRS, 205 route de Narbonne, 31077 Toulouse cedex, FRANCE. Tel.: 0033-(61)333100; FAX: 0033(61)553003

MERCOURI G. KANATZIDIS Department ofChemistry, Michigan State University, East Lansing MI 48824, USA; Tel: 001-(517)-3534511; FAX: 001-(517)-3531793; EI.Mail:KANATZIDIS@MSUCEM. BITNET

A.G.COUTSOLELOS University of Crete, Department of Chemistry, Laboratory of Bioinorganic Co ordination Chemistry University of Crete, P.O.Box 1470, 71409-Heraklion, Crete, GREECE; TeI.0030-(81)-235-014; FAX:0030-(81)-238-468; EI.Mail: THANOS @GREARN

BERNTKREBS Institute of Inorganic Chemistry, University of Münster, Wilhelm-Klemm Strasse 8, D-48149 Münster, GERMANY; Te1.:0049-(251)-833131; FAX:0049-(251)-838366; E1.Mail: KREBS VNWZOl@UNI-MUENSTER-DE

DIMITRIS P. KESSISSOGLOU Department of General & Inorganic Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54006, Greece; Tel:30-(31)-997723, FAX:30-(31 )-997723 E1.Mail:CCAZ13 @GRTHEUNl.BITNET

LIST OF PARTICIPANTS

ASI STUDENTS

Denmark

Ms. Inge Margrethe JENSEN, Graduate Student, Dept. of Chemistry, University of Odense, DK-5230 Odense M, DENMARK; Tel.: (66)158600; FAX: (66)158428; E1.Mail.: IMJ@OUKEMLOU.DK

France

Dr. Genevieve BLONDIN, Lab. de Chimie Inorganique, URA CNRS 420, Universite de Paris-Sud, 91405 Orsay Cedex FRANCE; Tel.: (0033)(1)69417436; FAX: (0033)(1)69855536; El.Mail.:LCI@CTH.U­PSUD.FR

Dr. Anne ROBERT, Laboratoire de Chimie de Coordination, C.N.R.S., 205 route de Narbonne, 31077 Toulouse cedex,FRANCE; Tel.: (0033)61333146, FAX:(0033) (61553003)

Germany

Ms. Martina HUBER, Graduate Student. Institute fur Physikalishe Chemie, Technische, Petersen Str. 20, 64287 Darmstadt, GERMANY; FAX:(0061 )(51)164298

Dr. Roland KRAM ER,

Hochschule Darmstadt, Tel.:(0061 )(51) 163698;

Anorganish-Chemisches Institute, University of Munster, Wilhelm-Klemm-Strasse 8, D-48149 Munster, GERMANY; Te.:(0061)(251)833158; FAX:(0061)(251)838366; E-mail: Kramerr@VNWZOI.UNI-MUENSTER.DE

Mr. Andre SCHREIBER, Graduate Student, Universitat Dortmund Fachbereich Chemie Anorganische Chemie, Otto­Hahn-Strasse 6, D-4600 Dortmund 50, GERMANY;Tel:0049-(231)-7553840; FAX:0049-231-755-3771; E1.Mail: UCH026@UNIDORZ.HRZ.UNI-DORTMUND.DE

Greece

Prof. Evagelos BAKALBASIS, Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 Thessaloniki, GREECE; Tel. (30)(31)997815; FAX:(30)(31 )997738

Prof. Christos BOLOS, Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 Thessaloniki, GREECE; Tel. (30)(31)997705; FAX:(30)(31)997738

Mr. Vage1is DAVORAS, Graduate Student, University of Crete, Dept. of Chemistry, 71409 Iraklion Crete, GREECE; Te1.:(30)(81 )238468; FAX:(30)(81 )21 0951

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Ms. Dimitra DAPHNOMILI Graduate Student, Thenon 45, Heraklion, Crete, GREECE; Te1.:(30)(81)310352; FAX:(30)(81 )210951

Dr. Catherine DENDRINOU-SAMARA Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 Thessaloniki, Greece; Tel. (30)(31)997738; FAX:(30)(31)997738

Ms. Marietta HADJILIADI-LAMERA, Hospital "The hope" Trichonidos & Dimitsanis, Ampelokipoi, Athens, GREECE; Tel. 0030-(1 )-6444529

Prof. Dimitris KYRIAKIDIS Aristotle University of Thessaloniki, Dept. of Org. Chemistry & Biochemistry, 54006 Thessaloniki, GREECE; Tel. (30)(31 )997771; FAX:(30)(31 )997738

Ms. Dora MALAMAT ARI Graduate Student, Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 Thessaloniki, GREECE; Tel. (30)(31 )997739; FAX:(30)(31 )997723

Prof. George MANOUSSAKIS, Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 l'hessaloniki, GREECE; Tel. (30)(31 )997781; FAX:(30)(31 )997738

Mr. Athanassios PAPADOPOULOS, Graduate Student, Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 Thessaloniki, GREECE; Tel. (30)(31)997739; FAX:(30)(31)997738

Prof. Raphael RAPTIS, University of Crete, Dept. of Chemistry, 71409 IrakIion Crete, GREECE; Tel.:0030-(81)-238400; FAX:(30)(81)210951

Dr. Cathemine RAPTOPOULOU, Institute of Material Science, N.R.C. Demokritos,Ag. Paraskevi, 15310 Athens, GREECE, Tel.:(30)(31)651311I; FAX:(30)(31)6519430

Mr. Spyros SERVES, Graduate Student, Department of Chemistry, University of Patras, GREECE; home address: Stravonos 20, 25100 Aigion, GREECE; Tel. 0030-(61)27031

Mr. George SPYROULIAS, Graduate Student, University of Crete, Dept. of Chemistry, 71409 IrakIion Crete, GREECE; Te1.:(30)(81 )238468; FAX:(30)(81 )2lO951; El.Mail.: Spyroulias@talos.cc.uch.gr

Dr. Hariklia STASSINOPOULOU, Institute Of Biology, NRCPS "Demokritos", 15310 Agia Paraskevi Attikis, GREECE; Tel. 0030-(1 )-6513111; FAX: 0030-1-6511767

Dr. Leandros TZA VELLAS Aristotle University of Thessaloniki, Dept. of Gen. & Inorg. Chemistry, 54006 Thessaloniki, Greece; Tel. (30)(31 )997786; FAX:(30)(31 )997738

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Italy

Dr. Giuseppe Enrico ARENA, Dipartimento di Chimica Inorganica, Analytica E. Struttura Molecolare Universita delgi Studi di Messina Salita sperone 31, Villagio S. Agata 98166 Messina, IT AL Y; Tel.: 0039-90-392901; FAX:0039-90-393756

Mr. Gianantonio BATTISTUZZI, Graduate Student. Dept. of Chemistry, University of Modena, via Campi, 183, 41100 Modena, ITALY;Tel.: (0039)(59)378421, FAX:(0039)(59) 373543

Dr. Giulia GRAS SO, Dipartimento di scienze Chirniche, Universita di Catania V.le A.Doria 8, 95125 Catania, ITALY; Tel: 0039-95-337678; FAX: 0039-95-580138

Dr. Graziella VECCHlO, Dipartimento di scienze Chirniche, Universita di Catania V.le A.Doria 8, 95125 Catania, ITALY; Tel: 0039-95-337678; FAX: 0039-95-580138

The N etherlands

Prof. Jan REEDIJK Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O.Box 95502,2300 RA Leiden, THE NETHERLANDS; Tel. 0031-71-274459; FAX; 0031-71-27 4451; EI.Mail: Reedijk@rulgca.Leidenuniv.nl

Norway

Prof. lorum AMBJORG-SLETTEN, Department ofChemistry, University ofBergen, N-5007 Bergen, NORWAY; Tel; 0047-(55)-213352;FAX:0047-(55)-329058; EI.Mail: EINAR@MVII.KJ. UIB.NO

Prof. Willy NERDAL, Dept. of Chemistry, University of BergenAllegt. 41, N5007 Bergen, NORWAY; Te!.: ( 47)55213353; FAX: (47)55329058; EI.Mail.: Willy.nerdal@kj.uib.no

Ms. Signe STEINKOPF, Graduate Student, Kjemisk Institutt, Universitetet i Bergen, Allegt. 41, N-5007 Bergen, NORWA Y; TeI.:(55)213359; FAX: (55)3229058; EI. Mail: Signe.Steinkopf@kj.uib.no

Portugal

Ms. Maria Marise Simoes de ALMEIDA, faculdade de Ciencias de Lisboa, Dept. of Chemistry, Campo Grande, 1700 Lisboa, PORTUGAL

Ms. Maria lose FEIO, Graduate Student, Centro de Tecnologia Quimica e Biologica(CTQB), Rua da Quinta Grande, 6, Apartado 127, 2780 OElRAS PORTUGAL; (00351)(01)4426146; FAX: (00351)(01)4428766

Prof. Antonio V. XAVIER, Centro de Tecnologia Quimica e Biologica(CTQB) Rua da Quinta Grande, 6, Apartado 127, 2780 OElRAS PORTUGAL, Tel:00351-(l)-4426146; FAX:00351-1-4428766

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Spain

Prof. Juan Antonio Rodriguez RENUNCIO, J.A.R., Professor, Facultad de Quimica Universidad Complutense, E-28040 Madrid, SPAIN; Tel.: (341)3944120; FAX: (341)3944135; El.Mail: mendu@quim.ucm.es

Turkey

Ms. Meray BASTURKMEN, Ortadogu Teknik Universitesi Fen Edebiyat Fakultesi Kimya Bolumu 06531 Ankara, TURKEY; TEL.: 0090-312-2101000; FAX: 0090-312-2101280

Ms Guller GOZEL, Graduate Student, Middle East Teclmical University Chemistry Dept. 06531 Ankara, TURKEY; Tel: (0090)(4210) 10003210; El.Mail.: A09984@TR METIS

Prof. Renat ZHDANOV, Orta Dogu Teknik Universitesi, Middle East Technical University, Dept. of Biology, 06531 Ankara, Turkey; Tel: (0090)(4)2101000/3105; FAX:(0090)(4)2101289; EI.Mail.: Zhdanov@vm.cc.metu.edu.tr

United Kingdom

Mr. Nadeem AURANGZEB, Graduate Student, Dept. of Chemistry, UMIST, Sackvill Street, Manchester, M601QD, United Kingdom;Tel. (0044)(61)2363311; FAX:(0044)(61)2287040

Dr. Elisabeth A. MARSEGLIA, Univeristy of Cambridge, Dept. of Physics, Cavendish Laboratory, Madingley Road, Cambridge, CB30HE, U.K .. Tel.: 0044-(223)- 337277; FAX: 0044-(223)-353397; El.Mail.: EMI0@PHY.CAM.AC.UK

Mr. Michael WATKINSON, Graduate Student, 80 Philip Street, Eccles, Manchester M30 OWE, United Kingdom; Tel.: (0044)(61 )7894048

U.S.A.

Prof. Peggy CARVER, College ofPharmacy, University ofMichigan, 428 Church St., Ann Arbor, MI 48109-1065, USA; Tel:(OO 1 )(313)764-9384, FAX:(OO 1 )(313)763-2022: El.Mail: USERGDEL@ UMICH.UM.EDU

Mr. Kostas DEMADIS, Draduate Student,Dept. of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA; Tel: 001-(313)-764-7339, FAX:001-(313)-747-4865; El.Mail: Dimitri Coucouvanis@um.cc. umich.edu

Mr. Andrew FEIG, Graduate Student,Department of Chemistry, Room 18-290, Massachusetts Institute of Technology, Cambridge, MA 02139,USA Tel.:001-(617)253-1892; FAX:001-(617)-258-8150 E1.Mail: LIPPARD@LIPPARD.MIT.EDU

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Mr. Brian GIBNEY, Graduate Student,Dept. of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA, Tel:001-(3l3)-7631519;FAX: 001-(3l3)-747-4865; E1.Mail: USERLB4D@UM.CC.UMICH.EDU

Prof. Martin L. KlRK, Dept. ofChemistry, University ofNew Mexico Albuquerque, New Mexico 87131-1096, USA; Tel:(OOI)(505)277-5992; FAX:(OOI)(505)277-2609; EI.Mail. mkirk@hydra.unm.edu

Dr. Helen PAPP A, Dept. of Molecular Biology & Biochemistry, University of Califomia, Irvine, Califomia 92717, USA;FAX:(OO 1 )(714)856-8540; El..mail: poulos@uci.edu

Ms. Di QIU, Graduate Student, Dept. of Chemistry, Princeton University, Princeton, NJ 08544, USA;Tel. :(00 1)(609)258-3908; FAX:(OO 1)(609)258-6746; EI.Mail:Qiu@Chemvax.Princeton. edu

Mr. M. SCOTT, Graduate Student, Dept. ofChemistry, Harvard University, Cambridge, Massachusetts 02l38, USA, FAX:(OOl)(617)496-9289, EI.Mail.:HOLM@FEMOCO. HARVARD.EDU

Prof. Michael J. THERlEN, Dept. OfChemistry, University ofPennsylvania, Philadelphia, PA 19104-6323, USA

Mr. Jason TELFORD, Graduate Student, Dept. of Chemistry, University of Califomia, Berkeley, Berkeley, CA 94720,USA; Tel. (001)(510)642-5589; FAX(OOl)(51O)486-5283; EI.Mail.: KNRGROUP@GARNET.BERKELEY.EDU

Austria

Mr. Erwin HERLINGER Graduate Student, Dept. of Inorg Chemistry, Technical University Estreidemarkt 9/153, A-1060 Vienna, AUSTRlA; Tel.: (0043)(1)58801-4623; FAX: (0043)(1)5874835

Bulgaria

Prof. Stoyan SHISHKOV, Faculty of Biology, University of Sofia, 8 Dragan Tzankov Str, 1421 Sofia, BULGARlA; Tel.: 63301(293); FAX: (00359)(2)463589

Czech Republic

Dr. Jana ZACHOVA, Institute of Physics of the Charles University, Ke Karlovu 5, CZ-121 16 Prague 2, CZECH REPUBLIC; Tel.:(0042)(2)292544; FAX: (0042)(2)296764; EI.Mail.: Florian@CSPGUKll

Hungary

Mr. Jozsef KAIZER, Dept. of Organic Chemistry, University ofVeszprem, 8201 Veszprem, HUNGARY; Tel.: (0036)(88)422022; FAX: (0036)(88)426016; EI.Mail.: H2107SPE@ HUELLA.BITNET

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Mr. Istuan LIPPAI, Graduate Student, H-8201 Veszprern, P.O.Box 158 HUNGARY, Tel.: (0036)(88)422022; FAX: (0036)(88)426016; EI.Mail: H2107SPE@ HUELLA.BITNET

Prof. Laszlo NAGY, A. Jozsef University, Dept of Inorg. & Analytical Chernistry, 6720 Szeged, Dom ter 7, Hungary, Tel. (0036)(62)311622; FAX: (0036)(62)312505

Poland

Dr. Justyn OCHOCKI, Medical University of Lodz, Dept. of Pharmacy PI 90-151 Lodz, Muszynskkiego 1, Poland; Tel.: (0048)(42)785570; FAX: (0048)(42) 322347; EI. Mail; PHARMACY@PLUNL051.BITNET

Mr. Krzysztof SLOWINSKI, Graduate Student, Dept. of Chernistry, University of Warsaw, 02093 Warsaw, Pasteura 1, Poland; Tel.: (0048)(22)220211; FAX: (0048)(22)225996; EI.Mail.: SLOWIK@CHEM.UW.EDU.PL

Rurnania

Prof. Claudia SUPURAN, University of Bucharest, Dept of Chernistry Bd. Carul 1 (Republicia) 13, Bucharest, Rournania; Tel: (0040)(1 )6163449 FAX: (0040)(1 )6130296

Russian Federation

Dr. Lyudrnila OREKHOV A, Institute of Biorganic Chern. ul. Miklukho-Maklaya 16/10, Moscow 117871, RUSSIA. FAX: 007095(00359)3357103; EI. Mail.: ORL@BCH.SIOBO.MSK.SU

Ukraine

Dr. Igor FRITSKY, Institute of Chernistry, University of Wroclaw, 50383, Wroclaw, Poland; Tel: (0048)(71 )204313; FAX: (0048)(71 )222348; El.Mail.: Arka@ Plwruw II.Bitnet