B. Catoire (Editor)

Electron Spin Resonance (ESR) Applications in Organic and Bioorganic Materials

Proceedings of the First European Meeting January 1990, Lyon, France

Publication partially sponsored by MRT (French Ministry of Research and Technology)

With 115 Figures and 31 Tables

Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Barcelona Budapest

B. Catoire Groupe d'Applkation de la Resonance Paramagnetique Electronique 1.T.F.Lyon Avenue Guy de Collongue, B.P. 60, F-69132 Ecully Cedex

Library of Congress Cataloging-in-Publication Data Electron spin resonance (ESR) applications in oragnic and bioorganic materials proceedings of the first European meeting, January 1990, (France, Lyon) I B. Catoire (ed.). "Publication partially sponsored by MRT (French Ministry of Research and Technology)." ISBN-13: 978-3-642-77216-0 e-ISBN-13: 978-3-642-77214-6 DOl: 10.1007/978-3-642-77214-6

1. Electron paramagnetic resonance spectroscopy--Congresses. I. Catoire, B. II. France. Ministere de la recherche et de la technologie QP519.9.E433E44 1992 574.l9'285-dc20 91-42660

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Preface

E.S.R. techniques which are mature from a fundamental point of view. now constitute a routine investigation tool in chemistry as well as in biophysics in order to study and to follow the behaviour of radical species.

Among the practical applications. let us mention for instance :

- diffusion phenomena (solid - solid. liquid - solid such as the diffusion of molecules through membranes. films fibers ... ).

- study of radical species to improve the elaboration of materials with high added value (composites).

- detection of ionised food.

- liquid crystals. polymers.

- radiochemistry.

- targetting of drugs. toxicology.

A better understanding of basic phenomena allows to optimize industrial products and processes applied as well as in advanced fields as in well established ones.

The high sensivity of ESR Spectroscopy and its derived specific techniques (spin labelling. spin probe. spin trapping ... ) offer information on the fme morphological structure of the matter as well as on its behaviour under various treatments otherwise not available.

A Symposium was organized in Lyon (France) in January 1990 to promote the use of ESR. Its originality was to deal with the practical applications of ESR to organic and bioorganic materials. The scope of this meeting was to enlarge the field of application from basic research to more applied subjects and this may concern industrial as well as academic researchers. Moreover. the purpose of this symposium was to promote exchanges between European specialists working in public or private areas.

The French ESR Application Group (GARPE) organizing committee hopes that the communications collected in this volume will be useful.

The GARPE would like to thank all the contributors.

We sincerely acknowledge the MRT (French Ministry of Research and Technology) for partially sponsoring this pUblication.

LeGARPE Secretary B. CATOIRE

Institut Tutile de France B'p.6()

F-69132 ECUUY CEDEX

List of Contributors

Dr J.P. AGNEL, Departement de Physiologie du Vegetal et Ecosystemes, CEN Cadarache, F-13108 Saint-Paul-lez-Durance

O. AKERMANN, INRA, Laboratoire de Nutrition et Securite Alimentaire, F-78352 Jouy-en­Josas Cedex

S. A YNIE, Laboratoire de Biologie Physico-chimique, Ecole Nationale Superieure de Biologie Appliquee a la Nutrition et a l'Alimentation, Campus Universitaire Montmuzard, F-21000 Dijon

Dr J. BARTHE, Commissariat a l'Energie Atomique, IPSN/DPT/SIDR, B.P. 6, F-92265 Fontenay aux Roses Cedex

Dr C.M. BA TTESTI, Laboratoire de Radiochimie des Constituants des Aliments, Departement de Physiologie Vegetale et Ecosystemes, CEN de Cadarache, F-13108 Saint-Paul-Iez-Durance

Dr F. BERMANN, Commissariat a l'Energie Atomique, IPSN/DPT/SIDR, B.P. 6, F-92265 Fontenay aux Roses Cedex

F. BONOSI, Department of Chemistry, University of florence, Via G. Capponi 9, 1-50121 Firenze

Prof. F. BONON, Universita di Padova, Dipartimento di Chimica Fisica, Padova (Italy)

Prof. M. BRUSTOLON, Universita di Padova, Dipartimento di Chimica Fisica, Padova (Italy)

Prof. M. CAMPS, Universite de Saint-Etienne, 23 Rue du Dr Michelon;F-42100 Saint-Etienne

G. CARUBIA, Department of Chemistry, University of Florence, Via G. Capponi 9, 1-50121 Firenze

Dr B. CASSIER, Universite de Bourgogne, Faculte de Pharmacie, 7 Boulevard Jeanne D'Arc, F-21033 Dijon Cedex

Dr B. CATOIRE, Institut Textile de France - Section Lyon, B.P. 60, F-69132 Ecully Cedex

Dr C. CHACHATY, Departement de Recherches sur l'Etat Condense, DRECAM/SCM/BP 121, Centre D'Etudes Nucleaires de Saclay, F-91191 Gif sur Yvette Cedex

Prof. B. CHAlLOT, Universite de Bourgogne, FacuIte de Pharmacie, 7 Boulevard Jeanne D'Arc, F-21033 Dijon Cedex

Dr O. CHAIX, URA 69, CNRS, Institut Dolomieu, Universite Joseph Fourier, 15 Rue Maurice Gignoux, F-38031 Grenoble

Dr H. CHARCOSSET, Institut de Recherche sur la Catalyse, 2 Avenue A. Einstein, F-69626 Villeurbanne Cedex

Prof. M. CHE, Laboratoire de Reactivite de Surface et Structure, URA 1106 CNRS, Universite P. et M. Curie, 4 Place Jussieu, F-75252 Paris Cedex 05

VII

Dr C. CHOPARD, Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Unite associee au CNRS (URA 400), Universite Rene Descartes, 45 Rue des Saints-Peres, F-75270 Paris Cedex 06

Dr C.L. DAVIES, School of Chemistry and Applied Chemistry, University of Wales College of Cardiff, P.O. Box 912, Cardiff CFl 3TB, UK

Dr P. DERACHE, Universite Paul Sabatier, Faculte des Sciences Pharmaceutiques, Laboratoire de Biochimie, 35 Chemin des Maraichers, F-31052 Toulouse cedex

Dr J.M. DI MEGLIO, UA 792 du CNRS, Laboratoire de Physique de la Matiere Condensee, II Place Marcelin Berthelot, F-75231 Paris Cedex 05

Dr J.C. EVANS, School of Chemistry and Applied Chemistry, University of Wales College of Cardiff, P.O. Box 912, Cardiff CFI 3TB, UK

Prof. J. FAURE, Physicochimie des Rayonnements, Bat 350, Universite Paris Sud UA 75 du CNRS, F-91405 Orsay Cedex

Prof. A. FEIGENBAUM, INRA, Laboratoire de Nunition et S6curit6 Alimentaire, F-78352 Jouy-en-Josas Cedex

Mol. FILDES, Shell Research Ltd, Thornton Research Centre, P.O. Box I, Chester CHI 3SH, UK

Prof. G. GABRIELLI, Department of Chemistry, University of Florence, Via G. Capponi 9, 1-50121 Firenze

A. GAUDEMER, Universit6 Paris-Sud, UA 255, F-91405 Orsay

Dr R. GRAY, Food and Agricultural Chemistry Research Division, Department of Agriculture for Northern Ireland, Belfast BT9 5PX, Northern Ireland, UK

Prof. A. GUYOT, CNRS - LMO, B.P. 24, F-69390 Vernaison

Dr M.A. HEMMING A, Laboratory of Dairing and Food Physics, Department of Food Science, Wageningen Agricultural University, PO Box 8128, NL-6700 ET Wageningen

Dr A. JEUNET, LEDSS, Universite Joseph Fourier, 15 Rue Maurice Gignoux, F-38031 Grenoble

Dr V. KAMENOPOULOU, Commission a l'Energie Atomique Grecque, G-1531O Aghia Paraskevi Attikis

Dr P. LABRUDE, Universite de Nancy I, France

DJ;. M. LE MESTE, Laboratoire de Biologie Physico-chimique, Ecole Nationale Sup6rieure de Biologie Appliquee a la Nunition et a l'Alimentation, Campus Universitaire Montmuzard, F-21000 Dijon

Dr F. LETERRIER, Unite de Biophysique du C.R.S.S.A., F-38702 La Tronche Cedex

Dr L. LIU, Physicochimie des Rayonnements, Bat. 350, Universite Paris Sud UA 75 du CNRS, F-91405 Orsay Cedex

Dr C. LOUIS, Laboratoire de Reactivite de Surface et Structure, URA 1106 CNRS, Universite P. et M. Curie, 4 Place Jussieu, F-75252 Paris Cedex 05

VIII

Prof. A.L. MANlERO, Universita di Padova, Dipartimento di Chimica Fisica, Padova (Italy)

Prof. G. MARTINI, Deparnnent of Chemistry, University of florence, Via G. Capponi 9, 1-50121 Firenze

Prof. M. MAS SOL, Universite Paul Sabatier, Laboratoire de Chimie Bioinorganique, INSERM U-305, 38 Rue des 36 Ponts, F-31400 Toulouse

Dr A. MICHEL, Laboratoire des Matenaux Organiques, CNRS, B.P. 34, F-69390 Vernaison

Prof. J.P. MONTHEARD, Universite de Saint-Etienne, 23 Rue du Dr Michelon;F-42100 Saint­Etienne

Prof. F. NEPVEU, Universite Paul Sabatier, Laboratoire de Chimie Analytique, 31 Allee Jules Guesde, F-31400 Toulouse

Dr B. NICKEL-PEPIN-DONAT, Ecole Nonnale SupCrieure, en detachement au DRFMC/SP2M1PMS, Centre d'Etudes Nucleaires de Grenoble, BP 85X, F-38041 Grenoble Cedex

Prof. M.F. OTT A VIANI, Deparnnent of Chemistry, University of Florence, Via G. Capponi 9, 1-50121 Firenze

Dr R. PANSU, Physicochimie des Rayonnements, Bat 350, Universite Paris Sud UA 75 du CNRS, F-91405 Orsay Cedex

Dr G. PASCAL, INRA, Laboratoire de Nutrition et S&:urit6 Alimentaire, F-78352 Jouy-en­JosasCedex

Dr G. PORTAL, Commissariat a I'Energie Atomique, IPSN/DPT/SIDR, B.P. 6, F-92265 Fontenay aux Roses Cedex

Dr G. POUPEAU, Institut Dolomieu, Universite Joseph Fourier, 15 Rue Maurice Gignoux, F-38031 Grenoble

Dr David QUERE, UA 792 du CNRS, Laboratoire de Physique de la Matiere Condensee, 11 Place Marcelin Berthelot, F-7523I Paris Cedex 05

Dr J. RAFFI, Departement de Physiologie du Vegetal et Ecosystemes, CEN Cadarache, F-13108 Saint-Paul-Iez-Durance

Prof. A. RASSAT, Ecole Nonnale Superieure, 24 Rue Lhomond, F-75005 Paris

Dr A. REVILLON, Laboratoire des Matenaux Organiques, CNRS, B.P. 34, F-69390 Vernaison

Dr A.M. RIQUET, INRA, Laboratoire de Nutrition et S&:urit6 Alimentaire, F-78352 Jouy-en­JosasCedex

Dr S. RIVOMANANA, Universite Paul Sabatier, Laboratoire de Chimie Bioinorganique, INSERM U-305, 38 Rue des 36 Ponts, F-31400 Toulouse

Dr J. RONCIN, Physicochimie des Rayonnements, Bat. 350, Universite Paris Sud UA 75 du CNRS, F-91405 Orsay Cedex

Dr M.J.G.W. ROOZEN, Laboratory of Dairing and Food Physics, Department of Food Science, Wageningen Agricultural University, PO Box 8128, NL-6700 ET Wageningen

IX

Dr A.M. ROSSI, Institut Dolomieu, Universite Joseph Fourier, 15 Rue Maurice Gignoux, F-38031 Grenoble

Dr C.C. ROWLANDS, School of Chemistry and Applied Chemistry, University of Wales College of Cardiff, P.O. Box 912, Cardiff CFl 3TB, UK

Y. SANDRA Y, Dorlyl, Usine du Havre, B.P. 1152, F-76063 Le Havre Cedex

Prof. U. SEGRE, Universita di Padova, Dipartimento di Chimica Fisica. Padova (Italy)

Dr Z. SOJKA, Jagellonian University, ul. Karasia 3, Krakow, Poland

Dr Edgar SOULIE, Departement de Recherches sur I'Etat Condense, DRECAM/SCM/BP 121, Centre D'Etudes NuclCaires de Saclay, F-91191 Gif sur Yvette Cedex

Prof. M. H. STEVENSON, Food and Agricultural Chemistry Research Division, Department of Agriculture for Northern Ireland, The Queen's University of Belfast. Newforge Lane, Belfast BT9 5PX, Northern Ireland, UK

Dr C.L. THIERY, Laboratoire de Radiochimie des Constituants des Aliments, Departement de Physiologie Vegetale et Ecosystemes, CEN de Cadarache, F-13108 Saint-Paul-Iez-Durance

Dr J.M. THIERY, Modelisation et Genie Logiciel, Departement de Physiologie Vegetale et Ecosystemes, CEN de Cadarache, F-13108 Saint-Paul-Iez-Durance

Dr B. TILQUIN, Laboratoire d'analyse chimique et physico-chimique des medicaments, CHAM 72.30, 72 Avenue E. Mounier, B-1200 Bruxelles

Dr J.B. TRIOLET, Laboratoire de Radiochimie des Constituants des Aliments, Departement de Physiologie Vegetale et Ecosystemes, CEN de Cadarache, F-13108 Saint-Paul-Iez-Durance

Dr T. VAN LIET, Laboratory of Dairing and Food Physics, Department of Food Science, Wageningen Agricultural University, PO Box 8128, NL-6700 ET Wageningen

Dr V. VERNEY, Laboratoire des Materiaux Organiques, CNRS, B.P. 34, F-69390 Vemaison

Dr P.B. VINCENT, Laboratoire de Radiochimie des Constituants des Aliments, Departement de Physiologie Vegetale et Ecosystemes, CEN de Cadarache, F-13108 Saint-Paul-Iez-Durance

Dr J. VIRET, Unite de Biophysique du C.R.S.SA, F-38702 La Tronche Cedex

Dr P. WALSTRA, Laboratory of Dairing and Food Physics, Department of Food Science, Wageningen Agricultural University, PO Box 8128, NL-6700 ET Wageningen

Dr C. WOLF, URA CNRS 524, C H U St-Antoine, 27 Rue Chaligny, F-75012 Paris

Dr'F. ZEEGERS, Laboratoire d'analyse chimique et physico-chimique des medicaments, CHAM 72.30, 72 Avenue E. Mounier, B-1200 BruxelJes

Dr J.L. ZIMMERMANN, Service de Biophysique, Departement de Biologie, CEN de Saclay, F-91191 Gif sur Yvette

Contents

C. CHACHATY, E. SOULIE and C. WOLF Some Recent Applications of Computer Simulations of ESR Spectra to the Dynamics of Spin Probes in Gels and Membranes 1

S. A YNIE and M. LE MESTE An Electron Spin Resonance Study of the Interactions Between Proteins and Lipids 21

MJ.G.W. ROOZEN, P. W ALSTRA, T. VAN LIET and M.A. HEMMINGA A Spin Probe ESR Study of Sugar Water Mixtures in the Liquid and Glassy State 31

J. VIRET andF. LETERRIER Spin Labelling and Membrane Fluidity 53

J. FAURE, R. PANSY, J. RONCIN and L. LIU Potentiel Transmembranaire dans les Vesicules Artificelles. Fragmentation des Vesicules. Encapsulation 69

G. MARTINI, F. BONOSI, G. CARUBIA, M.F. OTTAVIANI and G. GABRIELLI Electron Spin Resonance as a Tool for the Study of Langmuir-Blodgett Films of Nitroxides and Metal Alcanoates 77

S. RIVOMANANA, M. MASSOL, P. DERACHE and F. NEPVEU Comparison of the Superoxide Scavenging Activity of Various Manganese Compounds by Use ofESR Spectroscopy 105

B. CATOIRE, V. VERNEY andA. MICHEL Thermal Decomposition Kinetics of Polypropylene Peroxides in the Polymer Matrix by ESR 113

C.CHOPARD Spin-Trapping in Biological Systems 125

J. RAFFl and J.P. AGNEL Electron Spin Resonance Identification of Ionized Foodstuffs 135

M.H. STEVENSON and R. GRAY Some Factors Influencing the ESR Signal from Irradiated Poultry Products Containing Bone 145

A.M. ROSSI, G. POUPEAU, O. CHAIX, J. RAFFl, J.P. AGNEL and A. JEUNET Paramagnetic Species Induced in Bioapatites by Foodstuff Ionisation 151

J. BARTHE, V. KAMENOPOULOU, B. CATOIRE, F. BERMANN and G. PORTAL Electron Spin Resonance Spectra of Irradiated Textiles: Applications to the Dosimetry of Ionising Radiations 167

C. LOUIS, M. CHE and Z. SOJKA The Use ofEPR Spectroscopy in the Molecular Approach to the Preparation of Supported Catalysts and to Catalytic Processes 189

XI

B. NICKEL-PEPIN-DONAT, A. JEUNET, A. RASSAT and H. CHARCOSSET Application de la RPE a la Caracterisation d'un Materiau Fossile: Ie Charbon 211

B. CHAlLOT, B. CASSIER and P. LABRUDE EPR Studies of Oxidation of Iron and Free Radicals Fonnation after Dessication of Oxyhemoglobin by Freeze-Drying and Spray-Drying 217

J.L. ZIMMERMANN CW and Pulsed EPR as a Tool for Studying the Structure of the Oxygen-evolving Enzyme of Photosystem H 223

C.L. DAVIES, J.C. EVANS, C.C. ROWLANDS and M.l FILDES An ESR/ENDOR Study of Solvent Radical Adducts of 2,4,6-Tri-Tert-Butylnitrosobenzene (BNB) 231

C.L. THIERY, lB. TRIOLET, IP.L. AGNEL, C.M. BAITESTI, P.B. VINCENT, U. RAFFI and 1M. THIERY Comparative ESR Spin Trapping Study of Gamma Induced Radicals in Some Mono- and Oligosaccharides: Multicomponent ESR Spectra Simulation with the VOYONS Program 249

A.M. RIQUET, O. AKERMANN, A. FEIGENBAUM, G. PASCAL, A. GAUDEMER and Y. SANDRA Y Compatibility of Packing with Food 259

J.M. DI MEGLIO and D. QUERE Determinatien of the Thickness of Thin Liquid Films on Curved Surfaces 271

A. GUYOT, A. REVILLON, M. CAMPS, J.P. MONTHEARD and B. CATOIRE Electron Spin Resonance Measurement of Nitroxy Probes Mobility, Attached to a Polymer Through a Spacer Ann 277

F. BONON, M. BRUSTOLON, A.L. MANIERO and U. SEGRE An ENDOR Study of Methyl Dynamics at Low Temperature 285

F. ZEEGERS and B. TILQUIN Etude par Resonance Paramagn6tique Electronique (RPE) de la D6croissance Radicalaire dans les Medicaments Irradi6s 291