DYNAMIC ASPECTS OF CONFORMATION CHANGES

IN BIOLOGICAL MACROMOLECULES

DYNAMIC ASPECTS OF

CONFORMATION CHANGES IN

BIOLOGICAL MACROMOLECULES

PROCEEDINGS OF THE 23RD ANNUAL MEETING

OF THE SOCIETE DE CHIMIE PHYSIQUE

ORLEANS, 19-22 SEPTEMBER 1972

Edited by

CHARLES SAD RON

Professeur au Museum National d'Histoire Naturelle Directeur du Centre de Biophysique MoIeculaire

(C.N.R.S.)

D. REIDEL PUBLISHING COMPANY

DORDRECHT-HOLLAND! BOSTON-U.S.A.

First printing: December 1973

Library of Congress Catalog Card Number 72-97962

ISBN-13: 978-94-010-2581-2 e-ISBN-13: 978-94-010-2579-9 DOl: 10.1007/978-94-010-2579-9

Published by D. Reidel Publishing Company, P.O. Box 17, Dordrecht, Holland

Sold and distributed in the U.S.A., Canada, and Mexico by D. Reidel Publishing Company, Inc.

306 Dartmouth Street, Boston, Mass. 02116, U.S.A.

All Rights Reserved Copyright © 1973 by D. Reidel Publishing Company, Dordrecht, Holland

Softcover reprint of the hardcover 1st edition 1973 No part of this book may be reproduced in any form, by print, photoprint, microfilm,

or any other means, without written permission from the publisher

T ABLE OF CONTENTS

PREFACE ~I

ORGANIZING COMMITTEE IX

ACKNOWLEDGMENTS IX

LIST OF PARTICIPANTS XI

B. PULLMAN / Quantum-Mechanical Studies on the Conformation of Bio-molecules 1

M. PT AK / Analyse conformationnelle des biopolymeres par les methodes semi-empiriques 23

M. GOLDBERG / l'Etat natif est-ill'etat fondamental? 57 E. M. BRADBUR Y, P. D. CAR Y, C. CRANE-ROBINSON, and H. w. E. RATTLE /

Conformations and Interactions of Histones and Their Role in Chromosome Structure 67

c. TONIOLO / Conformational Equilibria and Stability of Oligopeptides 87 A. HVIDT / Isotopic Hydrogen Exchange in Solutions of Biological Macro-

molecules 103 P. COLSON and J. P. GASPARD / Determination of the Relaxation Spectrum of

Macromolecules in Solution by the Analysis of the Electric Birefringence 117 PH. WAHL and J. c. BROCHON / Resolution of the Fluorescence Spectra of

Proteins Using Decay Measurements 129 L. F. TEN EYCK and P. D. PULSINELLI / Tertiary and Quaternary Structural

States of Hemoglobin 137 K. WUTHRICH, R. M. KELLER, and R. BAUMANN / Proton and Carbon-13

Nuclear Magnetic Resonances in Hemes and Hemoproteins: New Aspects for the Investigation of the Molecular Conformations 151

R. G. SHULMAN, D. R. KEARNS, B. R. REID, and Y. P. WONG / A High Resolu-tion NMR Study of Hydrogen Bonded Protons in tRNA 165

B. ALPERT, R. BANERJEE et L. LINDQVIST / Cinetique des changements de conformation tertiaires de l'hemoglobine etudiee par photolyse-Iaser 171

A. BAli D R AS / Transitions reversibles d'activite et de structure quaternaire de la L ( + ) lactate: cytochrome C oxydoreductase (cytochrome bz) de la levure Hansenula anomala 181

J. WYMA N / On Allosteric Models 207 H. BUC, M. H. BUC, M. MORANGE, L. c. OUDIN, and H. WINKLER / Conforma­

tional Changes in Glycogen Phosphorylase b from Rabbit Skeletal Muscle. Equilibrium and Kinetic Studies 225

VI TABLE OF CONTENTS

R. CERF / Quelques problemes de cinetique conformationnelle de systemes co-operatifs 247

D. THUSIUS, G. FOUCAULT, and F. GUILLAIN / The Analysis of Chemical Re­laxation Amplitudes and Some Applications to Reactions Involving Macro-molecules 271

M. LAZDUNSKI, c. LAZDUNSKI, c. PETITCLERC, D. CHAPPELET, M. FOSSET,

c. GACHE, et M. DELAAGE / Mecanismes enzymatiques de type flip-flop 285 J. P. EBEL / Structure tridimensionnelle des acides ribonucleiques de transfert 301

J. J. HOPFIELD, S. OGAWA, and R. G. SHULMAN / The Rate of Carbon Mon-

oxide Binding to Hemoglobin Kansas 327 J. RAMSTEIN, J. F. HOGREL, M. DOURLENT, M. LENG, et C. HELENE / Inter­

actions de la proflavine avec differents ADN et polynucleotides de synthese 333

c. HELENE, H. BORAZAN, J. L. DIMICOLI, J. C. MAURIZOT, M. DURAND, et

J. J. TOULME / Interactions des acides amines aromatiques avec les acides

nUcleiques 349

D. GENEST and PH. WAHL / Energy Transfers Study in the DNA-Ethidium

Bromide Complex by means of Anisotropy Decay 367

M. LENG, V. DEUBEL, et J. C. THRIERR / Etude des interactions entre l'acide

polyribo-uridylique ou l'acide polyribobromo-uridylique et des polycations 381

F. TRAVERS, A. M. MICHELSON, et P. DOUZOU / Acide poly-uridylique a basse temperature 393

w. GUSCHLBAUER,D. THIELE,M.-T. SARoccHI,etcH. MARCK / Phenomenes

d'hysterese dans les polynucIeotides 401

D. VASILESCU, M. TEBOUL, H. KRANCK, et B. CAMOUS / Etude de la trans­

conformation thermique du Na-DNA en solution par la spectrographie de

bruit 411

SH. LIFSON / Recent Developments in the Consistent Force Field Calculations 421

M. IWATSUBO, J. M. JALLON, et A. DI FRANCO / Etude cinetique des change­

ments conformationnels de la glutamate deshydrogenase par substrats et effecteurs 431

J. M. YON et J.-P. TENU / Mouvements moleculaires consecutifs a la fixation de

metaux dans la p-galactosidase 447

B. LABOUESSE / Mouvements intramoleculaires dans la chymotrypsine 459

R. D. KORNBERG / The Diffusion of Phospholipids in Membranes 477

PH. DEVAUX, C. J. SCANDELLA, et H. M. MCCONNELL / Etude par marquage

de spin de la diffusion laterale dans les membranes biologiques 487

s. FERMANDJIAN, D. GREFF, et P. FROMAGEOT / Angiotensine II et analogues:

Etudes conformationnelles comparatives 493 J. P. CHANGEUX / Caracterisation, isolement et purification de la proteine re-

ceptrice de l'acetylcholine a partir de l'organe electrique du gymnote 511

PREFACE

On the day after the 1959 Cambridge Congress, during which the International Union of Pure and Applied Biophysics was founded, a biophysics section was formed within the Society of Physical Chemistry (Societe de Chimie Physique).

Since then, three of the Society's annual meetings (the 11th, 17th, and 23rd) were devoted exclusively to the physico-chemical study of biological systems.

The first of these was held in June 1961 at a hotel in Col de Voza, at the foot of an alpine glacier above Chamonix.

The second, in May 1967, took place in the more learned setting of the venerable rooms of the National Museum of Natural History in Paris.

The third - the one dealt with in the present volume - was recently held at Orleans-La Source in the newly built lecture theatres of the young University, which is near the great Institutes of the National Centre for Scientific Research (CNRS), on the Sologne plateau.

These three stages are milestones of an evolution which characterises (at least schematically) the explosive evolution of biological physico-chemistry.

The first colloquium, with the title 'Deoxyribonucleic Acid: Structure, Synthesis and Functions', actually marks the first contact of the physical chemist with one of the then most prestigious biological macromolecules, the structure of which had just been discovered, and in this way celebrated one of the first and most striking successes of molecular biology.

The second, less biologically orientated, was devoted to the general study of helicoidal macromolecules in solution, thus marking a return to the fundamental pre­occupations of the physical chemistry of macromolecules.

The third, however, represents a considerable leap forward because it not only examines critically the problems of the determination of a variety of structures but also of the dynamics of the structural changes these molecules undergo under the influence of physical as well as chemical agents, thus showing the way towards a general study of the relationship between structure and function.

It should perhaps be emphasised that, in spite of everything, we are still confined to the study of the macromolecular compounds in isolation from their native structural unit, and still far removed from the latter's complexities.

Nevertheless we would like to point out that the last session of the congress was devoted to membranes and their properties, thus providing an important starting point leading to the physico-chemical study of the structures within the organic entity of the living cell.

Without resorting to the daring extrapolations sometimes indulged in by the physical chemist when he allows himself to be too easily seduced by the wonderful

VIII PREFACE

world of biological facts, we do believe that this colloquium - no doubt one of many others equally as significant - represents a step forward on the long road towards combining in one unified theory both inanimate and living nature. We have been profoundly and sincerely inspired by all the eminent scientists, from abroad and from France, who honoured us with their presence and to whom we extend our warmest feelings of gratitude.

c. SADRON

Chairman of the Orgallizing Committee

ORGANIZING COMMITTEE

C. Sadron, Chairman C. Troyanowsky, General Secretary R. Banerjee P. Bothorel H.Buc J. Coursaget M. Daune

L. Monnerie J. Monod M. Ptak B. Pullman A. Rassat Miss J. Yon Mrs. O. Yovanovitch

ACKNOWLEDGMENTS

The 23rd Annual Meeting of the Societe de chimie physique was organized with the financial help of the following organizations: Delegation generale a la recherche scienti­fique et technique; Ministere de l'education nationale: Direction de la cooperation universitaire internationale; Direction des recherches et moyens d'essais; Commis­sariat a l'energie atomique; and the following firms and industrial groups: Compagnie franQaise de raffinage; Laboratoires Sandoz; Societe l'Air Liquide; Societe Kodak PatM; Union des industries chimiques. We should like to renew our thanks to all the above.

LIST OF PARTICIPANTS

Albiser, G., Laboratoire de biophysique, Nancy Alfsen, Mme, Facu!te de Medecine, Laboratoire des Etats lies mo!ecu!aires, Paris Alpert, B., Institut de biologie physico-chimique, Paris Arrio, B., Institut de biochimie, Orsay Aslanian, Mme, Physique des solides, Ecole Normale Superieure, Paris Aufauvre, F., Centre Universitaire des Sciences et Techniques, Clermont-Ferrand Banerjee, R., Institut de biologie physico-chimique, Paris Baudras, A., Institut de physiologie, Toulouse Bechet, J. J., Enzymologie physico-chimique et moleculaire, Orsay Berliner, C., Chimie generale II, Universite de Bruxelles (Belg.) Berteaud, A. J., Laboratoire du CNRS, Bellevue Blandin, Mme, Centre de genetique moleculaire, Gif s/Yvette Bothorel, P., Centre de recherches Paul Pascal, 33-Talence Bottreau, A. M., Optique ultra-hertzienne, 33-Talence Bouhet, J. c., Service de biochimie, CEN, Sac1ay Bourgarit, J. J., Unite de physique biologique, Paris VII Bourgoin, D., Institut Pasteur, Service de biophysique, Paris Bradbury, E. M., Biophysics Laboratories, Portsmouth Polytechnic (G.B.) Brochon, J. c., Centre de biophysique moleculaire, Orleans Buc, H., Biochimie cellulaire, Institut Pasteur, Paris Buc, M. H., Mme, Biochimie cellulaire, Institut Pasteur, Paris Caloin, M., Acoustique moleculaire, Strasbourg Cambrai, M., Laboratoire de recherches Unilever, La Plaine St Denis Cardinaud, R., Departement de biologie, CEN, Gif s/Yvette Castaing, Mme, Laboratoire de biochimie physique, Orsay Cerf, Acoustique moleculaire, Universite B. Pascal, Strasbourg Chaillot, B., Biologie physico-chimique, IBANA, Dijon Chambron, 1., Institut de physique biologique, Strasbourg Changeux, J. P., Neurobiologie moleculaire, lnstitut Pasteur, Paris Charlier, M., Centre de biophysique moleculaire, Orleans Charmasson, R., Laboratoire de physique des liquides, Universite de Provence,

Marseille Checcucci, A., Laboratorio per 10 studio delle pro prieta fisiche di bimolecule e cellule,

Pi sa (Ital.) Clar, Mme, Laboratoire de recherches Unilever, La Plaine St Denis Claverie, 1. M., Unite de physique biologique, Universite Paris VII Clement, R., Groupe de biophysique du CRM, Strasbourg

XII LIST OF PARTICIPANTS

Colonna-Cesari, F., Laboratoire de biophysique, Nancy Colson, P., Service de chimie physique, Universite de Liege (Belg.) Colson-Guastalla, Mme, Laboratoire de biologie physico-chimique, Universite de

Montpellier Cotrait, M., Laboratoire de cristallographie et de physique cristalline, Talence Coursaget, 1., Departement de biologie du CEA, Gif s/Yvette Daune, M., Universite Blaise Pascal, CRM, Strasbourg De Coen, 1. L., Departement de biologie moleculaire, U niversite de Bruxelles ( Belg.) Delbos, G., Optique ultra-hertzienne, 33-Talence Devaux, P., Stanford University, California (U.S.A.) Di Franco, A., MIle, Enzymologie physico-chimique et moleculaire, Orsay Donzel, 8., Centre de biophysique moleculaire, Orleans Dornand, 1., EN SCM, Montpellier Douzou, P., Institut de biologie physico-chimique, Paris Dunand, 1. 1., Societe CAMECA, Courbevoie Ebel, 1. P., Laboratoire de chimie biologique, Universite L. Pasteur, Strasbourg Ellenberger, M., Departement de biologie, CEN, Saclay Engelborghs, Y., Departement de biologie moleculaire, Universite de Bruxelles (Belg.) Fermandjian, S., Service de biochimie, CEN Saclay., Gif s/Yvette Filitti-Wurmser, S., Mme, Institut de biologie physico-chimique, Paris Finer, E. G., Laboratoire de recherches Unilever, Welwyn (G.B.) Fougnot, c., Mile, Centre scientifique et poly technique, Saint-Denis Fredericq, E., Laboratoire de chimie physique, Universite de Liege (Belg.) Freymann, R., Laboratoire de Physique moleculaire experimentale, Universite de

Paris VI Fuchs, R., Laboratoire de biophysique du CRM, Strasbourg Gache, c., Centre de biochimie et de biologie moleculaire, Marseille Garnier, 1., Laboratoire de biochimie physique de l'INRA, Orsay Garrigou-Lagrange, c., MIle, Centre de recherches P. Pascal, 33-Talence Gaspard, 1. P., Institut Laue-Langevin, 38-Grenoble Genest, D., Centre de biophysique moleculaire, Orleans Gentou, c., Service de biochimie medicale, Faculte de medecine, Clermont-Ferrand Gerard, D., Laboratoire de physique, UER de Sciences, Strasbourg Gingold, Service de biophysique, CEN Saclay, Gif s/Yvette Goldberg, M., Biochimie cellulaire, Institut Pasteur, Paris Grosjean, H., Laboratoire de chimie biologique, Universite Iibre de Bruxelles (Belg.) Grouselle, M. 1., Institut de biochimie, Orsay Guinand, S., MIle, Laboratoire de biologie physico-chimique, Orsay Guschlbauer, W., Service de biochimie du CEN Saclay, Gif s/Yvette Hanss, M., U.E.R. de medecine et biologie, Bobigny Helene, c., Centre de biophysique moleculaire, Orleans Hellemans, L., BioI. Dynamics, Universite de Louvain (Belg.) Her, c., Laboratoire de recherches Unilever, La Plaine St-Denis

LIST OF PARTICIPANTS

Holguin-Hueso, J., Departement de biologie du CEA, Gif s/Yvette Horn, P., Laboratoire de biophysique, Centre 1 er cycle, Nancy Huet, Mme, Unite de physique biologique, Paris VII Hvidt, A., Mme, Laboratoire de chimie III, Universite de Copen hague (P.B.) Iwatsubo, M., Centre de genetique moleculaire, Gif s/Yvette Joly, M., Service de biophysique, Institut Pasteur, Paris Jozefonvicz, J., Mme, Centre scientifique et poly technique, Saint-Denis

XIII

Kamenka, Mme, Laboratoire des Interactions moleculaires, Universite de Mont-pellier

Karplus, M., Harvard University - Institut de biologie physico-chimique, Paris Kellershorn, Enzymologie physico-chimique et moleculaire, Orsay Kornberg, R., Stanford Univ., USA - MRC, Molecular biology, Cambridge, U.K. Labeyrie, F, Mme, Centre de genetique moleculaire, Gif s/Yvette Labouesse, B., Laboratoire de biochimie, Universite de Bordeaux, 33-Talence Lam, T. H., Departement de biologie du CEN Saclay, Gif s/Yvette Lami, H., Laboratoire de physique, UER Pharmacie, Strasbourg Lang, M., Centre de recherches sur les macromolecules, Strasbourg Lawrence, J. J., Laboratoire de biologie cellulaire, CEN Grenoble Lazdunski, M., Centre de biologie moleculaire, Marseille Lecompte, Mile, Centre scientifique universitaire, Saint-Denis Lefevre, J. F., Centre de recherches sur les macromolecules, Strasbourg Leicknam, J. P., SRIRMA, CEN Saclay, Gif s/Yvette Lenfant, J. P., Laboratoire de biochimie physique, INRA, Orsay Leng, M., Centre de biophysique moleculaire, Orleans Levilliers, Mile, Institut de biochimie, Orsay - Hopital Cochin, Paris Lifson, S., Weizmann Institute, Rehovot, (lsr.) Loze, C de, Mlle, Service de chimie physique, CNRS, Thiais Lussan, C, Centre de recherches Paul Pascal, 33-Talence Magat, M., Physico-chimie des rayonnements, Orsay Maigret, B., Institut de bio]ogie physico-chimique, Paris Majoube, Departement de biologie, CEN Saclay, Gif s/Yvette Mani. J. C, ENSCM, Montpellier Marche, P .. Departement de biologie, CEN Saclay, Gif s/Yvette Mareschi. M., Centre d'etudes cryogeniques de l'Air Liquide, 38-Sassenage Marzat, C, Optique ultra-hertzienne, Universite de Bordeaux Matricon. J., Laboratoire de physique des soli des, Universite de Paris VII Maurizot, J. C, Centre de biophysique moleculaire, Orleans Melki, G., Laboratoire de biophysique, Centre anticancereux, Rennes Menezes, L. C, Institut de biochimie, Orsay Mestdagh, Mile, Universite de Louvain (Belg.) Metzger, G., Centre de recherche sur les macromolecules, Strasbourg Michels, B., Acoustique moleculaire, Universite L. Pasteur, Strasbourg Monsigny, M., Centre de biophysique moleculaire, Orleans

XIV LIST OF PARTICIPANTS

Morange, M., Biologie moleculaire, Institut Pasteur, Paris Morel, J. E., Departement de biologie du CEN Saclay, Gif sjYvette Morgat, J. L., Service de biochimie du CEA, Gif sjYvette Morin, P., Laboratoire de biologie physico-chimique, Universite de Montpellier Muller, D., Centre scientifique universitaire de Saint-Denis Murcia, X. de, Laboratoire de biophysique, Universite L. Pasteur, Strasbourg Nabredick, E., Mme, Departement de biologie, CEN Saclay, Gif sjYvette Pairault, X., H6pital Cochin, Paris Pantaloni, D., Laboratoire d'enzymologie du CNRS, Gif s/Yvette Pernollet, J. c., Laboratoire de biochimie physique, INRA, Orsay Persoons, A., Universite de Louvain (Belg.) Pinset, I., Mme, Departement de biologie, CEN Saclay, Gif s/Yvette Popot, J. L., Unite de neurobiologie moleculaire, Institut Pasteur, Paris Pouradier, J., Societe Kodak PatM, Vincennes Pouyet, J., Centre de recherches sur les macromolecules, Strasbourg Premillat, S., Laboratoire de biophysique, centre de ler cycle, Nancy Ptak, M., Centre de biophysique moleculaire, Orleans Pudles, J., Institut de biochimie, Orsay Pullman, B., Institut de biologie physico-chimique, Paris Ramstein, J., Centre de biophysique moleculaire, Orleans Rassat, A., Centre d'Etudes Nucleaires de Grenoble Reiss, C., Centre de genetique moleculaire, Gif s/Yvette Rinaudo, M., Mme, CERMA V, Grenoble Rodriguez, J. M. Ruysschaert, J. M., Chimie generale II, Universite libre de Bruxelles (Belg.) Sadron, c., Centre de biophysique moleculaire, Orleans Sanson, A., Centre de biophysique moleculaire, Orleans Schmitt, B., Unite de physique biologique, Universite Paris VII Schott, B., Groupe de physique des solides, Universite Paris VII Schreiber, J. P., Centre de recherches sur les macromolecules, Strasbourg Schulz, J. A., Laboratoire d'acoustique moleculaire, Strasbourg Schweitz, H., Centre de biochimie moleculaire, Marseille Shulman, R. G., Bell Laboratories, Murray Hill (U.S.A.) Sturm, Centre de recherches sur les macromolecules, Strasbourg Tassin, J. J., Societe CAMECA, Courbevoie Tchuempe-Tchuente, G., Laboratoire de physique medicale, Rennes Teissie, J., Chimie macromoleculaire, EPCI, Paris Ten Eyck, L. F., MRC Laboratories of Molecular Biology, Cambridge (G.B.) Tenu, J. P., Laboratoire d'enzymologie physico-chimique et moleculaire, Orsay Thiele, Mme, Departement de biologie, CEN Saclay, Gif sjYvette Thierry, c., Mme, Departement de biologie, CEN Saclay, Gif s/Yvette Thiery, J., Departement de biologie, CEN Saclay, Gif s/Yvette Thiriet, Y., Acoustique moleculaire, Strasbourg

LIST OF PARTICIPANTS

Thusius, D., Laboratoire d'enzymologie physico-chimique et moleculaire, Orsay Toniolo, c., Institut de chimie organique, Universite de Padoue (Ital.) Travers, F., Institut de biologie physico-chimique, Paris Troyanowsky, c., Laboratoire de chimie physique, EPCI, Paris Vasilescu, D., Laboratoire de biophysique, Universite de Nice Venard, R., MIle, Laboratoire de biologie physico-chimique, Orsay ViaIlet, P., Laboratoire de chimie physique, Centre Universitaire de Perpignan Vigny, P., Laboratoire Curie, Institut du Radium, Paris Vincent, J. P., Centre de biologie moleculaire du CNRS, Marseille Weill, G., Centre de recherches sur les macromolecules, Strasbourg Weintraub, Mme, Laboratoire des Hormones, H6pital du Kremlin-Bid:tre Wurmser, R., Imtitut de biologie physico-chimique, Paris Wuthrich, K., Institut de biologie moleculaire et biophysique, Zurich (Suisse) Yon, J., Mlle, Laboratoire d'enzymologie physico-chimique et moleculaire, Orsay Zana, R., Centre de recherches sur les macromolecules, Strasbourg

xv