Table Of ContentENVIRONMENT AL EFFECTS
ON MOLECULAR STRUCTURE AND PROPERTIES
THE JERUSALEM SYMPOSIA ON
QUANTUM CHEMISTRY AND BIOCHEMISTRY
Published by the Israel Academy of Sciences and Humanities,
distributed by Academic Press (N.Y.)
1st JERUSALEM SYMPOSIUM: The Physicochemical Aspects of Carcinogenesis
(October 1968)
2nd JERUSALEM SYMPOSIUM: Quantum Aspects of Heterocyclic Compounds in
Chemistry and Biochemistry (April 1969)
3rd JERUSALEM SYMPOSIUM: Aromaticity, Pseudo-Aromaticity, Antiaromaticity
(April 1970)
4th JERUSALEM SYMPOSIUM: The Purines: Theory and Experiment
(April 1971)
5th JERUSALEM SYMPOSIUM: The Conformation of Biological Molecules and Polymers
(April 1972)
Published by the Israel Academy of Sciences and Humanities,
distributed by D. Reidel Publishing Company (Dordrecht and Boston)
6th JERUSALEM SYMPOSIUM: Chemical and Biochemical Reactivity
(April 1973)
Published and distributed by D. Reidel Publishing Company (Dordrecht and Boston)
7th JERUSALEM SYMPOSIUM: Molecular and Quantum Pharmacology
(March/April 1974)
VOLUME 8
ENVIRONMENTAL EFFECTS
ON MOLECULAR STRUCTURE
AND PROPERTIES
PROCEEDINGS OF THE EIGHTH JERUSALEM SYMPOSIUM ON
QUANTUM CHEMISTRY AND BIOCHEMISTRY HELD IN JERUSALEM,
APRIL 7TH-II TH 1975
Edited by
BERNARD PULLMAN
Universite de Paris, Institut de Bi%gie Physico-Chimique
(Fondation Edmond de Rothschild)
Paris, France
D. REIDEL PUBLISHING COMPANY
I
DORDRECHT-HOLLAND BOSTON-U.S.A.
Library of Congress Cataloging in Publication Data
Jerusalem Symposium on Quantum Chemistry and Biochemistry, 8th, 1975.
Environmental effects on molecular structure and properties.
(The Jerusalem symposia on quantum chemistry and biochemistry ; v. 8)
Bibliography: p.
Includes index.
1. Chemistry, Physical organic-Congresses. 2. Biological
chemistry-Congresses. 3. Solvation-Congresses. I. Pullman,
Bernard, 1918- II. Title. III. Series.
QD476.J38 1975 547'.1'3 75-35543
ISBN-\3: 978-94-010-1839-5 e-ISBN-13: 978-94-010-1837-1
DOl: IO.IOO7/978-94-010-1837-1
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.
Lincoln Building, 160 Old Derby Street, Hingham,
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All Rights Reserved
Copyright © 1976 by D. Reidel Publishing Company, Dordrecht, Holland
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 informational storage and
retrieval system, without written permission from the copyright owner
TABLE OF CONTENTS
PREFACE IX
OPENING WORDS
Prepared by the Late Professor Ernst David Bergmann XI
ALBERTE PULLMAN / Molecular Orbital 'Supermolecule' Approach to the
Solvation Problem 1
JOHN L. BURCH, KRISHN AN S. RAG HUVEER, and RALPH E. CHRISTOFFERSEN /
On the Development of Solvent Effect Models: Method Development and
Initial Applications 17
PETER KOLLMAN, DAVID HAYES, and IRWIN KUNTZ / Electrostatic Proper
ties of Proteins: Role of the Aqueous Solution in Determining Protein Sec-
ondary and Tertiary Structure 31
R. J. ABRAHAM / Approaches to the Problem of Solvation Calculations in Polar
and Charged Molecules 41
BERN ARD PULLMANN / Quantum-Mechanical Studies on the Effect of Water
on the Conformation of Two Biologically Important Zwitterionic Systems:
Polar Head of Phospholipids and GABA 55
P. KEBARLE / Solvent Effects on Acidity and Basicity from Gas Phase Ion
Equilibria Measurements 81
B. A. LEVINE and R. J. P. WILLIAMS / Conformation of Peptides in Water 95
v. RENUGOPALAKRISHNAN, s. NIR, and ROBERT REIN / Theoretical Studies
on the Conformation of Pept ides in Solution. II: Conformations ofN-Acetyl
L-Alanine N-Methyl Amide in CCl and H 0 and N-Acetyl Glycine N-
4 2
Methyl Amide in CCl 109
4
B. J. PRICE and c. M. VENKATACHALAM / Molecular Environmental Effects on
the Puckering of the Proline Ring 135
BIBUDHENDRA SARKAR, v. RENUGOPALAKRISHNAN, THEO P. A. KRUCK,
and SHOW-JY LAU / Molecular Design: Theoretical and Solution Studies on
Copper(II) Complex of Glycylglycyl-L-Histidine-N-Methyl Amide, a Peptide
Designed to Mimic the Copper(II)-Transport Site of Human Albumin 165
o. B. NAGY and J. B. NAGY / Molecular Complexes and Chemical Behaviour:
Competitive Preferential Solvation Theory and Its Applications 179
VI TABLE OF CONTENTS
C. A. SWENSON and D. B. HENSON / Calorimetric Studies of Hydrophobic
Interactions in Aqueous Solution 205
SHERRY LEWIN / Changes in the Adherence of Hydrophobic Groups, and Cor
responding Alterations in Molecular Conformation of Biopolymers, with
Changes in Interfacial Tension of Their Aqueous Solutions 215
MORDECAI RABINOVITZ / Solute-Solute and Solute-Solvent Interactions:
NMR Studies 229
GILDA LOEW, HAREL WEINSTEIN, and DONALD BERKOWITZ / Theoretical
Study of the Solvent Effect on Ionization and Partition Behavior in Related
Opiate Narcotics: Hydromorphone and Oxymorphone 239
F. CRASNIER, I.-F. KERUZORE, AND F. GALLAIS / Solvent Effect and Aro-
matic Compounds: Magneto-Optic Properties 259
WOLFRAM SAENGER /OI:-Cyclodextrin Inclusion Complexes: Mechanism of
Adduct Formation and Intermolecular Interactions 265
lAIN C. PAUL and DAVID Y. CURTIN / Correlation of Chemical Reactivity in
the Solid State with Crystal Structure 307
c. GHIO, E. SCROCCO, and J. TOMASI/The Effects of the Crystal Lattice on the
Electronic Distribution of the Nitrite Ion in the Ferroelectric Phase ofNa2N02 329
DEREK J. HODGSON and PHIRTU SINGH / Intra- and Intermolecular Inter-
actions in Azanucleosides 343
B. HONIG and A. D. GREENBERG / Chromophore Protein Interactions in Visual
Pigments and Their Analogs 355
PAUL E. BLATZ, H. KAWASHIMA, and ROBERT COCKCROFT / Effect of the
Counter Anion on the Oxidation of N-Benzyl-l,4-Dihydronicotinamide 363
GEORG ZUNDEL / Influence of Cations on Secondary Structures of Macro-
molecules and Membranes - IR Investigations 371
SHOSHANA J. WODAK, PETER KAHN, ARTEM K. DADIVANIAN, and CYRUS
LEVINTHAL / Hemoglobin Interaction in Sickle Cell Fibers: Theoretical
Approaches to the Molecular Contacts 389
HAR VE Y KAPLAN and RONALD G. DUGGLEBY / Application of Competitive
Labeling to the Study ofthe Effect of Environment on the Chemical Properties
of Groups in Proteins: Environmental Effects on Histidine Residues 409
JAKE BELLO, HELENE R. BELLO, and HELEN PATRZYC / The Stability of
Bovine Pancreatic Ribonuclease in Glycerol and Glycerol-Cosolvents 419
F. A. MOM ANY / A New Empirical Intermolecular Potential Energy Function
for Hydrogen Bonding: Application to the Gas Phase and Solid State of
Carboxylic Acids and Alcohols 437
TABLE OF CONTENTS VII
J AN HERMANS, DINO R. FERRO, JOHN E. MCQUEEN, and SHIRLEY C. WEI /
Use of Energy Calculations to Refine and Understand Structure and Func-
tion of Proteins 459
P. C. HEINRICH / Coenzyme Apoenzyme Interactions: Studies on the Binding
of Thiamine Diphosphate to Apotransketolase from Baker's Yeast 485
A. W ALEH and L. L. INGRAHAM / Electron Transport in Cytochrome C 505
PATRICK J. COZZONE, STANLEY J. OPELLA, and OLEG JARDETZKY /The
Effect of Temperature on the Structure of Lysozyme in Solution 517
c. SANDORFY / On the Anesthetic Potency of Fluorocarbons, Their Ionization
Potentials, and Their Dissociative Effect on Hydrogen Bonds 529
JOEL L. SUSSMAN and SUNG-HOU KIM / A Preliminary Refinement of Yeast
tRNAPhe at 3 A Resolution 535
DONALD S. BERNS, CHANG-HWEI CHEN, and ASHER ILANI / The Modifica-
tion by Biliproteins of Intensity and Direction of Electron Flow across
Chlorophyll-Containing Membranes 547
R. KORENSTEIN and K. A. MUSZKAT / Environmental Effects on Processes of
Excited Molecules - External Spinorbit Coupling Effects on Photochemical
Reactions of Bianthrone-like Molecules 561
ISRAEL AGRANAT, I. B. BERLMAN, and YERUHAM RICHTER / Ground-State
versus Excited-State Polarity of Triafulvenes: A Study of Solvent Effects on
Molecular Electronic Spectra 573
INDEX OF NAMES 585
PREFACE
The holding of the 8th Jerusalem Symposium was saddened by the sudden death of
Professor Ernst D. Bergmann at the very eve of this meeting. With him disappeared
one of the leading world scientists in the field of physical chemistry and biochemistry.
His innumerable friends and admirers over the whole world mourn him profoundly.
All those who knew him personally and among them the participants in the previous
Jerusalem Symposia will remember for ever the exceptional qualities of the scientist
and the unusual human warmth of the man.
With Ernst D. Bergmann the state of Israel lost one of the founders of its Science
and one of its most brilliant and renowned representatives. The spirit which he suc
ceeded to inoculate into his numerous disciples and pupils will, however, continue to
perpetuate his name and his work. The Jerusalem Symposia will continue as a living
testimony to his brilliant inspiration.
Before dying, Professor Bergmann has prepared a few opening remarks for the
8th Jerusalem Symposium. They are reproduced here.
BERNARD PULLMAN
OPENING WORDS
Prepared by the Late Professor Ernst David Bergmann
It gives me great pleasure to welcome you all on behalf of the President and the Rector
of the Hebrew University which is co-sponsoring this meeting, and of the President
and Council of the Israel Academy of Sciences and Humanities which for the eighth
time has put its premises at our disposal.
If we look at the central subject to which these symposia have been devoted we can
see a clear progress towards more and more complex problems, trying each time to
memorize what we know and to formulate the questions which remain open. This is
the first time that we deliberately leave the consideration of individual molecules and
try to assemble our knowledge of the effect of the surroundings on the individual
molecules.
Jerusalem is a unique city - there is none other like it. Many of you, perhaps most
of you, may have expected this symposium to take place in a warlike atmosphere.
It is true the country is at war, but you wiII see it is not militarized. This is true for the
country as a whole. We are ready to fight for our survival as a State but we are not
wiIIing to give up the normal pursuit of development generally and particularly in
the sciences.
We are grateful to the Baron Edmond de Rothschild and the Israel Academy of
Sciences and Humanities for the possibility to show our friends this phenomenon
which, in my opinion, is a good omen for the future, and I hope that you wiII enjoy
the serene and quiet atmosphere of this country, of this city and of this bUilding.
MOLECULAR ORBITAL 'SUPERMOLECULE'
APPROACH TO THE SOLVATION PROBLEM
ALBERTE PULLMAN
Institut de Bi%gie Physico-Chimique, Laboratoire de Biochimie TMorique,
associe au C.N.R.S., 13, rue P. et M. Curie - 75005, Paris, France
1. Introduction
Until very recently, the theoretical evaluation of the effect of the medium on the
behavior and properties of molecules was beyond the reach of quantum mechanical
computations, essentially due to the prohibitive size of the systems which would have
to be considered. Thus the habit evolved to treat essentially the isolated molecule and
be satisfied by qualitative considerations or, at best, approximate evaluations of the
bulk effect of the medium following early models [1]-[3]' The last few years have seen
a number of attempts at a refinement of these 'continuum' or 'macroscopic' represen
tations [4, 5, 6, 7]. One constant and essential inconvenience of these models is, how
ever, the absence of precision concerning the arrangement of the solvation layer(s)
around the solute, which is considered as residing in a cavity (generally spherical)
embedded in a polarizable dielectric. No information is obtainable in this way about
the details of the short-range solute-medium interactions.
Recently, a different line of research started to be developed which consists of a
'discrete' treatment, in which one tries to establish the individual effect of the medium
molecule(s) upon the system studies. This is achieved in general through the utiliza
tion of the 'supermolecule' model which combines, in a unique exploration, the molec
ular entities in interaction, such as the solute and the solvent molecule(s). Such an
approach became possible owing to the very recent considerable developments in the
applicability of the molecular orbital method: it is now possible to compute non
empirically a system solute + solvent of reasonable size, treating all the electrons in the
field of all the nuclei. In this fashion one may evaluate the most probable sites of
interaction and gather information about the nature of the binding, if any, the binding
energy and also the flexibility of the association.
This second way of approach is obviously particularly well adapted for dealing with
the problem of 'bound' water in a broad sense. Its particular aim is the detection of
the preferred, if such, modes of interaction of the solvent molecules with the receptor
and the characterization of such interactions. The second stage of the research consists
in determining the extent to which this primary interaction produces observable and
measurable effects.
We have applied this approach in our laboratory to the exploration of the hydration
scheme of a series of fundamental biological molecules, and in particular of the con
stituents of the biological polymers and related systems: formamide [8], N-methyla
cetamide [9], the hydrogen-bonded peptide linkages of proteins [10, 11], the amino
B. Pullman (ed.) , En~ironmental E;ffects on Molecular Structure and Properties, 1-15. All Rights Reserved
Copyright © 1976 by D. Reidel Publishing Company. Dordrecht-Holland
