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WATER
A COMPREHENSIVE TREATISE
Volume 4
Aqueous Solutions of
Amphiphiles and Macromolecules
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WATER
A COMPREHENSIVE TREATISE
Edited by Felix Franks
Volume 1 The Physics and Physical Chemistry of Water
Volume 2 Water in Crystalline Hydrates;
Aqueous Solutions of Simple Nonelectrolytes
Volume 3 Aqueous Solutions of Simple Electrolytes
Volume 4 Aqueous Solutions of Amphiphiles
and Macromolecules
Volume 5 Water in Disperse Systems
WATER
A COMPREHENSIVE TREATISE
Edited by Felix Franks
Unilever Research Laboratory
Sharnbrook, Bedford, England
Volume 4
Aqueous Solutions of
Amphiphiles and
Macromolecules
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Franks, Felix.
Aqueous solutions of amphiphiles and macromolecules.
(His Water: a comprehensive treatise, v. 4)
Bibliography: p.
1. Macromolecules. 2. Solution (Chemistry) I. Title.
QDl69.W3F7 vol. 4 [QD381] 553'.7'08's [547'.7] 74-17244
ISBN 978-1-4684-2960-2
ISBN 978-1-4684-2960-2 ISBN 978-1-4684-2958-9 (eBook)
DOI 10.1007/978-1-4684-2958-9
© 1975 Plenum Press, New York
Softcover reprint of the hardcover 15t edition 1975
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N.Y. 10011
United Kingdom edition published by Plenum Press, London
A Division of Plenum Publishing Company, Ltd.
4a Lower John Street, London WIR 3PD, England
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Preface
This volume of "Water-A Comprehensive Treatise" is devoted to aqueous
solutions of macromolecules and aqueous systems of small molecules which
exhibit reversible aggregation in solution. This latter type of behavior is
closely linked with the hydrophobic interaction and a chapter devoted to
this subject is therefore included in the volume.
As the volumes constituting this treatise progress from pure water
through solutions of simple molecules to the present volume, the level of
our understanding of observed phenomena decreases and the experimental
and theoretical techniques available become less adequate to provide the
detailed information required. Thus, for example, we have so far been unable
to include the generally acknowledged solvent effects in conformational
calculations on biopolymers. On the credit side, however, some of the in
formation gained from the study of simple aqueous solutions and water
by itself is now beginning to find application in the elucidation of the
properties of the systems discussed in this volume.
Perhaps an editorial explanation is required for lack of uniformity
of approach by the various contributing authors, but this is primarily due
to the historical development of the subjects covered. Thus the study of
lipids, nucleotides, proteins, and polysaccharides originated in the biological
disciplines where water has always been accepted as the natural substrate,
even though its role in promoting the various in vivo processes has only
recently been recognized. On the other hand the subject of aqueous solutions
of synthetic macromolecules has grown out of classical polymer physics
and chemistry where water as a solvent is generally avoided, and for good
reasons. It is nevertheless my view that water-soluble and water-sensitive
polymers have considerable technological potential and it is my hope that
the material collected in this volume may help in the exploitation of these
interesting substances.
All the subjects covered by this book are still in a state of rapid develop
ment so that much of what is written here may look out of date two years
v
vi Preface
from now. It is nevertheless my hope that the approaches taken by the
authors will provide new slants on well established phenomena.
Once again my thanks are due first and foremost to Mrs. Joyce Johnson
for her invaluable and cheerful help with preparation of manuscripts,
mdexing, checking references, and communicating with authors and pub
lishers. I should also like to thank my colleagues and many friends in the
"International Water Fraternity" for advice and guidance.
October, 1974 F. FRANKS
Contents
Contents of Volume 1 xv
Contents of Volume 2 XVll
Contents of Volume 3 XIX
Contents of Volume 5 XXI
Chapter 1
The Hydrophobic Interaction
F. Franks
1. Introduction
2. Phenomenology and Nomenclature 2
3. Physical Properties of Infinitely Dilute Aqueous Solutions of "Ef-
fectively Hydrophobic" Molecules . . . . . . . . . . . . .. 5
3. I. Thermodynamic Characterization . . . . . . . . . . .. 5
3.2. A Formal Description of the Hydrophobic Hydration Phe-
nomenon . . . . . . . . . . . . . . . . . . . 13
3.3. The Microscopic Nature of Hydrophobic Hydration 18
3.4. Theoretical Approaches to Hydrophobic Hydration 26
3.5. Summary and Conclusions . . . . . . . . . . . 36
4. The Manifestation of Hydrophobic Association Effects in Aqueous
Solutions of Simple Alkyl Derivatives . . . . . . . . . . .. 37
4.1. Thermodynamics of Moderately Dilute Solutions .... 37
4.2. Evaluation of Molecular Interactions from Thermodynamic
Data ........................ 45
4.3. Direct Investigation of Time-Averaged Structures in Solution 53
4.4. Time-Dependent Properties . . . . . . . . . . . . . .. 59
4.5. Theoretical Studies of the Hydrophobic Interaction between
Simple Molecules . . .. ............. 67
vii
viii Contents
5. The Hydrophobic Interaction in Complex Aqueous Systems 81
5.1. Thermodynamic Studies in Perturbed Aqueous Media . 85
5.2. Spectroscopic Identification of the Hydrophobic Interaction
in Complex Systems . . 91
5.3. Summary and Prospects . . . . . . . . . . . . . . .. 93
Chapter 2
Surfactants
G. C. Kresheck
I. Introduction 95
2. Critical Micelle Concentration . 96
2.1. Methods of Determination 96
2.2. Importance of the Side Chain 98
2.3. Temperature . . . . . 103
2.4. Salts. . . . ..... 105
2.5. Nonelectrolyte Additives 114
2.6. D 0 ..... . 119
2
3. Aggregation Number 120
4. Shape and Hydration 122
5. Counterion Binding . 125
6. Pre-Micellar Association 132
7. Post-Micellar Association 133
8. Mixed Micelles . . . 134
9. Nonaqueous Micelles 140
10. Thermodynamics of Micelle Formation 144
11. Kinetics of Micelle Formation 163
12. Conclusion ....... . 166
Chapter 3
Dyestuffs
D. G. Duff and C. H. Giles
1. Introduction 169
2. The Nature of the Dyestuffs 170
Contents ix
2.1. Cationic Dyes 171
2.2. Anionic Dyes 173
3. Spectral Characteristics of Dyes in Solution . 174
3.1. Aqueous Solutions .... . . . . . 174
3.2. Apparent Deviations from Beer's Law .. 182
4. Methods of Measuring the Degree of Aggregation of Dyes in
Aqueous Solution . . . . . . . . . . . . . . . . 184
4.1. Methods Employing Electromagnetic Radiation 185
4.2. Methods Based on Diffusion Properties . . . 187
4.3. Methods Based on the Electrical Properties of Dyes in
Solution . . . . . 190
4.4. Other Methods . . 191
4.5. Summary of Results 191
5. Dye Aggregates . . . . 193
5.1. The Nature of the Aggregates 194
5.2. Nature of the Bonding in Aggregates 198
6. The Role of Water 204
7. Conclusions 207
Chapter 4
Lipids
H. Hauser
1. Introduction 209
2. Physical Properties of Lipids 213
2.1. Amphipathic Character 213
2.2. Surface Properties . . . 213
2.3. Physical Properties of the Solid State 215
3. Lipid-Water Phase Behavior . 232
3.1. Lyotropic Mesomorphism 232
3.2. Phospholipid-Water Phases 235
3.3. Conformation and Molecular Motion of the Hydrocarbon
Chains in Lyotropic, Liquid Crystalline Phases . 245
4. Hydration of Phospholipids . . . . . . . . . . . . 254
4.1. Water Vapor Adsorption to Phosphatidylcholine 256
4.2. Hydrodynamic Measurements 257
x Contents
4.3. Thermal Analysis . . . . . . . . . . . . . . . . . . . 261
4.4. X-Ray Diffraction . . . . . . . . . . . . . . . . . . . 262
4.5. Diffusion Coefficient of Water in Lamellar Liquid Crystalline
Phosphatidylcholine-Water Systems . . . . 263
4.6. Proton Magnetic Resonance Measurements 268
4.7. Deuteron Magnetic Resonance Measurements 275
4.8. Mixed Lipid Systems 284
4.9. Conclusions 288
5. Hydration of Glycerides 289
6. Summary 297
Chapter 5
Nucleic Acids, Peptides, and Proteins
D. Eagland
I. Introduction 305
2. Experimental Techniques 319
2.1. Optical Rotation, Rotary Dispersion, and Circular Dichroism 319
2.2. Spectrophotometry ............ 323
2.3. High-Resolution Nuclear Magnetic Resonance 327
2.4. Calorimetry 330
2.5. Other Techniques . . . . . . . . . . . . . 332
3. The Importance of Water and Hydration Interactions in Deter
mining the Conformational Stability of Biomacromolecules in
Aqueous Solution . . . . . . . . . . . . . . . . . . . 335
3.1. Conformational Transitions in Nonfibrous Proteins and
Polypeptides. . . . . . . . . . . . . . . . . . . . 335
3.2. The Helix-Coil Transition in Nucleic Acids, Nucleosides, and
Nucleotides . . . . . . . . . . . . . . . . . . . . . . 354
3.3. The Helix-Coil Transition of Native Collagen and Soluble Tro
pocollagen and the Development of the Collagen Fold by
Gelatins in Aqueous Solution . . . . . . . . . . 363
3.4. Hydration Structures Associated with Biopolymers 390
4. Solvent Structure Effects on Macromolecular Structure, Confor
mational Stability, and Transitions in the Presence of Neutral
Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . 423
