Chemical and Biological Applications of Relaxation Spectrometry: Proceedings of the NATO Advanced Study Institute held at the University of Salford, Salford, England, 29 August–12 September, 1974

503 Pages·1975·11.207 MB·English

by  Jørgen Rassing (auth.), E. Wyn-Jones (eds.)

Chemical and Biological Applications of Relaxation Spectrometry
NATO ADVANCED STUDY INSTITUTES SERIES
Proceedings of the Advanced Study Institute Programme, which aims
at the dissemination of advanced knowledge and
the formation of contacts among scientists from different countries
The series is published by an international board of publishers in conjunction
with NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht and Boston
D Behavioral and Sijthoff International Publishing Company
Social Sciences Leiden
E Applied Sciences Noordhoff International Publishing
Leiden
Series C - Mathematical and Physical Sciences
Volume 18 - Chemical and Biological Applications of Relaxation Spectrometry
Chemical and Biological
Applications of
Relaxation Spectrometry
Proceedings of the NATO Advanced Study Institute
held at the University of Salford, Salford, England,
29 August-12 September, 1974
edited by
E. WYN -J 0 NES
Department of Chemistry and Applied Chemistry, University of Salford, Salford, England
D. Reidel Publishing Company
Dordrecht-Holland / Boston-U.S.A.
Published in cooperation with NATO Scientific Affairs Division
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute, University of Salford, 1974.
Chemical and biological applications of relaxation spectrometry.
(NATO advanced study institutes series: C, mathematical and physical sciences; 18)
Bibliography: p.
I. Relaxation spectroscopy-Congresses. I. Wyn-Jones, Evan. II. Title.
III. NATO advanced study institutes series: Series C, mathematical and
physical sciences; 18.
QD96.R44N37 1974 543'.085 75-17765
ISBN-13:978-94-0 10 -1857-9 e-ISBN-13 :978-94-0 10 -1855-5
DOl: 10.1007/978-94-010-1855-5
Published by D. Reidel Publishing Company
P.O. Box 17, Dordrecht, Holland
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All Rights Reserved
Copyright © 1975 by D. Reidel Publishing Company, Dordrecht, Holland
Softcover reprint of the hardcover 1st edition 1975
No part of the material protected by this copyright notice may be reproduced or utilized
in any fonn or by any means, electronic or mechanical, including photocopying,
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without permission from the copyright owner
CONTENTS
PREFACE XI
J. E. Rassing
ULTRASONIC RELAXATION SPECTROMETRY
A. M. North
DIELECTRIC RELAXATION 17
J. Crossley
DIELECTRIC RELAXATION AT MICROWAVE FREQUENCIES 35
B. H. Robinson
THE STOPPED-FLOW AND TEMPERATURE-JUMP TECHNIQUES - PRINCIPLES
AND RECENT ADVANCES 41
Z. A. Schelly
THE SOLVENT-JUMP RELAXATION METHOD USING STOPPED AND
CONTINUOUS FLOW 49
1. Giannini
A LASER TEMPERATURE JUMP AND PHOTOLYSIS APPARATUS WITH
REPETITIVE TUNABLE EXCITATION 53
Z. A. Schelly
THE PROBLEM OF INHOMOGENEOUS HEATING IN LASER-T-JUMP
EXPERIMENTS 61
M. M. Farrow, N. Purdie, A. L. Cummings, W. Hermann, Jr.,
and E. M. Eyring
KINETIC STUDIES OF METAL ION COMPLEXATION AND DYE DlMERIZATION
BY LASER ULTRASOUND AND LASER T-JUMP 69
E. M. Eyring
THE ELECTRIC FIELD JUMP RELAXATION METHOD 85
W. Knoche
PRESSURE-JUMP METHODS 91
VI CONTENTS
W. Knoche
ON DATA PROCESSING, EVALUATION AND PRECISION OF RELAXATION
MEASUREMENTS \03
D. Thusius
THE ANALYSIS OF RELAXATION AMPLITUDES 113
C. F. Bernasconi
NORMAL MODE ANALYSIS OF CHEMICAL REACTIONS 121
R. Zana
BRIEF REVIEW OF THE CHEMICAL RELAXATION STUDIES OF MICELLAR
EQUILIBRIA 133
R. Zana
CHEMICAL RELAXATION STUDIES OF MICELLAR EQUILIBRIA 139
T. Yasunaga, K. Takeda, N. Tatsumoto, and H. Uehara
KINETIC STUDIES OF THE RAPID REACTIONS IN n-ALKYL SULFATE
SOLUTION 143
V. C. Reinsborough
ULTRASONIC PULSE SPECTROSCOPY IN MICELLAR SOLUTIONS 159
P. J. Sams, J. E. Rassing, and E. Wyn-Jones
KINETICS OF MICELLIZATION FROM ULTRASONIC RELAXATION STUDIES -
THE FAST PROCESS DESCRIBED BY THE TWO STATE MODEL 163
M. Almgren
COMMENTS ON THE FAST RELAXATION PROCESS OBSERVED IN THE STUDY
OF MICELLIZATION 171
U. Hermann and M. Kahlweit
ON THE KINETICS OF THE FORMATION OF NaDS MICELLES 175
H. Hoffmann
MECHANISM OF MICELLE FORMATION OF SODIUMDODECYLSULFATE (SDS) 181
J. Lang
KINETIC STUDIES OF THE DISSOCIATION OF NONIONIC DETERGENT
MICELLES 195
B. H. Robinson, N. C. White, C. Mateo, K. J. Ti~ns,
and A. James
DYNAMICS OF SMALL MOLECULE - MICELLE INTERACTIONS 201
J. D. Owen, M. Steggall, and E. M. Eyring
STOPPED FLOW AND TEMPERATURE JUMP STUDIES OF COLLOIDAL
SUSPENSIONS 211
CONTENTS VII
K. K. Fox
AN ATTEMPT TO MEASURE THE MONOMER-MICELLE EXCHANGE FREQUENCY
USING ELECTRON PARAMAGNETIC RESONANCE 215
E. A. G. Aniansson and S. N. Wall
KINETICS OF STEP-WISE MICELLE ASSOCIATION AND DISSOCIATION 223
E. A. G. Aniansson, M. Almgren, and S. N. Wall
THE RATE OF MICELLE DISSOCIATION 239
E. A. G. Aniansson
ON THE RATE OF MANY-STEP PROCESSES 245
B. H. Robinson and N. C. White
A COOPERATIVE MODEL FOR MICELLE FORMATION 255
W. Knoche
ON THE MECHANISM OF LIGAND SUBSTITUTION IN WEAK METAL
COMPLEXES IN AQUEOUS SOLUTIONS 265
T. Yasunaga, S. Harada, and K. Tamura
ULTRASONIC AND LASER T-JUMP STUDIES OF THE NICKEL CARBOXYLATE
COMPLEX FORMATION REACTION IN AN AQUEOUS SOLUTION 277
P. Hemmes
THE ASSOCIATION OF OPTICALLY ACTIVE IONS; ULTRASONIC INVESTI
GATION OF THE ASSOCIATION OF BIS AND TRIS (ORTHOPHENANTHROLINE)
ZINC (II) d-CAMPHORSULFONATE 291
H. Hoffmann
MECHANISM OF COMPLEX FORMATION IN NONAQUEOUS SOLVENTS 295
J. J. Delpuech, M. R. Khaddar, A. A. Peguy, and P. R. Rubini
LIGAND SUBSTITUTION PROCESSES. STU21. I. SOLVATION
~+NMR
SHELLS OF DIAMAGNETIC CATIONS Al AND Be 311
J. C. Boubel, J. J. Delpuech, and A. A. Peguy
LIGAND SUBSTITUTION SOLVATION SHELLS OF
PRO~~SSES. I2~
PARAMAGNETIC CATIONS Ni AND Co 323
R. Zana and C. Tondre
ULTRASONIC STUDIES OF POLYION - COUNTERION INTERACTIONS IN
POLYELECTROLYTES SOLUTIONS 333
C. F. Bernasconi
THE USE OF THE TEMPERATURE-JUMP METHOD IN THE STUDY OF
ORGANIC REACTION MECHANISMS 343
E. Wyn-Jones
CONFORMATIONAL ANALYSIS USING ULTRASONIC RELAXATION
SPECTROMETRY 353
VIII CONTENTS
P. Hemmes, L. Oppenheimer, and F. Jordan
ULTRASONIC ABSORPTION DETERMINATION OF THE THERMODYNAMICS
OF FAST ISOMERIZATION PROCESSES 359
B. Bianchin, J. Chrisment, J. J. Delpuech, M. N. Deschamps,
D. Nicole, and G. Serratrice
A COMPARISON OF PROTON TRANSFER RATES IN AQUEOUS AND NON-
AQUEOUS SOLUTIONS 365
M. W. Massey and Z. A. Schelly
ELECTRIC FIELD AND TEMPERATURE-JUMP STUDY OF THE COLOR CHANGE
KINETICS OF ETHANOLIC AND AQUEOUS PHENOLPHTHALEIN 375
C. F. Bernasconi and F. Terrier
RATES OF PROTON TRANSFERS IN 70% DMSO-30% WATER. MECHANISM OF
DEPROTONATION OF INTRAMOLECULARLY HYDROGEN BONDED SPECIES 379
M. M. Wong and Z. A. Schelly
SOLVENT-JUMP RELAXATION KINETICS OF THE ASSOCIATION OF
RHODAMINE TYPE LASER DYES 385
F. Hibbert
TEMPERATURE-JUMP STUDY OF THE RATES OF PROTON TRANSFER AND
THE STRENGTH OF INTRAMOLECULAR HYDROGEN BONDS IN PERI
SUBSTITUTED NAPHTHALENES 387
B. H. Robinson
FAST PROTON-TRANSFER REACTIONS IN APROTIC SOLVENTS 395
J. Lang
ULTRASONIC ABSORPTION STUDY OF AQUEOUS SOLUTIONS OF
NUCLEOTIDES AND NUCLEOSIDES 397
L. J. Slutsky and R. D. White
ULTRASONIC ABSORPTION IN PROTEIN SOLUTION 407
I. Giannini and G. Sodini
FAST RELAXATIONS IN HUMAN CARBONIC ANHYDRASE COMPLEXES WITH
SULFONAMIDES 423
D. Thusius
KINETICS OF GLUTAMATE DEHYDROGENASE SELF-ASSEMBLY 433
V. Vitagliano
INTERACTION BETWEEN CATIONIC DYES AND POLYELECTROLYTES 437
T. Yasunaga, H. Takenaka, T. Sano, and Y. Tsuji
KINETIC STUDY OF COOPERATIVE BINDING REACTION OF TOLUIDINE
BLUE TO POLy-a, L-GLUTAMIC ACID BY MEANS OF ELECTRIC FIELD
PULSE METHOD 467
CONTENTS IX
B. H. Robinson, A. Seelig-Loffler, and G. Schwarz
THE THERMODYNAMICS AND KINETICS OF ASSOCIATION OF ACRIDINE
DYES IN AQUEOUS MEDIA: A MODEL SYSTEM FOR THE STUDY OF
STACKING AND CHARGE-EFFECTS ON SELF-AGGREGATION 481
R. Zana
ULTRASONIC ABSORPTION STUDIES IN RELATION TO CONFORMATIONAL
CHANGES OF BIOPOLYMERS IN SOLUTION 487
T. Yasunaga, Y. Tsuji, T. Sano, and H. Takenaka
KINETIC STUDY OF HELIX-COIL TRANSITION IN AQUEOUS SOLUTIONS OF
POLY-a, L-GLUTAMIC ACID BY MEANS OF ELECTRIC FIELD PULSE
METHOD 493
A. L. Cummings and E. M. Eyring
ELECTRIC FIELD JUMP STUDY OF THE HELIX-COIL TRANSITION OF
AQUEOUS POLy-a, L-GLUTAMIC ACID 505
J. Rassing and E. Wyn-Jones
ULTRASONIC RELAXATION IN SOLUTION OF POLYSTYRENE AND
N-POLYVINYLPYRROLIDONE 509
A. M. North
THE ORIGIN OF ULTRASONIC RELAXATION IN POLYMER SOLUTIONS 513
G. Williams
MOTION IN AMORPHOUS POLYMERS AND VISCOUS LIQUIDS 515
PREFACE
Chemical relaxation spectrometry involves the application of
several different relaxation techniques to investigate the kinetics
and mechanisms of fast chemical reactions and also dynamic molecul
ar processes that occur in liquids in the time range 1 - 10-10 secs.
These methods have been used widely in several disciplines of the
natural sciences including molecular biology, biochemistry, organic
stereochemistry, detergent chemistry and inorganic chemistry.
The purpose of the Advanced Study Institute was to provide a
forum for scientists to discuss the role, scope and limitations of
the various applications of chemical relaxation methods in order
to stimulate discussion and interaction between workers in these
different fields. The papers described in this volume are a summary
of the contributions that were discussed at the meeting. The brief
given to the authors was to attempt to prepare an article contain
ing a good supply of references so that the book can be used not
only by those starting in the field, but also by the specialist
and research worker. These contributions cover a varied range of
topics summarizing the achievements, the current state of knowledge
and possible application in many disciplines. It is to be hoped
that this volume will help to point out some new directions towards
which research efforts are required and to attract new researchers
with fresh points of view. In a collection of this kind it is
inevitable that the style of presentation and length of the articles
are varied and also that a certain amount of overlap will occur. In
some discussion sessions, particularly the kinetics of micelle form
ation, this latter point provided an invaluable pointer towards
understanding detailed reaction mechanisms especially when the same
problem is approached using several different experimental methods.
In the preparation of this volume I am deeply grateful for
the invaluable assistance of my colleague John Gettins. I would
also like to thank the following people who assisted in the
preparation of the manuscript:- Mrs. J. Broadhead, Miss L. Cook,
Miss C. Lowe, Mr. Walter Owen and Mrs. G. Wyn-Jones.
Salford. Evan Wyn-Jones
March 1975.