Table Of ContentElectro -Optics
and Dielectrics of
Macromolecules and Colloids
Electro -Optics
and Dielectrics of
Macromolecules and Colloids
Edited by
Barry R. Jennings
Brunei University
Uxbridge, England
PLENUM PRESS . NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Main entry under title:
Electro-optics and dielectrics of macromolecules and colloids.
Includes index.
1. Colloids-Electric properties-Congresses. 2. Colloids-Optical properties
Congresses. 3. Macromolecules-Electric properties-Congresses. 4. Macromolecules
Optical properties-Congresses. I. Jennings, Barry Randall, 1939-
QD549.E44 547'.7 79-10117
ISBN-13: 978-1-4684-3499-6 e-ISBN-13: 978-1-4684-3497-2
001: 10.1007/978-1-4684-3497-2
Proceedings of the Conference on Electro-Optic and Dielectric Studies on Macromolecules
and Colloids, held at Brunei University, Uxbridge, United Kingdom, April 12-14, 1978.
©1979 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1979
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N.Y. 10011
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
Brunei University
UKbridge U,K,
'For any man with half an eye,
what stands before him may espy;
But optics sharp it needs, I ween,
to see what is not to be seen.'
JOHN TRUMBULL (1750-1831) McFinga1
'The time has come', the Walrus said, 'to talk of many things:'
Lewis Carroll (1832-1898) The Walrus and the Carpenter
In 1875, a scientific paper appeared in the Philosophical
Magazine under the title 'A new relation between electricity and
light'. Its author was John Kerr, a 51 year old ordained minister
of the Free Church of Scotland who, after ordination, seems to have
applied himself to the teaching and study of the natural philosophy
to which he had partially applied his mind during his university
career at Glasgow University. In those early days he had worked in
what was the first physical laboratory in a British university. Its
founder and director at the time was Professor William Thomson (Lord
Kelvin).
At the age of 33, John Kerr was appointed a lecturer in mathe
matics at the Glasgow Free Church Training College. He held this
position for some 44 years. During much of this period, he spent his
spare hours searching for an effect that would demonstrate the inter
relation between electrical and optical phenomena. In this respect,
he followed in the train of the renowned Michael Faraday. Using
nothing better than a paraffin candle or sunlight reflected from a
bright cloud as his light source, together with the potential differ
ence generated across the secondary terminals of a Ruhmkorff induction
machine as the origin of his electric field, Kerr demonstrated the
phenomenon of 'electric birefringence' in glass and liquids. Thus
was born the Kerr electro-optic effect. Briefly stated, it is the
ability of an apparently isotropic medium to act as a uniaxial,
anisotropic system when an electric field is applied across it. The
medium is viewed between crossed polarising devices in a direction
perpendicular to the electric field, application of which is accom
panied by the transmission of light. Since its discovery, the effect
has been used in a host of devices of which the best known is the
electro-optic shutter. This has been adapted for the measurement of
the velocity of light, for high speed photography and, more recently,
as an optical modulator in laser technology.
viii PREFACE
Some seven years before Kerr's death, Larmor proposed that
electric birefringence had its origin in the orientation of anisotropic
molecules or elements within the apparently isotropic medium. The
theory for this concept was formulated by Langevin. During the next
half century, occasional measurements were made both to characterise
the phenomenon and to evaluate the relevant physico-chemical parameters
of pure liquids and molecular fluids.
During the 1930-40 era, Staudinger and others demonstrated the
existence in nature of giant molecules and colloidal particles. Since
that time it has slowly but increasingly been realised that these big
molecules or particles often have relatively large dipole moments, are
generally anisotropic in structure and hence, in solution or suspension,
give rise to significant electric birefringence signals. Furthermore,
there have been three electronic innovations which have greatly eased
the experimental measurement of the effect for such materials. These
were the development of photomultiplier tubes for detection, of oscillo
scope~ for display and of high voltage generators developing bursts or
pulses of potential difference. The last mentioned enable the experi
menter to study the Kerr effect not only for its amplitude but also in
the time domain. The rates of molecular response to the switching of
the electric field lead directly to information on the size and geo
metry of the constituent molecules and particles in a dilute solution
or suspension. It is the combination of electrical, optical and geo
metrical information on a sample from a single, fast experimental method
that has resulted in the great escalation of interest in electro-optical
studies of macromolecules and colloids during the past twenty-five years.
It would be misleading and very restrictive to give the reader the
impression that the Kerr-Effect is the only electro-optical phenomenon.
One of the most rewarding and interesting aspects of current studies is
the way that younger researchers have been active in predicting, mani
festing, measuring and utilising a host of novel electro-optical pheno
mena for macromolecular characterisation. In response to pulsed applied
fields, changes in the scattered intensity, the fluctuations in the
scattered light, the absorption, linear dichroism, fluorescence, optical
rotation and circular dichroism have been measured. They all have their
origins in the structural anisotropy of the molecules of the medium
studied. It is not however, a refractive index anisotropy as in the
case of birefringence. Rather, each is a manifestation of a different
anisotropic optical and hence structural characteristic of the molecules.
It is this factor which promises so much for future investigations.
Furthermore, recent work in this laboratory has shown that the oscilla
ting electric vector associated with high powered laser beams is itself
capable of inducing electro-optical effects in macromolecules. These
are sometimes called optico-optical effects. They herald yet further
advances in the study of high frequency polarisation processes and,
because of the extremely short duration of switched laser pulses, offer
the possibility of studying the rotation rates of ever smaller molecules.
PREFACE
To date electro-optical methods have already been used to study
a wide variety of material classes. These include synthetic polymers,
polyelectrolytes, polypeptides, polynucleotides, nucleic acids, micro
organisms, cells, bacteria, veSicles, nerve axons, proteins, viruses,
membranes, lipids, liquid crystals, clay minerals, colloids and sur
factants.
It was against this historical background and in the face of
future promise, that the Electro-Optics Group of BruneI University
staged an International conference in April 1978. Such is the enthusiasm
of the ever-expanding community of researchers using electro-optic
methods for the study of macromolecules and colloids, that the partici
pants came from allover the world. No single country, not even that
of the hosts, dominated the meeting. The papers and discussion covered
such a diversity of experimental methods, classes of materials, analy
tical procedures and future proposals that the material of the meeting
well represented the current state-of-the-art of macromolecular and
colloidal electro-optical studies. For this reason, it was decided
that these proceedings be published. All but two of the works presen
ted at the conference are contained herein. It is hoped that, for
those who attended the meeting, this book will both remind them of a
memorable occasion and provide stimuli for future developments. The
more important function however, is to disseminate results on the
materials studied and to introduce the wider community to electro-optic
methods and the ways that these can be utilised to evaluate molecular
information on macromolecules and colloids of biological and synthetic
origin.
In editing these proceedings I should like to thank the following
members of the BruneI Electro-Optics Group for helping with details of
the conference and for proof reading the present text; K. Ballinger,
R. Fairey, E.Y. Hawkins, P. Hammond, P. Kolinsky, V.J. Morris, D. Oakley
and P.J. Ridler. Special thanks are extended to A.R. Foweraker who
co-organised the conference. Finally, thanks are expressed to Mrs.
S. Dunster who, over many months, has laboriously but accurately retyped
all the manuscripts and texts.
BruneI University B. R. JENNINGS
Uxbridge
'Knowledge is of two kinds. We know a subject ourselves, or we
know where we can find information upon it.'
Samuel Johnson (1709-1784) Letter to Lord Chesterfield
THEORETICAL ADVANCES
SPECIFIC KERR CONSTANTS OF RIGID, ELLIPSOIDAL MACROMOLECULES
IN CONDUCTING SOLUTION AT VERY LOW IONIC STRENGTH
S. Krause, B. Zvilichovsky and M.E. Galvin................... 3
TRANSIENT ELECTRIC BIREFRINGENCE OF MACROMOLECULAR SOLUTIONS
AT REVERSING FIELDS OF ARBITRARY STRENGTH AND DURATION
G. Koopmans, J. de Boer and J. Greve ..•.•....•.••...•........ 13
THE LIMIT OF THE NUMERICAL METHOD OF INVERTING THE LAPLACE
TRANSFORMATION AND THE UNIQUENESS OF RELAXATION DISTRIBUTION
FUNCTION OBTAINED BY THE METHOD
M. Matsumoto and H. Watanabe ..•.•.•••••.•.•.•........•.•..... 21
LOW ANGLE APPROXIMATIONS TO THE THEORY OF ALTERNATING ELECTRIC
FIELD LIGHT SCATTERING
T.J. Herbert................................................. 29
A THEORY OF DYNAMIC LIGHT-SCATTERING BY FLEXIBLE
MACROMOLECULES IN A FLUCTUATING ELECTRIC FIELD
W.G. Griffin................................................. 37
ELECTRO-OPTICAL RESPONSES OF CHIRAL SUBSTANCES
H. Watanabe.................................................. 43
xii CONTENTS
ABSORPTION PHENOMENA
AN INSTRUMENT FOR THE MEASUREMENT OF ELECTRIC DICHROISM
W.H.Rahe, R.J. Fraatz, L.K. Sun, D.R.C.Priore and F.S. Allen ... 57
SIMULTANEOUS MEASUREMENT OF DICHROISM AND BIREFRINGENCE
ON SUSPENSIONS OF ABSORBING PARTICLES
J.C. Ravey and C. Houssier................................... 67
ELECTRIC DICHROISM OF PURPLE MEMBRANE
K. Tsuji and K. Rosenheck.................................... 77
ELECTROCHROMISM OF ORGANIC DYES IN POLYMER MATRICES
E.E. Havinga and P. Van Pelt ....•......•..................... 89
ELECTRICALLY INDUCED FLUORESCENCE CHANGES FROM SOLUTIONS
OF DYE TAGGED POLYRIBONUCLEOTIDES
P.J. Rid1er and B.R. Jennings................................ 99
POLARIZED FLUORESCENCE IN AN ELECTRIC FIELD: THEORETICAL
CALCULATION AT ARBITRARY FIELDS. EXPERIMENTAL COMPARISON
WITH OTHER ELECTROOPTICAL EFFECTS. SATURATION OF THE
INDUCED DIPOLE MOMENT IN POLYELECTROLYTES
S. Sokerov and G. Weill ...................................... 109
NUCLEIC ACIDS AND POLYNUCLEOTIDES
DIELECTRIC PROPERTIES OF LOW-MOLECULAR WEIGHT DNA IN AQUEOUS
SOLUTIONS AT LOW IONIC STRENGTH
Th. Vreugdenhil, F. Van der Touw and M. Mandel ............... 123
ELECTRO-OPTIC MEASUREMENT OF V-RAY INDUCED DAMAGE IN DNA
C.T. O'Konski and R.S. Farinato .............................. 133
PHYSICAL STUDIES OF Hg(II) AND Ag(I) DNA COMPLEXES - THEORY
D. Ding and F. Allen ......................................... 143
ELECTRIC-FIELD INDUCED ORIENTATION OF POLYNUCLEOTIDES
E. Charney ................................................... 149
THE STABILIZED INDUCED DIPOLE IN SOLUTIONS OF POLYNUCLEOTIDES
M. Shirai ...........•..•..........•...••..............•...... 153
CONTENTS xiii
BIOLOGICAL SYSTEMS
ELECTRO-OPTICAL PROPERTIES OF NUCLEOSOMES AND NUCLEOSO¥~L DNA
B. Roux, C. Marion and J.C. Bernengo •.•.•.••...•...•......... 163
POLARISABILITY ANISOTROPY AS AN INDICATOR OF THE EFFECTS OF
AMINOGLYCOSIDE ANTIBIOTICS ON SENSITIVE, DEPENDENT AND
RESISTANT STRAINS OF E.co1i
V.J. Morris, B.R. Jennings, N.J. Pearson and F. O'Grady ...... 175
ROTATIONAL DIFFUSION COEFFICIENTS OF COMPLEX MACROMOLECULES
V.A. Bloomfield, J. Garcia de 1a Torre and R.W. Wilson ....... 183
DETERMINATION OF ROTATIONAL DIFFUSION COEFFICIENTS OF THE
BACTERIOPHAGES T4B AND T7 BY DEPOLARIZED DYNAMIC LIGHT
SCATTERING. THE INFLUENCE OF DOUBLE SCATTERING
P.C. Hopman, G. Koopmans and J. Greve ...•..•••...•...•....... 197
EFFECTS OF CALCIUM AND ATP ON THE CONFORMATION OF F-ACTIN
IN VIVO AND IN VITRO
M. Taniguchi .............•....•.•.............•.•............ 203
ELECTRIC BIREFRINGENCE OF CARTILAGE PROTEOGLYCAN AND ITS
ASSOCIATION WITH HYALURONIC ACID
E.Y. Hawkins, M. Isles, A.R. Foweraker, B.R. Jennings
T. Hardingham and H. Muir ...•.•..•....•.•.••...•............. 211
AN ELECTRICAL BIREFRINGENCE STUDY OF THE CONTRIBUTION OF PERMANENT
AND INDUCED DIPOLE MOMENTS TO ACID-SOLUBLE COLLAGEN POLARIZATION
J.C. Bernengo, B. Roux and D. Herbage .....••....•............ 219
POLYELECTROLYTES AND POLYMERS
ELECTRO-OPTICAL CHANGES IN BIOPOLYMERS - CHEMICAL AND
ROTATIONAL CONTRIBUTIONS
E. Neumann ....••...•.•.•..••.•..•.•..••.•.•.•................ 233
REVERSAL OF BIREFRINGENCE SIGN OF NATURAL AND SYNTHETIC POLY
ELECTROLYTES IN THE PRESENCE OF METAL CATIONS AND COORDINATION
COMPLEXES
C. Houssier and M. Tricot .................................... 247
ELECTRO-OPTIC STUDY OF THE CONFORMATIONAL CHANGES INDUCED IN
PARTIALLY CHARGED POLY-4-VINYLPYRIDINE BY IONS OF HEAVY METALS
M. Tricot ...••.•......••••••.•.•.•••••••...•.•............... 259
