Molecular Electro-Optics: Electro-Optic Properties of Macromolecules and Colloids in Solution

514 Pages·1981·10 MB·English

by  Sonja Krause (eds.)

Molecular Electro-Optics
Electro-Optic Properties of Macromolecules
and Colloids in Solution
NATO ADVANCED STUDY INSTITUTES SERIES
A series of edited volumes comprising multifaceted studies of contem
porary scientific issues by some of the best scientific minds in the world,
assembled in cooperation with NATO Scientific Affairs Division.
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Volume 62 - Radiationless Processes
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Volume 63 - Characterization of Crystal Growth Defects by X-Ray Methods
edited by Brian K. Tanner and D. Keith Bowen
Volume 64 - Molecular Electro-optics: Eiectro-optic Properties of
Macromolecules and Colloids in Solution
edited by Sonja Krause
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Molecular Electro-Optics
Electro-Optic Properties of Macromolecules
and Colloids in Solution
Edited by
Sonja Krause
Rensselaer Polytechnic Institute
Troy, New York
PLENUM PRESS. NEW YORK AND LONDON
Published in cooperation with NATO Scientific Affairs Division
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute on Molecular Electro-optics (1980: Rensselaer Polytechnic
Institute) Molecular electro-optics.
(NATO advanced study institutes series. Series B, Physics; v. 64)
"Proceedings of a NATO Advanced Study Institute on Molecular Electro-optics, held July
14-24,1980, at Rensselaer Polytechnic Institute, Troy, New York" - Verso of t. p.
Bibliography: p.
Includes index.
1. Macromolecules-Electric properties-Congresses. 2. Macromolecules-Optical properties
-Congresses. 3. Colloids-Electric properties-Congresses. 4. Colloids-Optical properties
Congresses. I. Krause, Sonja. II. Title. III. Series.
QD381.9.E38N22 1980 547.7'04572 81-1314
ISBN-13: 978-1-4684-3916-8 e-ISBN-13: 978-1-4684-3914-4 AACR2
DOl: 10.1007/978-1-4684-3914-4
Proceedings of a NATO Advanced Study Institute on
Molecular Electro-Optics, held July 14-24, 1980,
at Rensselaer Polytechnic Institute, Troy, New York
© 1981 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1981
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
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
The Advanced Study Institute on Molecular Electro-Optics was
held on the campus of the Rensselaer Polytechnic Institute, Troy,
New York, USA, from July 14 through July 24, 1980. This Advanced
Study Institute was attended by sixteen invited lecturers and by
forty-eight other participants.
The present volume contains the texts of all of the invited
lectures presented at the Institute. Although these lectures
were supplemented by many animated discussions and by numerous
short contributed papers, it was not possible to include these in
the present volume.
Molecular electro-optics is a difficult subject for research
because it incorporates areas of theoretical physics such as elec
tromagnetic theory and hydrodynamics of rotational diffusion, ex
perimental physics such as lasers, optics, electric pulsers, and
data collection via analog to digital converters and signal aver
agers, and physical chemistry of macromolecules and colloids in
solution (colloid science, biophysical chemistry, double layer
polarization). This volume includes chapters on all of these
subjects as well as introductions to magnets-optics and to elec
trophoretic light scattering.
The Advanced Study Institute was sponsored mainly by the
North Atlantic Treaty Organization whose financial support made
this meeting possible. Additional financial aid was supplied by
the National Institutes of Health of the USA through their
Fogarty International Center and the National Institute for
Arthritis, Metabolism, and Digestive Diseases. Industrial contri
buters consisted of the General Electric Company, Cober
Electronics, and Malvern Scientific Corporation.
I would like to thank all the people whose assistance during
the planning and operation of this Institute and during the pre
paration of this volume was indispensable.
v
vi PREFACE
Beth McGraw, who served as our Meeting Secretary and worked
tirelessly both during the meeting and during the preparation
of this Volume,
Jeff Boyer, a senior student in Chemistry who was our
meeting projectionist and who helped our visitors feel
at home,
Krystyna Szumilin, my postdoctoral associate, and
Nancy Letko, my graduate student, who worked hard during
the meeting with the various necessary tasks,
Robert Metzger, Manager of Special Events at Rensselaer
Polytechnic Institute who made everything flow smoothly,
Victoria R. Lee, who typed the major portion of this volume,
and Mary K. Nolan, Elizabeth R. Schoonmaker, Susan J. Mangione,
and Patricia S. Connell who typed the rest,
Walter W. Goodwin, my husband, who helped keep me on an even
keel before an during the meeting and during preparation
of this book,
all the lecturers and participants who made the meeting a
stimulating and friendly one.
Sonja Krause
Director of the Institute
CONTENTS
A History of Molecular Electro-optics 1
C. T. O'Konski
Introduction to Modern Electro-optics 27
B. R. Jennings
Small Molecules in Electric and Optical Fields . . . • . .. 61
A. D. Buckingham
Rotational Diffusion Coefficients 75
J. Garcia de la Torre
The Rotational Diffusion Function in an Electric Field . .. 105
S. P. Stoylov
Theory of the Kerr Constant 119
C. T. O'Konski
Electric Birefringence Dynamics 147
S. Krause and C. T. O'Konski
Kerr Effects of Flexible Macromolecules 163
R. L. Jernigan and S. Miyazawa
Light Scattering in Electric Fields 181
B. R. Jennings
Wavelength Dependent Aspects of Electric Birefringence
and Dichroism .............•.•. 213
E. Charney
Polarized Fluorescence in an Electric Field 229
G. Weill
vii
viii CONTENTS
Interaction of Electric Fields with Membrane-Bound
Polyionic Proteins 241
E. Neumann and K. Tsuji
Threshold Effects in Field-Induced Conformation Changes
and Binding of Ions - Including Peptides to
Polynucleotides 269
D. Porschke
Polyelectrolytes: A Survey 285
A. Mandel
Electro-optical Instrumentation Systems with their
Data Acquisition and Treatment 309
C. Roussier and C. T. O'Konski
The Electro-optics of Proteins 341
J. C. Bernengo
Investigating Nucleic Acids, Nucleoproteins,
Polynucleotides, and their Interactions with Small
Ligands by Electro-optical Methods . 363
C. Roussier
Electro-optics of Viruses and Bacteriophages 399
F. S. Allen
Application at Electro-optics to the Study of Colloids 417
S. P. Stoylov
Electro-optical Properties of Liquid Crystals 435
D. A. Dunmur
An Introduction to Magnetic Birefringence of Large
Molecules 473
C. Weill
Introduction to Laser Light Scattering Spectroscopy in
Electrophoresis 485
E. E. Uzgiris
List of Lecturers 505
Index 507
A HISTORY OF MOLECULAR ELECTRO-OPTICS
Chester T. O'Konski
Department of Chemistry
University of California
Berkeley, CA
PHENOMENOLOGICAL DESCRIPTION AND EQUATIONS OF THE KERR ELECTRO-OPTIC
EFFECT
Before describing Kerr's discovery of the first electro-optic
effect to be detected, let us consider the physical principles of
the phenomenon. Figure I illustrates the electric double refraction,
or birefringence, and introduces conventional terminology. A plane
polarized light beam enters a sample placed between plane parallel
electrodes connected to an external voltage source. The direction
of polarization of the light beam is specified by the direction of
its electric vector, E., which is normally oriented at 450 with re
spect to the directio~of the applied electric field, as illustrated
in the view along the direction of the light beam in Fig. l(a). The
vector of the incident light, E., may be decomposed into two compo
nents, one parallel to the dir~~tion of the applied electric field,
designated Ell' and the other, E l' perpendicular to the direction
of the applied electric field. These two vectors are in phase as
the electromagnetic radiation enters the medium. Under the influ
ence of the external field the refractive indexes of the medium
change and become unequal for the parallel and the perpendicular
components; the sample behaves like a uniaxial crystal with its
unique optic axis in the direction of the applied field·. The two
component rays traverse the medium at different velocities, and
emerge out of phase, as illustrated in Fig, l(b). The resultant,
Ee' produces a vector which describes an ellipse.
In the absence of an electric field, the light coming out of
the Kerr cell is plane polarized and is extinguished by the crossed
analyzer, but in the presence of the field, the emergent light has
1
2 c. T. O'KONSKI
Fig. 1. Apparatus for Kerr electro-optic effect (electric bire
fringence) experiments. Below it are shown the states of
polarization of light: (a) after passing through the
polarizer, (b) after passing through the cell, and (c)
after passing through the analyzer. E. is the electric
vector of the plane-polarized light in~ident upon the
sample, and it can be decomposed into two in-phase'compo
nents, Ell and E1, parallel and perpendicular, respectively,
to the applied electric field. E is the vector of the
elliptically polarized light emer~ing from the birefringent
solution in the cell, and E is the component of E trans-
t e
mitted by the analyzer.
an electric field component perpendicular to that of the incident
polarized light, so that a portion of the light is transmitted by
the analyzer, as shown by the vector E in Fig. l(c). The inten-
t
sity of the transmitted light, relative to that of the incident
light, is directly related to the degree of optical anisotropy pro
duced by the applied electric field.
The optical path length of the cell, for the parallel comp
nent of the light, may be expressed by