Table Of ContentInfrared and Raman Spectroscopy of
Biological Molecules
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
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B Physics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht, Boston and London
D Behavioral and Sijthoff International Publishing Company
Social Sciences Leiden
E Applied Sciences Noordhoff International Publishing
Leiden
Series C - Mathematical and Physical Sciences
Volume 43 - Infrared and Raman Spectroscopy of Biological Molecules
Infrared and
Raman Spectroscopy of
Biological Molecules
Proceedings of the NA TO Advanced Study Institute
held at Athens, Greece, August 22-31, 1978
edited by
THEO M. THEOPHANIDES
Universite de Montreal, Departement de Chimie, Montreal, Quebec, Canada and
National Hellenic Research Foundation, Athens, Greece
D. Reidel Publishing Company
Dordrecht: Holland / Boston: U.S.A. / London: England
Published in cooperation with NATO Scientific Affairs Division
library of Congress Cataloging in Publication Data CltJ
Nato Advanced Study Institute, Athens, Greece, 1978.
Infrared and Raman spectroscopy of biological molecules.
(NATO Advanced Study Institutes series: Series C, Mathematical and physical sciences; v. 43)
Bibliography: p.
Includes index.
1. Infra-red spectroscopy -Congresses. 2. Raman spectroscopy -Congresses. 3. Molecular
biology - Techniques-Congresses. I. Theophanides, Theo M. II. Title. III. Series.
QH324.9.15N371978 574.1'9285 78-31633
ISBN-13: 978-94-009-9414-0 e-ISBN-13: 978-94-009-9412-6
DOl: 10.1007/978-94-009-9412-6
Published by D. Reidel Publishing Company
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Copyright © 1979 by D. Reidel Publishing Company, Dordrecht, Holland
Softcover reprint of the hardcover 1st edition 1979
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CONTENTS
Preface ix
INTRODUCTION AND HISTORICAL SURVEY
Introduction to the Raman Spectroscopy of Biological Molecules.
Lucien Bernard 3
Historical Survey of the Infrared and Raman Spectroscopic Study of Biological Molecules
J. R. Durig and D. J. Gerson 35
CLASSICAL THEORY OF VIBRA TIONS AND GROUP FREQUENCIES
Classical Theory of Molecular Vibrations
J. R. Durig and W. J. Natter 47
Correlation of Group Frequencies with Molecular Conformation
J. R. Durig and W. J. Natter 59
Vibrational Spectra of Solids
J. R. Durig 69
Group Frequencies and the Chemical Bond
R. Norman Jones 81
APPLICATIONS
Vibrations of Chain Molecules
Jack L. Koenig 97
Vibrational Spectroscopy of Polypeptides and Proteins
Jack L. Koenig 109
Vibrational Spectroscopy of Carbohydrates
Jack L. Koenig 125
vi CONTENTS
Conformational Analysis of Snake Toxins by Laser Raman Spectroscopy
Anthony T. Tu 139
The Raman Spectroscopy of Nucleic Acids
W. L. Peticolas and M. Tsuboi 153
Estimation of the Distortion of the Geometry of Nucleic-Acid Bases in the Excited
Electronic State from the Ultra-Violet Resonance Raman Enhancement of Certain
Normal Modes
Warner L. Peticolas and Dan C. Blazej 167
15N Isotope Effects on the Raman Spectra of 5'UMP and 5'UMP-d3
H. Haruyama, Y. Nishimura and M. Tsuboi 175
Interaction of Metal Ions with Nucleic Acids
T. Theophanides 187
Vibrational Spectroscopy of Metal Nucleic Acid Systems
T. Theophanides 205
Interaction of Metal Ions with Peptides in Aqueous Medium as Studied by Infrared and
Raman Spectroscopy
M. Tasumi 225
Applications of Raman Spectroscopy to Biomembrane Structure
Bruce P. Gaber, Paul Yager and Warner L. Peticolas 241
Resonance Raman Spectra of Model Metallo Porphins
H. J. Bernstein 261
Resonance Raman Spectroscopy of Heme Proteins
Thomas G. Spiro 267
HYDROGEN BONDED SYSTEMS
Vibrational Spectroscopy of Hydrogen Bonded Systems
A. Novak 279
Overtones and Combination Tones: Application to the Study of Molecular Associations
C.Sandorry 305
Infrared Studies on Anesthetic Compounds
C. Sandorfy and G. Trudeau 319
CONTENTS vii
EXPE RIM ENT AL TECHNIQUES
Experimental Techniques of Resonance Raman Spectroscopy Applied to Biological
Molecules
M. Berjot, M. Manfait and T. Theophanides 327
Techniques of Raman Spectroscopy
Michel Delhaye 355
Index 367
PREFACE
For this summer school in Athens, Greece, August 22-21, 1978, I took as my objective the
presentation of a timely representative account of the application of infrared and Raman spectro
scopy to biological molecules.
A summer school is made up of a number of things - ideas, people, organization international
collaboration and sponsorship. The exchange of ideas the student-lecturer interaction in the
discussion periods and the tutorials satisfy the urgent need of all the participants to meet and
discuss topics of current scientific interest. It seems therefore appropriate to publish this summer
school proceedings in order to make it a lasting event and that appreciation be shown to those
people and institutions that made it all possible.
The summer school was held under the auspices of the Greek Ministry of Culture and Sciences
under the sponsorship of the NATO Scientific Affairs Division in Brussels. In addition, support was
provided by the National Hellenic Research Foundation and the Ministry of Culture and Sciences
for several social and scientific functions.
Thanks to the use of laser beams as exciting sources in Raman spectroscopy and the introduction
of computers and computer analysis of the spectra this technique can actually provide a wealth of
information, not only on the small and medium molecules, but also on the very large macromolec
ular structures which constitute the living matter. It is thus of utmost importance to organize
meetings between the spectroscopists and the people who are working with low forms of life i.e.,
the biologists, chemists and biochemists. Plant physiologists and medical researchers were also
among the participants in the program. The presentation included general talks, review and back
ground material for the students and a few reports of original research.
It was hoped that there would be a balance of infrared and Raman lectures and participants.
However, Raman spectroscopists were predominant showing the present trend of interest among
those applying vibrational spectroscopy.
Thanks to a great many people who helped in various ways either with the school itself or the
publication of the manuscripts. First of all, I must thank the authors, for sending in their manuscripts
on time. I would also like to thank Professor L. Bernard for secretarial assistance and help in the
social events and for advise which was instrumental in arranging the summer school.
National Hellenic Research Foundation, Director THEO M. THEOPHANIDES
Physical Chemistry and Spectroscopy
Centre B. Constantinou Ave,
Athens 501, Greece, and
Professor
Universite de Montreal
Departement de Chimie
Montreal, Quebec, CANADA
ix
INTRODUCTION AND HISTORICAL SURVEY
INTRODUCTION TO THE RAMAN SPECTROSCOPY OF BIOLOGICAL MOLECULES
Lucien BERNARD
Laboratoire de Recherches Optiques,Universite de REIMS
FRANCE
In March 1928 it was published in Nature, by two physi
cists C.V. Raman and K.S. Krishnan, a new phenomenon which
revolutionized our techniques, commonly used to investigate
matter; this new technique was called the Raman spectroscopy.
This effect was also observed independently in June
of the same year by the Russians Landsberg and Mandelstam. The
Raman effect was predicted theorically by Smekal in 1923.
The French physicist J. Cabannes had also observed this
phenomenon in experiments with scattered light in high atmosphere
on photographic plates. However, he believed that these new lines
were due to some artefact. Cabannes confirmed immediatly after,
the discovery of the Raman effect.
In this paper we will not be concerned about the
important discovery itself. Raman was largely responsible, because
he was the first one to show this effect conclusively and for
which he was awarded the Nobel Prize in Physics in 1930.
From then onwards, the Raman effect was proved to be
an extraordinary tool for research because ten years later there
were·more than 2000 papers published and today there are tenths
of thousands of them on the same subject.
We shall give a brief description of this phenomenon.
A monochromatic beam of frequency v falls on a sample
(solid, liquid or gas) the light diffused byOthe molecules of
the sample contains not only the frequency v , but also the
frequencies Vo ± vj ' which are characteristi2 of the molecular
3
Theo M. Theophanides (ed.), Infrared and Raman Spectroscopy of Biological Molecules, 3-34.
All Rights Reserved. Copyright © 1979 by D. Reidel Publishing Company, Dordrecht, Holland.
