Table Of ContentNMR APPLICATIONS
IN BIOPOlY MERS
BASIC LIFE SCIENCES
Ernest H. Y. Chu, Series Editor
The University of Michigan Medical School
Ann Arbor, Michigan
Alexander Hollaender, Founding Editor
Recent volumes in the series:
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Edited by Gilbert S. Omenn
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Volume 50 CLINICAL ASPECTS OF NEUTRON CAPTURE THERAPY
Edited by Ralph G. Fairchild, Victor P. Bond,
and Avril D. Woodhead
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FOR NEUTRON CAPTURE THERAPY
Edited by Otto K. Harling, John A. Bernard, and Robert G. Zamenhof
Volume 55 IN VIVO BODY COMPOSITION STUDIES: Recent Advances
Edited by Seiichi Yasumura, Joan E. Harrison, Kenneth G. McNeill,
Avril D. Woodhead, and F. Avraham Dilmanian
Volume 56 NMR APPLICATIONS IN BIOPOLYMERS
Edited by John W. Finley, S. J. Schmidt, and A. S. Serianni
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NMR APPLICATIONS
IN BIOPOlY MERS
Edited by
J. W. Finley
Nabisco Brands, Inc.
East Hanover, New Jersey
S. J. Schmidt
University of Illinois
Urbana, Illinois
and
A. S. Serianni
University of Notre Dame
Notre Dame, Indiana
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging-in-Publlcatlon Data
American Chemical Soclety Symposium on Applications of NMR in
Blcpolymers (1988 Los Angeles, Calif.)
NMR applications ln biopolymers / edite~ by J.~. Finley, S.J.
Schmidt9 and A.S. Serlanni.
p. cm. -- (Basic life sciences; v. 56)
"Proceedings based on an American Chemical Society Symposium on
Appl ications of NMR in Biopolymers, held September 25-28, 1988, in
Los Angeles, California, and an American Chemlcal Society Symposium
on Recent Developments in NMR Spectroscopy of Carbohydrates, held
June 5-8, 1988, in Toronto, Canada"--T.p. verso.
Ine 1u des b; b 11 ograph; ca 1 references and 1 ndex.
ISBN-13: 978-1-4684-5870-1
1. Nuclear magnetic resonance spectroscopy--Congresses.
2. Biopolymers--Structure--Congresses. I. Finley, John ~., 1942-
II. Schmldt, S. J. III. Serianni, Anthony Stephen. IV. American
Chemical Society. V. Amerlcan Chernlcal SOclety Sy~posium on Recent
Developments in NMR Spectroscopy of Carbohydrates (1988 Toronto,
Ont.) VI. Title. VII. Series.
QP519.9.N83A44 1988
574. 19'285--dc20 90-47280
CIP
Proceedings based on an American Chemical Society Symposium on Applications of NMR in
Biopolymers, held September 25-28, 1988, in Los Angeles, California, and an American
Chemical Society Symposium on Recent Developments in NMR Spectroscopy of Carbohydrates,
held June 5-8, 1988, in Toronto, Canada
ISBN-13: 978-1-4684-5870-1 e-ISBN-13: 978-1-4684-5868-8
001: 10.1007/978-1-4684-5868-8
© 1990 Plenum Press, New York
Softcover reprint of the hardcover 1s t edition 1990
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
Elucidating the structures of biopolymers as they exist in nature has
long been a goal of biochemists and biologists. Understanding how these
substances interact with themselves, other solutes, and solvents can
provide useful insights into many areas of biochemistry, agriculture, food
science and medicine. Knowledge of the structure of a protein or complex
carbohydrate in its native form provides guidelines for the chemical or
genetic modifications often desired to optimize these compounds to specific
needs and applications. For example, in the pharmaceutical industry,
structure-function relationships involving biopolymers are studied rou-
tinely as a means to design new drugs and improve their efficacies.
The tools to conduct structure investigations of biopolymers at the
molecular level are limited in number. Historically X-ray crystallography
has been the most attractive method to conduct studies of this type. How-
ever, X-ray methods can only be applied to highly ordered, crystalline
materials, thus obviating studies of solution dynamics that are often
critical to attaining a global understanding of biopolymer behavior. In
recent years, nuclear magnetic resonance (NMR) spectroscopy has evolved to
become a powerful tool to probe the structures of biopolymers in solution
and in the solid state. NMR provides a means to study the dynamics of
polymers in solution, and to examine the effects of solute, solvent and'
other factors~n polymer behavior. With the development of 2D and 3D forms
of NMR spectroscopy, it is now possible to assess the solution conforma-
tions of small proteins, oligonucleotides and oligosaccharides.
This book grew from two recent symposia sponsored by the American
Chemical Society: "Recent Developments in the NMR Spectroscopy of
Carbohydrates" sponsored by the Division of Carbohydrate Chemistry at the
Toronto meeting in June 1988, and "NMR Applications in Food Chemistry"
sponsored by the Agricultural and Food Division at the Los Angeles meet-
ing in September 1988. The complementarity in subject matter between
these two events suggested that contributions be brought together under
one cover. This volume provides the NMR spectroscopist, whether new to
the field or experienced, with discussions of recent techniques and
results pertaining to complex molecular systems such as proteins and
v
complex carbohydrates. It also provides the practitioners of biochemis-
try, food chemistry and carbohydrate chemistry with valuable information
on the behavior of various biopolymers in solution and in the solid
state. Perhaps the most exciting feature is the wide range of NMR appli-
cations found in this volume, a testimony to the impact that the NMR
method has made on many fields of scientific inquiry. It is our hope
that this book will be intellectually rewarding to its readers, and that
it will stimulate new, future applications of the NMR method.
J. Finley
A. Serianni
S. Schmidt
ACKNOVLEDGMENTS
The editors gratefully acknowledge and thank all of the contributors
who devoted their time to prepare the chapters of this book; without
their significant effort, this book would not have been possible. Their
efforts are particularly significant in light of the fact that the roy-
alties from this book will be given to the Carbohydrate Chemistry, and
Agricultural and Food, Divisions of the American Chemical Society to
support future symposia.
The editors also thank Susie Anderson of EG&G Vashington Analytical
Services Center, Inc., for retyping the manuscripts in the correct format
for publication and for her endless patience during the editorial pro-
cess, and Fran Osborne of Nabisco Brands, Inc., for "reminding" the
contributors to submit their contributions and for expediting the review
process.
vii
CONTENTS
Applications of NMR in Agriculture and Biochemistry 1
S.J. Schmidt, A.S. Serianni, and J.~. Finley
Carbohydrate Stereochemistry, and NMR Spectroscopy 7
A.S. Perlin
Applications of 2D NMR Spectroscopy to Carbohydrates. . . . . . .. 17
L. Lerner
Two-Dimensional NMR Spectrum Editing of Carbohydrates 27
B. Coxon
Determination of Complex Carbohydrate Structure Using Carbonyl
Carbon Resonances of Peracetylated Derivatives . . . • 47
~.J. Goux
Selective Excitation Techniques for ~ater Suppression in One- and
Two-Dimensional NMR Spectroscopy . . . . . . . . . . . . . 63
V. Sklenar
Oxygen Exchange and Bond Cleavage Reactions of Carbohydrates
13
Studied Using the 180 Isotope Shift in C NMR Spectroscopy 85
T.L. Mega and R.L. Van Etten
Computer-Aided Conformational Analysis Based on NOESY Signal
Intensities ......... . 95
N.H. Andersen, X. Lai, P. K. Hammen and T.M. Marschner
Determination of DNA and Protein Structures in Solution Via
Complete Relaxation Matrix Analysis of 2D NOE Spectra 135
T.L. James, B.A. Borgias, A.M. Bianucci, and N. Zhou
The Structure and Behavior of the Starch Granule as Studied
by NMR . . . . . . . . . . . . . . ... 155
J.M.V. Blanshard, E.M. Jaroszkiewicz and M.J. Gidley
~ater Interactions in Bovine Casein: 2H NMR Relaxation and
Small-Angle X-Ray Scattering Studies 175
H. Pessen, T.F. Kumosinski and H.M. Farrell, Jr.
Carbon-13 NMR Studies of Native, Gelled, Heat- and Chemically-
Denatured Soy Glycinin and a-Conglycinin at Neutral pH 199
M.S. Fisher, ~.E. Marshall and H.F. Marshall, Jr.
NMR Studies of the Structure and Environment of the Milk Protein
a-Lactalbumin . . . . . . . . 231
L.J. Berliner, R. Kaptein, K. Koga, and G. Musci
ix
Applications of Multinuclear NMR in the Solid State to Structural
and Dynamical Problems in Macromolecular Chemistry . . .. 255
R.G. Bryant, S.D. Kennedy, C.L. Jackson, T.M. Eads,
W.R. Croasmun, and A.E. Blaurock
Heterogeneity of Intact Collagen by Solid State Multinuclear
Magnetic Resonance .. ............. . 273
Y. Hiyama and D.A. Torchia
Forage Digestibility and Carbon-13 Solid State NMR . . . . . . . .. 287
N. Cyr, R.M. Elofson and G.W. Mathison
NMR of Carbohydrates at the Surface of Cells 303
H.C. Jarrell and I.C.P. Smith
Studies of Evolving Carbohydrate Metabolism in vivo by 13C
Surface-Coil NMR Spectroscopy . . . . 317
N.N. Becker and J.J.H. Ackerman
Uptake, Metabolism, and Storage of Phosphate and Nitrogen in Plant
Cells; an NMR Perspective . . . .. ...... 329
H.J. Vogel and P. Lundberg
In Vivo Phosphorus NMR Studies of the Hepatic Metabolism of Amino
Sugars. ...... . . . . . . . . . .. 349
R.E. London, S.A. Gabel and M.E. Perlman
Multinuclear Spin Relaxation and High-Resolution Nuclear Magnetic
Resonance Studies of Food Proteins, Agriculturally
Important Materials and Related Systems . . . . . . . .. 361
I.C. Baianu, T.F. Kumosinski, P.J. Bechtel,
P.A. Myers-Betts, P. Yakubu and A. Mora
1H and 2H NMR Studies of Water in Work-Free Wheat Flour Doughs 391
D.A. d'Avignon, Chi-Cheng Hung, M.T.L. Pagel, B. Hart,
G.L. Bretthorst and J.J.H. Ackerman
Characterization of Water in Foods by NMR 415
S.J.R. Schmidt
13 17
Use of C and 0 NMR to Study Wheat Starch-Water-Sugar
Interactions with Increasing Temperatures . . . .. 461
D. Sobczynska, C. Setser, H. Lim, L. Hansen and J. Paukstelis
Application of the Low Resolution Pulsed NMR "Minispec" to
Analytical Problems in the Food and Agriculture
Industries . . . . . . . . . . . . . . . . . . 481
P.J. Barker and H.J. Stronks
Automatic Use of Small Nuclear Magnetic Resonance Spectrometers
for Quality Control Measurements. . . . . . . . . . . . 499
R.M. Pearson and J.Q. Adams
Index 511
x
APPLICATIONS OF NMR IN AGRICULTURE AND BIOCHEMISTRY
S. J. Schmidt(a), A. S. Serianni(b) and J. Y. Finley(c)
(a) Division of Foods and Nutrition
University of Illinois
Urbana, IL
(b) Department of Chemistry and Biochemistry
University of Notre Dame
Notre Dame, IN
(c) Nabisco Biscuit Company
East Hanover, NJ
AN OVERVIEY
The complex relationship between molecular structure and biological
function is a central theme of most contemporary biochemical studies. The
specific interactions of biomacromolecules with themselves, solvents, sub-
strates and other solutes determine their biological functions in living
systems. For decades organic chemists have explored structure-reactivity
correlations in small organic molecules by studying the effects of thought-
ful, systematic changes in molecular structure on chemical behavior. Now,
with the tools of modern molecular biology at their disposal, biochemists
may systematically alter protein structure to assess the structure-function
relationships in this important class of biopolymers. Such studies promise
to identify and quantify the molecular factors that confer specificity to
protein-substrate binding, and the factors that are responsible for the rate
enhancements of enzyme-catalyzed reactions. This information is essential,
for example, to the rational design of artificial enzymes and the develop-
ment of specific enzyme inhibitors for use in the treatment of human
metabolic disorders.
Yith the ability to prepare proteins and other biopolymers of defined
structure almost at will comes the need to establish their three-dimensional
structures and their solution behaviors in a routine and timely fashion.
Although other analytical methods are available to study biopolymer struc-
ture and behavior, in recent years nuclear magnetic resonance (NMR) spectro-
scopy has emerged as a very powerful and versatile tool to address these
problems at the molecular level. The NMR method is complemented frequently
NMR Applications in Biopolymers, Edited by 1
J. W. Finley et al., Plenum Press, New Yark, 1990
