Autoxidation in Food and Biological Systems

652 Pages·1980·53.338 MB·English

by  William A. Pryor, Donald G. Prier, John W. Lightsey, Daniel F. Church (auth.), Michael G. Simic, Marcus Karel (eds.)

Autoxidation in
Food and Biological
Systems
Autoxidation in
Food and Biological
Systems
Edited by
Michael G. Simic
Center for Radiation Research
National Bureau of Standards
Washington, D.C.
and
Marcus Karel
Massachusetts Institute of Technology
Cambridge, Massachusetts
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Library of Congress Cataloging in Publication Data
Main entry under title:
Autoxidation in food and biological systems.
"Proceedings of an international workshop on autoxidation processes in food and
related biological systems held October 29-31, 1979, in Natick, Massachusetts.
Several contributions were presented at the IFT basic symposium on food lipids held
June 8-9, 1979, in St. Louis, Missouri."
Includes bibliographical references and index.
I. Oxidation, Physiological-Congresses. 2. Food-Analysis-Congresses. 3. Anti
oxidants-Congresses. I. Simic, Michael G. II. Karel, Marcus.
QP177 A97 664 80-23849
ISBN 978-1-4757-9353-6 ISBN 978-1-4757-9351-2 (eBook)
DOi 10.1007/978-1-4757-9351-2
Proceedings of the Workshop on Autoxidation Processes,
held at the U.S. Army Natick Research and Development Command
Natick, Massachusetts October 29-31, 1979.
© 1980 Springer Science+ Business Media New York
Originally published by Plenum Press, New York in 1980
Softcover reprint of the hardcover 1st edition 1980
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 material presented in this book deals with basic mechanisms
of free radical reactions in autoxidation processes and anitoxidant
suppression of autoxidation of foods, biochemical models and biologi
cal systems. Autoxidation in foods and corresponding biological
effects are usually approached separately although recent mechanistic
developments in the biochemistry and free radical chemistry of per
oxides and their precursors tend to bring these two fields closer.
Apparent ability of antioxidants in diets to reduce the inci
dence of cancer has resulted in scrutiny of autoxidized products and
their precursors as possibly toxic, mutagenic and carcinogenic
agents. Mechanisms of any of these effects have been barely ad
dressed. Yet we know now that free radicals, as esoteric as they
were only a few decades ago, are being discovered in foods, biochem
ical and biological systems and do play a role in the above-mentioned
causalities.
The purpose of the Workshop and the resulting book was to give
a unifying approach towards study of beneficial and deleterious
effects of autoxidation, based on rigorous scientific considerations.
It is our hope that the material presented in this book will not only
provide a review of the "state of the art" of autoxidation and anti
oxidants, but also reflect the interaction which occurred during the
Workshop between workers using model sytems, and food and biological
systems.
Michael G. Simic
Marcus Karel
v
ACKNOWLEDGEMENTS
The contributions in this book result mainly from the Interna
tional Workshop on "Autoxidation Processes in Food and Related
Biological Systems" organized jointly by the U.S. Army Research and
Development Command and Massachusetts Institute of Technology and
held at Natick, October 29-31, 1979. A few contributions were pre
sented at the IFT Basic Symposium on "Food Lipids" in St. Louis,
Missouri on June 8-9, 1979.
We take this opportunity to acknowledge active support of Dr.
Hamed E]_ Bisi, Deputy Technical Director, and Colonel Robert J.
Cuthbertson, Commander of the U.S. Army NARADCOM. Direct assistance
of Dr. William L. Porter, co-chairman of the Workshop as well as of
the NARADCOM organizing committee including Dr. S. David Bailey and
Dr. J. Walter Giffee has been greatly appreciated. We are grateful
for secretarial assistance of Janice Call-Rosado, Ruth Fortner, and
Anna M. Devine.
Special gratitude is expressed to U.S. Army Research Office for
financial support of the Workshop and Dr. W. F. Morthland, Chief,
Life Sciences Program, whose comprehensive background in diverse
fields greatly contributed towards the success of the Workshop and
delightful interactions.
The editorial assistance of Colleen Cathcart and of Janet Copley
was particularly essential to the timely completion of the book, and
we gratefully acknowledge it.
vii
CONTENTS
MECHANISMS OF AUTOXIDATION
1. Initiation of the Autoxidation of Poly
unsaturated Fatty Acids (PUFA) by
Ozone and Nitrogen Dioxide . . . . 1
W.A. Pryor, D.G. Prier, J.W. Lightsey,
and D.F. Church
2. Kinetic and Mechanistic Studies of
Peroxy, Vitamin E and Anti
Oxidant Free Radicals by Pulse
Radiolysis . . . . . . . . . . 17
M.G. Simic
3. Singlet Oxygen-Initiated Photooxidation
of Unsaturated Fatty Acid Esters
and Inhibitory Effects of
Tocopherols and 6-Carotene 27
S. Matsushita and J. Terao
4. EPR Studies in Autoxidation 45
K.M. Schaich and D.C. Borg
5. Spin Trapping of Radical Species Involved
in the Propagation of Lipid
Peroxidation . . . . . . . . . . . . 71
G.M. Rosen, E.J. Rauckman, and
E. Finkelstein
6. Dioxygen Complexes as Intermediates in
Metal-Catalyzed Oxidation of
Organic Substances . . . . . . . 89
A.E. Martell
7. The Autoxidation of Cholesterol 119
L.L. Smith
ix
CONTENTS
X
FOOD AND MODEL SYSTEMS
8. Activities of FDA'S Division of Nutrition
Regarding Cholesterol Oxides . . . . 133
A.J. Sheppard and C-s.J. Shen
9. Analytical Methods Used in the Study of
Autoxidation Processes . 141
E.N. Frankel
10. Rapid Instrumental Analysis of Lipid
Oxidation Products . . . . . 171
A.J. St. Angelo, M.G. Legendre,
and H.P. Dupuy
11. Simplified Tests for Fat Deterioration 185
S. Matsushita and T. Asakawa
12. Lipid Oxidation, Secondary Reac.tions, and
Water Activity of Foods ..... . 191
M. Karel
13. Autoxidation of Fats and Oils at Elevated
Temperatures . . . . . . 207
W.W. Nawar and A. Witchwoot
14. Lipid Hydroperoxide Induced Oxidation of
Cysteine in Peptides ...... . 223
J.W. Finley and R.E. Lundin
15. Degradation Products of L-Tryptophan Reacted
with Peroxidizing Methyl Linoleate 237
S.H. Yong, S. Lau, Y. Hsieh,
and M. Karel
16. Oxidative Crosslinking of Proteins and
Other Biopolymers . . . . . 249
H. Neukam
ANTIOXIDANTS
17. Natural Antioxidants 261
L.R. Dugan
18. Natural Antioxidants of Soybeans and Other
Oil-Seeds . . . . . . 283
D.E. Pratt
CONTENTS xi
19. Recent Trends in Food Applications of
Antioxidants 295
W.L. Porter
20. Antioxidative Effect of Maillard Reaction
Intermediates 367
K. Eiclmer
21. Antioxidants as Blocking Agents Against
Nitrosamine Formation ..• 387
W.J. Mergens and H.L. Newmark
22. Optimization of the Antioxidant System
in a Dietary Supplement . • . . . 405
L.L. Yaeger and J. Bjorksten
BIOCHEMICAL SYSTEMS
23. Peroxidation of Lipids in Model Systems
and in Biomembranes • • . . • • 413
J.F. Mead, R.A. Stein, G-S. Wu,
A. Sevanian, and M. Gan-Elepano
24. Superoxide Radical and Superoxide
Dismutases: Threat and Defense 429
K. Brawn and I. Fridovich
25. Lipid Enzymes: Lipases, Lipoxygenases,
and "Hydroperoxidases" . . . . . 447
H. W. Gardner
26. Enzyme-Catalyzed Lipid Oxidation in
Muscle Microsomes . . . . . . 505
H.O. Hultin
27. Lipoxygenase-Catalysed Oxidation of
Linoleic Acid . • . . . . 529
J.F.G. Vliegenthart and G.A. Veldink
28. Lipid Peroxidation: The Role of Hepatic
Fad-Monooxygenase . . . . . • • . . 541
J.D. George, G.M. Rosen, E.J. Rauckman,
and D.M. Ziegler
BIOLOGICAL SYSTEMS
29. Intracellular Mechanisms for Lipid
Peroxide Decomposition 563
P.J. O'Brien
xii CONTENTS
30. Biological Effects of Some Products of
Cholesterol Autoxidation 589
A.A. Kandutsch
31. Possible Role of Oxidized Lipids in
Atherosclerosis 599
F.A. Kummerow
32. Arterial Wall Injury and Repair Due to
Oxygenated Sterols and Possible
Precursors 613
H. Imai
33. Is Peroxidation Important in the Cancer
Process 639
R.J. Shamberger
Index 651