The Maillard Reaction Consequences for the Chemical and Life Sciences Edited by RAPHAEL IKAN Hebrew University of Jerusalem, Israel JOHN WILEY & SONS Chichester • New York • Brisbane • Toronto • Singapore Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com Copyright © 1996 by John Wiley & Sons Ltd, Baffins Lane, Chichester, West Sussex POI9 IUD, England National 01243 779777 International ( + 44) 1243 779777 All rights reserved. No part of this book may be reproduced by any means, or transmitted, or translated into a machine language without the written permission of the publisher. Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, USA Jacaranda Wiley Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W ILl, Canada John Wiley & Sons (SEA) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 0512 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0-471-96300-3 Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com To my wife, Yael, and our favorite offspring, who enjoy her tasty Maillard-flavored food. Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com Contents List of Contributors .............................................. ix Preface ......................................................... xi List of Abbreviations ............................................. xiii 1 Geochemical Aspects of the Maillard Reaction ..................... R. Ikan, Y. Rubinsztain, A. Nissenbaum and l. R. Kaplan 2 Thermal Generation of Maiilard Aromas ......................... 27 C.-T. Ho 3 The Role of Oxidation in the Maillard Reaction in Vivo ............. 55 J. W. Baynes 4 Free Radicals and Glycation Theory ............................. 73 S. P. Wolff 5 Scavenging of Active Oxygen by Melanoidins ...................... 89 F. Hayase The Impact of the Maillard Reaction on the Nutritional Value of Food Proteins ....... ....................................... 105 M. Friedman 7 Genotoxicity of Maiilard Reaction Products ....................... 129 J. W. Wong and T. Shibamoto 8 DNA-Advanced Glycosylation ................................... 161 R. Bucala and A. Cerami Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com viii Contents 9 Maillartl Reaction under Microwave Irradiation .................... 183 V. A. Faylayan Author Index .................................................... 199 Subject Index .................................................... 211 Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com List of Contributors PROFESSOR JOHN W. BAYNES Department of Chemistry and Biochemistry and School of Medicine, University of South Carolina, Columbia, SC 29208, USA PROFESSOR RICHARD BUCALA The Picower Institute for Medical Research, 350 Community Drive, Manhasset, NY 11030, USA PROFESSOR ANTHONY CERAMI The Picower Institute for Medical Research, 350 Community Drive, Manhasset, NY 11030, USA DR MENDEL FRIEDMAN USDA-ARS, Western Regional Research Center, 800 Buchanan Street, Albany, CA 94710, USA PROFESSOR F. HAYASE Department of Agricultural Chemistry, Meiji University, 1-1-1 Higashi-mita, Tama-ku, Kawasaki, Kanagawa 214, Japan PROFESSOR CHI-TANG HO Department of Food Science, Rutgers State University, PO Box 231, New Brunswick, NJ 08903-0231, USA PROFESSOR RAPHAEL IKAN Department of Organic Chemistry, Hebrew University of Jerusalem, Jerusalem 91904, Israel PROFESSOR I. R. KAPLAN Institute of Geophysics and Planetary Physics, University of California Los Angeles, USA Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com x List of Contributors PROFESSOR A. NISSENBAUM Weizmann Institute of Science, Rehovot, Israel PROFESSOR TAKAYUKI SHIBAMOTO Department of Environmental Toxicology, University of California Davis, Davis, CA 95616, USA DR Y. RUBINSZTAIN Department of Organic Chemistry, Hebrew University of Jerusalem, Jerusalem 91904, Israel PROFESSOR SIMON P. WOLFF Formerly of Toxicology Laboratory, Department of Medicine, University College London Medical School, London WC1E 6JJ, England DR JON W. WONG Department of Environmental Toxicology, University of California Davis, Davis, CA 95616, USA PROFESSOR V. A. YAYLAYAN Department of Food Science and Agricultural Chemistry, McGill University, 2111 Lakeshore Road, Ste Anne de Bellevue, Quebec, Canada H9X 3 V9 Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com Preface The term MaiUard reaction, or nonenzymatic browning, was coined in honor of its inventor, Louis-Camille Maillard. It is related to the reaction between amines and carbonyl compounds, especially reducing sugars. It has been detected in heated, dried or stored foods and in the mammalian organisms. In food stuffs, the Maillard reaction is responsible for changes in the flavor, color, nutritive value and the formation of mutagenic compounds. In vivo aging and the complications of diabetes are partly ascribed to the interaction of glucose and proteins. Mauron has divided the Maillard reaction into three stages: early, advanced and final. The first corresponds to the chemically well-defined stages, without browning (flavors, etc.), and the second to the innumerable reactions leading to the final stage of formation of insoluble brown polymers (melanoidins). Maillard reactions are strongly dependent on the reaction conditions. The most important parameters are duration and temperature of heating, moisture content, pH and type of sugar present. This book tries to show the present state of the art in the development of new horizons and approaches of the Maillard reactions in the following topics: the Maillard reaction under physiological conditions, its impact on aging, its anticarcinogenic effects, free radicals and glycation theory, genotoxicity, generation of aromas, the effect on nutritional values of food, nonenzymatic glycation, geochemical aspects, DNA cleavage of glycated proteins, biological recognition of Maillard reaction products, scavenging of active oxygens and microwave-induced Maillard reaction. The wealth of information presented in this book by well-known scientists on the multidisciplinary nature of the Maillard reaction may open up the way for a cross-fertilization between the various disciplines. Although this book cannot give a complete account of the Maillard reaction, we hope that it will furnish important information on its various aspects. The Maillard reaction is regarded as a 'simple' and an easy reaction to carry out in the laboratory; however, the mechanism of this reaction is rather complex. Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com xii Preface Furthermore, its involvement in many interdisciplinary fields is remarkable. In this respect it is incomparable to any other chemical reaction. This book might be of interest to scientists engaged in research in the following areas: biochemistry, biology, chemistry, geochemistry, nutrition, food, physiology, toxicology and other areas. I would like to take this opportunity to express my gratitude to the contributing authors and the publisher. Raphael Ikan Department of Organic Chemistry, Laboratory of Natural Products and Organic Geochemistry, Hebrew University of Jerusalem, Israel and The Institute of Geophysics and Planetary Physics, University of California Los Angeles (UCLA), USA Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com List of Abbreviations AGE Advanced Glycosylation End-products BSA Bovin Serum Albumin 13C-CP-MAS NMR 13C-Cross Polarized Magic Angle Spinning Nuclear Magnetic Resonance CML Carboxymethyllysine EDTA Ethylene Diamine Tetra Acetate ESR Electron Spin Resonance FFI Furoyl Furanyl Imidazole GC-MS Gas Chromatography-Mass Spectrometry HHA Heterocyclic Aromatic Amines HPLC High Performance Liquid Chromatography HS Humic Substances LC-MS Liquid Chromatography-Mass Spectrum LDL Low Density Lipoproteins MRP Maillard Reaction Products NFP Novel Fluorophore NMR Nuclear Magnetic Resonance NPR Net Protein Ratio NPU Net Protein Utilization PER Protein Efficiency Ratio PNV Protein Nutritional Value UV Ultra Violet Copyright © 1996 John Wiley & Sons Retrieved from: www.knovel.com 1 Geochemical Aspects of the Maillard Reaction R. IKAN 1, Y. RUBINSZTAIN l, A. NISSENBAUM 2 and I. R. KAPLAN 3 ~Department of Organic Chemistry, Hebrew University of Jerusalem, Israel 2Weizmann Institute of Science, Rehovot, Israel 3Institute of Geophysics and Planetary Physics, University of California Los Angeles, USA Brown acidic polymers known as humic substances account for much of the organic material that occurs in soils, natural waters and recent sediments (Borkovsky, 1965). It has long been recognized that the degradation products of lignin can react with proteins and amino acids to form humic substances (Flaig, 1964). Since the work of Maillard (1913), evidence has accumulated which suggests that natural humic substances may also be produced by condensation reactions between sugars and amino acids (Enders and Theis, 1938; Hodge, 1953; Abelson and Hare, 1971). This evidence is based upon chemical similarities between natural humic substances and sugar-amino acid condensation products (melanoidins) produced in the laboratory (Hoering, 1973) and upon the occurrence of indigenous humic substances in marine environments, where carbohydrates and proteins or their degradation products, because of their abundance, are more likely precursors of humic substances