vitamin in food

DK4945_half 9/8/05 1:18 PM Page VITAMINS IN FOODS Analysis, Bioavailability, and Stability © 2006 by Taylor & Francis Group, LLC DK3926_series.qxd 9/8/05 2:50 PM Page FOOD SCIENCE AND TECHNOLOGY A Series of Monographs, Textbooks, and Reference Books Editorial Advisory Board Gustavo V Barbosa-Cánovas Washington State University–Pullman P Michael Davidson University of Tennessee–Knoxville Mark Dreher McNeil Nutritionals, New Brunswick, NJ Richard W Hartel University of Wisconsin–Madison Lekh R Juneja Taiyo Kagaku Company, Japan Marcus Karel Massachusetts Institute of Technology Ronald G Labbe University of Massachusetts–Amherst Daryl B Lund University of Wisconsin–Madison David B Min The Ohio State University Leo M L Nollet Hogeschool Gent, Belgium Seppo Salminen University of Turku, Finland James L Steele University of Wisconsin–Madison John H Thorngate III Allied Domecq Technical Services, Napa, CA Pieter Walstra Wageningen University, The Netherlands John R Whitaker University of California–Davis Rickey Y Yada University of Guelph, Canada 76 77 78 79 80 81 82 83 84 85 86 87 88 Food Chemistry: Third Edition, edited by Owen R Fennema Handbook of Food Analysis: Volumes and 2, edited by Leo M L Nollet Computerized Control Systems in the Food Industry, edited by Gauri S Mittal Techniques for Analyzing Food Aroma, edited by Ray Marsili Food Proteins and Their Applications, edited by Srinivasan Damodaran and Alain Paraf Food Emulsions: Third Edition, Revised and Expanded, edited by Stig E Friberg and Kåre Larsson Nonthermal Preservation of Foods, Gustavo V Barbosa-Cánovas, Usha R Pothakamury, Enrique Palou, and Barry G Swanson Milk and Dairy Product Technology, Edgar Spreer Applied Dairy Microbiology, edited by Elmer H Marth and James L Steele Lactic Acid Bacteria: Microbiology and Functional Aspects, Second Edition, Revised and Expanded, edited by Seppo Salminen and Atte von Wright Handbook of Vegetable Science and Technology: Production, Composition, Storage, and Processing, edited by D K Salunkhe and S S Kadam Polysaccharide Association Structures in Food, edited by Reginald H Walter Food Lipids: Chemistry, Nutrition, and Biotechnology, edited by Casimir C Akoh and David B Min © 2006 by Taylor & Francis Group, LLC DK3926_series.qxd 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 9/8/05 2:50 PM Page Spice Science and Technology, Kenji Hirasa and Mitsuo Takemasa Dairy Technology: Principles of Milk Properties and Processes, P Walstra, T J Geurts, A Noomen, A Jellema, and M A J S van Boekel Coloring of Food, Drugs, and Cosmetics, Gisbert Otterstätter Listeria, Listeriosis, and Food Safety: Second Edition, Revised and Expanded, edited by Elliot T Ryser and Elmer H Marth Complex Carbohydrates in Foods, edited by Susan Sungsoo Cho, Leon Prosky, and Mark Dreher Handbook of Food Preservation, edited by M Shafiur Rahman International Food Safety Handbook: Science, International Regulation, and Control, edited by Kees van der Heijden, Maged Younes, Lawrence Fishbein, and Sanford Miller Fatty Acids in Foods and Their Health Implications: Second Edition, Revised and Expanded, edited by Ching Kuang Chow Seafood Enzymes: Utilization and Influence on Postharvest Seafood Quality, edited by Norman F Haard and Benjamin K Simpson Safe Handling of Foods, edited by Jeffrey M Farber and Ewen C D Todd Handbook of Cereal Science and Technology: Second Edition, Revised and Expanded, edited by Karel Kulp and Joseph G Ponte, Jr Food Analysis by HPLC: Second Edition, Revised and Expanded, edited by Leo M L Nollet Surimi and Surimi Seafood, edited by Jae W Park Drug Residues in Foods: Pharmacology, Food Safety, and Analysis, Nickos A Botsoglou and Dimitrios J Fletouris Seafood and Freshwater Toxins: Pharmacology, Physiology, and Detection, edited by Luis M Botana Handbook of Nutrition and Diet, Babasaheb B Desai Nondestructive Food Evaluation: Techniques to Analyze Properties and Quality, edited by Sundaram Gunasekaran Green Tea: Health Benefits and Applications, Yukihiko Hara Food Processing Operations Modeling: Design and Analysis, edited by Joseph Irudayaraj Wine Microbiology: Science and Technology, Claudio Delfini and Joseph V Formica Handbook of Microwave Technology for Food Applications, edited by Ashim K Datta and Ramaswamy C Anantheswaran Applied Dairy Microbiology: Second Edition, Revised and Expanded, edited by Elmer H Marth and James L Steele Transport Properties of Foods, George D Saravacos and Zacharias B Maroulis Alternative Sweeteners: Third Edition, Revised and Expanded, edited by Lyn O’Brien Nabors Handbook of Dietary Fiber, edited by Susan Sungsoo Cho and Mark L Dreher Control of Foodborne Microorganisms, edited by Vijay K Juneja and John N Sofos Flavor, Fragrance, and Odor Analysis, edited by Ray Marsili Food Additives: Second Edition, Revised and Expanded, edited by A Larry Branen, P Michael Davidson, Seppo Salminen, and John H Thorngate, III Food 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Process Design, Zacharias B Maroulis and George D Saravacos 127 Handbook of Dough Fermentations, edited by Karel Kulp and Klaus Lorenz 128 Extraction Optimization in Food Engineering, edited by Constantina Tzia and George Liadakis 129 Physical Properties of Food Preservation: Second Edition, Revised and Expanded, Marcus Karel and Daryl B Lund 130 Handbook of Vegetable Preservation and Processing, edited by Y H Hui, Sue Ghazala, Dee M Graham, K D Murrell, and Wai-Kit Nip 131 Handbook of Flavor Characterization: Sensory Analysis, Chemistry, and Physiology, edited by Kathryn Deibler and Jeannine Delwiche 132 Food Emulsions: Fourth Edition, Revised and Expanded, edited by Stig E Friberg, Kare Larsson, and Johan Sjoblom 133 Handbook of Frozen Foods, edited by Y H Hui, Paul Cornillon, Isabel Guerrero Legarret, Miang H Lim, K D Murrell, and Wai-Kit Nip 134 Handbook of Food and Beverage Fermentation Technology, edited by Y H Hui, Lisbeth Meunier-Goddik, Ase Solvejg Hansen, Jytte Josephsen, Wai-Kit Nip, Peggy S Stanfield, and Fidel Toldrá 135 Genetic Variation in Taste Sensitivity, edited by John Prescott and Beverly J Tepper 136 Industrialization of Indigenous Fermented Foods: Second Edition, Revised and Expanded, edited by Keith H Steinkraus 137 Vitamin E: Food Chemistry, Composition, and Analysis, Ronald Eitenmiller and Junsoo Lee 138 Handbook of Food Analysis: Second Edition, Revised and Expanded, Volumes 1, 2, and 3, edited by Leo M L Nollet 139 Lactic Acid Bacteria: Microbiological and Functional Aspects: Third Edition, Revised and Expanded, edited by Seppo Salminen, Atte von Wright, and Arthur Ouwehand 140 Fat Crystal Networks, Alejandro G Marangoni 141 Novel Food Processing Technologies, edited by Gustavo V Barbosa-Cánovas, M Soledad Tapia, and M Pilar Cano 142 Surimi and Surimi Seafood: Second Edition, edited by Jae W Park 143 Food Plant Design, Antonio Lopez-Gomez; Gustavo V Barbosa-Cánovas 144 Engineering Properties of Foods: Third Edition, edited by M A Rao, Syed S.H Rizvi, and Ashim K Datta 145 Antimicrobials in Food: Third Edition, edited by P Michael Davidson, John N Sofos, and A L Branen 146 Encapsulated and Powdered Foods, edited by Charles Onwulata © 2006 by Taylor & Francis Group, LLC DK3926_series.qxd 9/8/05 2:50 PM Page 147 Dairy Science and Technology: Second Edition, Pieter Walstra, Jan T M Wouters and Tom J Geurts 148 Food Biotechnology, Second Edition, edited by Kalidas Shetty, Gopinadhan Paliyath, Anthony Pometto and Robert E Levin 149 Handbook of Food Science, Technology, and Engineering - Volume Set, edited by Y H Hui 150 Thermal Food Processing: New Technologies and Quality Issues, edited by Da-Wen Sun 151 Aflatoxin and Food Safety, edited by Hamed K Abbas 152 Food Packaging: Principles and Practice, Second Edition, Gordon L Robertson 153 Seafood Processing: Adding Value Through Quick Freezing, Retortable Packaging, Cook-Chilling and Other Methods, Vazhiyil Venugopal 154 Ingredient Interactions: Effects on Food Quality, Second Edition, edited by Anilkumar Gaonkar and Andrew McPherson 155 Handbook of Frozen Food Processing and Packaging, Da-Wen Sun 156 Vitamins In Foods: Analysis, Bioavailability, and Stability, George F M Ball © 2006 by Taylor & Francis Group, LLC DK4945_title 9/8/05 1:18 PM Page VITAMINS IN FOODS Analysis, Bioavailability, and Stability GEORGE F M BALL Boca Raton London New York A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc © 2006 by Taylor & Francis Group, LLC dk4945_Discl.fm Page Wednesday, September 21, 2005 3:48 PM Published in 2006 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2006 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group No claim to original U.S Government works Printed in the United States of America on acid-free paper 10 International Standard Book Number-10: 1-57444-804-8 (Hardcover) International Standard Book Number-13: 978-1-57444-804-7 (Hardcover) Library of Congress Card Number 2005049926 This book contains information obtained from authentic and highly regarded sources Reprinted material is quoted with permission, and sources are indicated A wide variety of references are listed Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Library of Congress Cataloging-in-Publication Data Ball, G.F.M Vitamins in foods : analysis, bioavailability, and stability / by George F.M Ball p cm (Food science and technology ; 156) Includes bibliographical references and index ISBN 1-57444-804-8 (alk paper) Food Vitamin content I Title II Food science and technology (Taylor & Francis) ; 156 TX553.V5B358 2005 613.2'85 dc22 2005049926 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com Taylor & Francis Group is the Academic Division of Informa plc © 2006 by Taylor & Francis Group, LLC and the CRC Press Web site at http://www.crcpress.com Dedication This work is dedicated to my wife and dearest friend, Kazuko (Kako) © 2006 by Taylor & Francis Group, LLC About the Author George Ball has accumulated many years of commercial and research laboratory experience in pharmaceutical analysis, clinical analysis, biochemical analysis, and food analysis He has contributed to original research publications relating to biochemistry (platelet function) and endocrinology (control of ovulation) and is the author of several books and book chapters on vitamins He received the B.Sc honors degree in agricultural sciences from the University of Nottingham, UK in 1975 © 2006 by Taylor & Francis Group, LLC Preface Optimal vitamin status is a prerequisite for good health, and governmentapproved food fortification strategies are deemed necessary to ensure adequate intake of certain vitamins Knowledge about vitamin bioavailability from food is essential for the estimation of dietary requirements Equally important is knowledge of a vitamin’s stability toward postharvest handling of food, processing, storage, and preparation for consumption To acquire this knowledge, one must learn about vitamin chemistry and how the vitamin is absorbed and metabolized Successful research into vitamin bioavailability and stability is entirely dependent on the development and validation of suitable analytical methods Vitamin bioavailability from food is subject to many variables imposed by food constituents and the preparation of food Great progress has been made over the past decade, largely attributable to innovative analytical methodology, but there are many inconsistencies and the continuation of a multipronged research effort from independent laboratories must be encouraged to achieve solid and vital data I would like to acknowledge the expertise and diligence of Lynn Saliba at the British Library George F M Ball © 2006 by Taylor & Francis Group, LLC 3.3.2.4 Provitamin A Carotenoids 3.3.3 Vitamin A Equivalency 3.3.4 Applicability of Analytical Techniques 3.4 Intestinal Absorption, Metabolism, and Transport 3.4.1 Absorption 3.4.2 Metabolic Events Within the Enterocyte 3.4.2.1 Esterification of Retinol 3.4.2.2 Conversion of Provitamin Carotenoids to Retinoids 3.4.3 Liver Uptake of Chylomicron Remnants and Storage of Vitamin A 3.4.4 Plasma Transport of Retinol and Carotenoids 3.4.5 Tissue Uptake and Metabolism of Retinol 3.5 Bioavailability 3.5.1 Introduction 3.5.2 In vivo Methods of Assessing b-Carotene Bioavailability 3.5.2.1 Use of Radioisotopes in Cannulated Patients 3.5.2.2 Animal Models 3.5.2.3 Serum, Plasma, or Chylomicron Responses not Involving Isotopic Tracers 3.5.2.4 Methods Involving Stable Isotopes 3.5.3 In vitro Methods of Assessing b-Carotene Bioaccessibility and Bioavailability 3.5.3.1 In vitro Digestion Methods to Assess b-Carotene Bioaccessibility 3.5.3.2 In vitro Studies of b-Carotene Absorption Using Caco-2 Cells 3.5.4 Host-Related Factors Affecting the Bioavailability of b-Carotene 3.5.5 Dietary Factors Affecting the Bioavailability of b-Carotene 3.5.5.1 Location of Carotenoids in the Plant Source 3.5.5.2 Food Matrix 3.5.5.3 Dietary Protein 3.5.5.4 Dietary Fat and Energy 3.5.5.5 Dietary Fiber 3.5.5.6 Plant Sterols 3.5.6 Conclusions 3.6 b-Carotene Supplementation 3.6.1 Effect of Vegetable Consumption on Vitamin A Status in Populations at Risk of Vitamin A Deficiency © 2006 by Taylor & Francis Group, LLC 57 60 61 61 62 63 63 63 66 66 67 67 67 68 68 69 69 71 74 74 76 77 77 77 78 80 81 86 87 88 88 88 3.6.2 Effects of b-Carotene Supplementation on Breastmilk Carotenoids 90 References 92 Chapter Vitamin D 4.1 Background 4.2 Chemical Structure, Biopotency, and Physicochemical Properties 4.2.1 Structure and Biopotency 4.2.2 Physicochemical Properties 4.2.2.1 Appearance and Solubility 4.2.2.2 Stability in Nonaqueous Solution 4.3 Vitamin D in Foods 4.3.1 Occurrence 4.3.2 Stability 4.3.3 Expression of Dietary Values 4.3.4 Applicability of Analytical Techniques 4.4 Intestinal Absorption, Transport, and Metabolism 4.5 Bioavailability References Chapter Vitamin E 5.1 Background 5.2 Chemical Structure, Biopotency, and Physicochemical Properties 5.2.1 Structure 5.2.2 Biopotency 5.2.3 Physicochemical Properties 5.2.3.1 Appearance and Solubility 5.2.3.2 Stability in Nonaqueous Solution 5.2.3.3 In Vitro Antioxidant Activity 5.3 Vitamin E in Foods 5.3.1 Occurrence 5.3.2 Stability 5.3.3 Expression of Dietary Values 5.3.4 Applicability of Analytical Techniques 5.4 Intestinal Absorption and Transport 5.4.1 Absorption 5.4.2 Plasma Transport and Distribution 5.4.3 Preferential Secretion of 2R-a-Tocopherol Stereoisomers by the Liver 5.4.4 Storage 5.5 Bioavailability 5.5.1 Efficiency of Vitamin E Absorption © 2006 by Taylor & Francis Group, LLC 107 108 108 108 108 109 110 110 112 113 113 114 115 116 119 120 120 121 122 122 122 122 123 123 126 128 128 128 129 129 129 130 130 130 5.5.2 Effects of Polyunsaturated Fats on Vitamin E Absorption 5.5.3 Effects of Dietary Fiber on Vitamin E Absorption 5.5.4 Effect of Plant Sterols on Vitamin E Bioavailability 5.6 Vitamin E Requirements References Chapter Vitamin K 6.1 Background 6.2 Chemical Structure, Biopotency, and Physicochemical Properties 6.2.1 Structure and Biopotency 6.2.2 Physicochemical Properties 6.2.2.1 Appearance and Solubility 6.2.2.2 Stability in Nonaqueous Solution 6.3 Vitamin K in Foods 6.3.1 Occurrence 6.3.2 Stability 6.3.2.1 Effects of Hydrogenation 6.3.3 Applicability of Analytical Techniques 6.4 Intestinal Absorption and Transport 6.4.1 Absorption and Transport of Dietary Vitamin K 6.4.2 Bacterially Synthesized Menaquinones as a Possible Endogenous Source of Vitamin K 6.5 Bioavailability References Chapter Thiamin (Vitamin B1) 7.1 Background 7.2 Chemical Structure, Biopotency, and Physicochemical Properties 7.2.1 Structure and Potency 7.2.2 Physicochemical Properties 7.2.2.1 Appearance and Solubility 7.2.2.2 Stability in Aqueous Solution 7.3 Thiamin in Foods 7.3.1 Occurrence 7.3.2 Stability 7.3.3 Applicability of Analytical Techniques 7.4 Intestinal Absorption 7.5 Bioavailability 7.5.1 Bioavailability of Thiamin in Foods 7.5.2 Antithiamin Factors © 2006 by Taylor & Francis Group, LLC 131 131 132 132 132 137 138 138 139 139 139 139 139 141 142 142 143 143 143 145 146 149 149 149 150 150 150 151 151 152 154 154 155 155 156 7.5.2.1 Thiaminases 7.5.2.2 Polyphenols 7.5.3 Effects of Alcohol 7.5.4 Effects of Dietary Fiber References Chapter Flavins: Riboflavin, FMN, and FAD (Vitamin B2) 8.1 Background 8.2 Chemical Structure, Biopotency, and Physicochemical Properties 8.2.1 Structure and Potency 8.2.2 Physicochemical Properties 8.2.2.1 Appearance and Solubility 8.2.2.2 Stability in Aqueous Solution 8.3 Vitamin B2 in Foods 8.3.1 Occurrence 8.3.2 Stability 8.3.3 Applicability of Analytical Techniques 8.4 Intestinal Absorption 8.4.1 Absorption of Dietary Vitamin B2 8.4.2 Absorption of Bacterially Synthesized Vitamin B2 in the Large Intestine 8.5 Bioavailability References Chapter Niacin 9.1 Background 9.2 Chemical Structure, Biopotency, and Physicochemical Properties 9.2.1 Structure and Potency 9.2.2 Physicochemical Properties 9.2.2.1 Appearance, Solubility, and Other Properties 9.2.2.2 Stability in Aqueous Solution 9.3 Niacin in Foods 9.3.1 Occurrence 9.3.2 Stability 9.3.3 Applicability of Analytical Techniques 9.4 Intestinal Absorption 9.5 Bioavailability 9.5.1 Niacin 9.5.2 Tryptophan References © 2006 by Taylor & Francis Group, LLC 156 157 159 160 160 165 165 165 167 167 167 168 168 169 171 171 171 172 173 173 177 178 178 179 179 179 179 179 181 182 183 183 183 187 187 Chapter 10 Vitamin B6 10.1 Background 10.2 Chemical Structure, Biopotency, and Physicochemical Properties 10.2.1 Structure and Potency 10.2.2 Physicochemical Properties 10.2.2.1 Appearance and Solubility 10.2.2.2 Stability in Aqueous Solution 10.3 Vitamin B6 in Foods 10.3.1 Occurrence 10.3.2 Stability 10.3.3 Applicability of Analytical Techniques 10.4 Intestinal Absorption 10.5 Bioavailability 10.5.1 Bioavailability of Vitamin B6 in Foods 10.5.2 Effects of Alcohol 10.5.3 Effects of Dietary Fiber 10.5.4 Glycosylated Forms of Vitamin B6 References Chapter 11 Pantothenic Acid 11.1 Background 11.2 Chemical Structure, Biopotency, and Physicochemical Properties 11.2.1 Structure and Potency 11.2.2 Physicochemical Properties 11.2.2.1 Appearance and Solubility 11.2.2.2 Stability in Aqueous Solution 11.3 Pantothenic Acid in Foods 11.3.1 Occurrence 11.3.2 Stability 11.3.3 Applicability of Analytical Techniques 11.4 Intestinal Absorption 11.4.1 Digestion and Absorption of Dietary Pantothenic Acid 11.4.2 Absorption of Bacterially Synthesized Pantothenic Acid in the Large Intestine 11.5 Bioavailability References 189 190 190 191 191 192 193 193 194 197 198 199 199 201 201 202 205 211 211 211 212 212 213 213 213 213 216 216 216 217 217 218 Chapter 12 Biotin 12.1 Background 221 12.2 Chemical Structure, Biopotency, and Physicochemical Properties 221 © 2006 by Taylor & Francis Group, LLC 12.2.1 12.2.2 Structure and Potency Physicochemical Properties 12.2.2.1 Appearance and Solubility 12.2.2.2 Stability in Aqueous Solution 12.3 Biotin in Foods 12.3.1 Occurrence 12.3.2 Stability 12.3.3 Applicability of Analytical Techniques 12.4 Intestinal Absorption 12.4.1 Digestion and Absorption of Dietary Biotin 12.4.2 Absorption of Bacterially Synthesized Biotin in the Large Intestine 12.5 Bioavailability References Chapter 13 Folate 13.1 Background 13.2 Chemical Structure, Biopotency, and Physicochemical Properties 13.2.1 Structure and Potency 13.2.2 Physicochemical Properties 13.2.2.1 Appearance, Solubility, and Ionic Characteristics 13.2.2.2 Stability in Aqueous Solution 13.3 Folate in Foods 13.3.1 Occurrence 13.3.2 Stability 13.3.3 Applicability of Analytical Techniques 13.4 Absorption, Transport, and Metabolism 13.4.1 Deconjugation of Polyglutamyl Folate 13.4.2 Absorption of Dietary Folate 13.4.3 Influence of Folate-Binding Protein on the Absorption of Folate from Milk 13.4.4 Adaptive Regulation of Folate Absorption 13.4.5 Salvage of Dietary 5-Methyl-5,6-DHF 13.4.6 Absorption of Bacterially Synthesized Folate in the Large Intestine 13.4.7 Plasma Transport and Intracellular Metabolism 13.4.8 Folate Homeostasis 13.5 Bioavailability 13.5.1 Introduction 13.5.2 Methods for Assessing Folate Bioavailability 13.5.2.1 Plasma Response © 2006 by Taylor & Francis Group, LLC 221 222 222 223 223 223 223 225 226 226 227 228 229 231 232 232 233 233 234 236 236 238 244 245 245 246 247 249 249 250 251 251 252 252 252 252 13.5.2.2 Stable-Isotopic Methods 13.5.2.3 Use of Ileostomy Subjects 13.5.3 Inherent Bioavailability of Monoglutamyl and Polyglutamyl Folates 13.5.4 Bioavailability of Naturally Occurring Folate in Fruits and Vegetables 13.5.5 Bioavailability of Folate in Milk 13.5.6 Effects of Soluble Food Components on Folate Bioavailability 13.5.7 Effects of Dietary Fiber on Folate Bioavailability 13.5.8 Bioavailability of Folate in Fortified Foods 13.5.9 Effects of Alcohol on Folate Status References Chapter 14 Vitamin B12 (Cobalamins) 14.1 Background 14.2 Chemical Structure, Biopotency, and Physicochemical Properties 14.2.1 Structure and Potency 14.2.2 Physicochemical Properties 14.2.2.1 Appearance and Solubility 14.2.2.2 Stability in Aqueous Solution 14.3 Vitamin B12 in Foods 14.3.1 Occurrence 14.3.2 Stability 14.3.3 Applicability of Analytical Techniques 14.4 Absorption and Conservation 14.4.1 Digestion and Absorption of Dietary Vitamin B12 14.4.2 Conservation of Vitamin B12 14.5 Bioavailability 14.5.1 Efficiency of Absorption 14.5.2 Bioavailability Studies 14.5.2.1 Effects of Dietary Fiber 14.5.2.2 Effects of Alcohol 14.5.2.3 Effects of Smoking References 253 255 256 257 258 260 262 263 264 264 275 276 276 277 277 278 278 278 279 281 281 282 283 283 283 284 284 284 285 285 Chapter 15 Vitamin C 15.1 Background 289 15.2 Chemical Structure, Biopotency, and Physicochemical Properties 290 15.2.1 Structure and Potency 290 © 2006 by Taylor & Francis Group, LLC 15.2.2 Physicochemical Properties 15.2.2.1 Solubility and Other Properties 15.2.2.2 Stability in Aqueous Solution 15.3 Vitamin C in Foods 15.3.1 Occurrence 15.3.2 Stability 15.3.3 Applicability of Analytical Techniques 15.4 Intestinal Absorption 15.4.1 General Principles 15.4.2 Transport Mechanisms 15.4.2.1 Ascorbic Acid 15.4.2.2 Dehydroascorbic Acid 15.4.3 Efficiency of Ascorbate Absorption in Humans 15.5 Bioavailability 15.5.1 Bioavailability of Vitamin C in Foods 15.5.2 Effects of Dietary Fiber 15.5.3 Effects of Alcohol References Part II 291 291 292 292 292 294 299 300 300 301 301 302 302 303 303 304 305 305 Analysis of Vitamins Chapter 16 Analytical Considerations 16.1 Bioassays 16.2 In Vitro Analytical Techniques 16.3 Analytical Approach 16.4 Preparation of Sample Extracts for Analysis 16.4.1 Extraction 16.4.2 Cleanup 16.5 Method Evaluation 16.5.1 Measurement Value and Uncertainty 16.5.2 Quality Assurance 16.5.3 Food Reference Materials 16.5.4 Method Validation References Chapter 17 17.1 17.2 17.3 17.4 Extraction Techniques for the Water-Soluble Vitamins Vitamin B1 Vitamin B2 Niacin Vitamin B6 311 312 312 313 314 314 314 314 316 316 318 320 © 2006 by Taylor & Francis Group, LLC 321 322 323 326 17.5 Pantothenic Acid 17.6 Biotin 17.7 Folate 17.8 Vitamin B12 17.9 Vitamin C References Microbiological Methods for the Determination of the B-Group Vitamins 18.1 Introduction 18.2 General Principles 18.2.1 Turbidimetric Methods 18.2.2 Methods Based on the Measurement of Metabolic Carbon Dioxide 18.3 Conventional Turbidimetric Method Using Test Tubes 18.3.1 Summary 18.3.2 Laboratory Facilities and Cleaning of Glassware 18.3.3 Media 18.3.4 General Assay Procedure 18.3.4.1 Maintenance of Stock Cultures 18.3.4.2 Preparation of the Inoculum Culture 18.3.4.3 Preparation of the Assay (Basal) Medium 18.3.4.4 Extraction of the Vitamin from the Test Material 18.3.4.5 Setting Up the Assay 18.3.4.6 Quantification 18.3.5 Partial Automation of the Assay Procedure 18.4 Turbidimetric Method Using Microtiter Plates 18.5 Assays of Individual B-Group Vitamins 18.5.1 Vitamin B1 18.5.2 Vitamin B2 18.5.3 Niacin 18.5.3.1 Determination of Total Niacin 18.5.3.2 Determination of Bound Nicotinic Acid 18.5.3.3 Determination of Added Nicotinic Acid 18.5.4 Vitamin B6 18.5.5 Pantothenic Acid 18.5.6 Biotin 18.5.7 Folate 18.5.8 Vitamin B12 References 328 328 329 331 332 333 Chapter 18 © 2006 by Taylor & Francis Group, LLC 339 339 339 341 342 342 343 344 344 345 346 347 348 348 349 350 350 351 351 352 354 354 355 356 356 359 360 360 361 363 Chapter 19 19.1 19.2 19.3 19.4 19.5 19.6 19.7 19.8 Physicochemical Analytical Techniques (Excluding HPLC) AOAC Titrimetric Method for Vitamin C Direct Spectrophotometric Determination of Vitamin C Colorimetric Methods for Niacin and Vitamin C 19.3.1 Determination of Niacin by the Ko¨nig Reaction (AOAC Method) 19.3.2 Colorimetric Methods for Vitamin C Fluorometric Methods for Thiamin, Riboflavin, Vitamin B6, and Vitamin C 19.4.1 Thiamin (AOAC Method) 19.4.2 Riboflavin (AOAC Method) 19.4.3 Vitamin B6 19.4.4 Vitamin C (AOAC Method) Enzymatic Methods for Nicotinic Acid and Ascorbic Acid 19.5.1 Nicotinic Acid 19.5.2 Ascorbic Acid Continuous-Flow Analysis 19.6.1 Segmented-Flow Methods 19.6.2 Flow-Injection Analysis 19.6.3 Applications to Food Analysis 19.6.3.1 Fat-Soluble Vitamins 19.6.3.2 Thiamin 19.6.3.3 Riboflavin 19.6.3.4 Thiamin and Riboflavin Simultaneously 19.6.3.5 Niacin 19.6.3.6 Vitamin C Gas Chromatography 19.7.1 Principle 19.7.2 Column Technology 19.7.3 Detectors 19.7.4 Derivatization Techniques 19.7.5 Quantification 19.7.6 Applications to Food Analysis 19.7.6.1 Vitamin E 19.7.6.2 Thiamin 19.7.6.3 Niacin 19.7.6.4 Vitamin B6 19.7.6.5 Pantothenic Acid Supercritical Fluid Chromatography 19.8.1 Principle 19.8.2 Instrumentation © 2006 by Taylor & Francis Group, LLC 369 372 373 373 374 375 375 375 376 377 378 378 379 380 380 380 381 381 381 382 382 382 383 385 385 385 386 386 387 387 387 388 388 388 389 390 390 391 19.8.3 Columns 19.8.4 Applications to Food Analysis 19.9 Capillary Electrophoresis 19.9.1 Principle 19.9.2 Capillary Zone Electrophoresis 19.9.3 Micellar Electrokinetic Capillary Chromatography 19.9.4 Operational Aspects 19.9.5 Applications to Food Analysis 19.9.5.1 Thiamin 19.9.5.2 Riboflavin, FMN, and FAD 19.9.5.3 Niacin 19.9.5.4 Vitamin C References 393 394 394 394 396 396 397 399 399 399 406 408 409 Chapter 20 Determination of the Fat-Soluble Vitamins by HPLC 20.1 Nature of the Sample 20.2 Extraction Procedures 20.2.1 Alkaline Hydrolysis (Saponification) 20.2.1.1 Vitamin A 20.2.1.2 Carotenoids 20.2.1.3 Vitamin D 20.2.1.4 Vitamin E 20.2.2 Alcoholysis 20.2.3 Enzymatic Hydrolysis 20.2.4 Direct Solvent Extraction 20.2.4.1 Vitamin A and Carotene 20.2.4.2 Carotenoids 20.2.4.3 Vitamin D 20.2.4.4 Vitamin E 20.2.4.5 Vitamin K 20.2.5 Matrix Solid-Phase Dispersion 20.2.6 Supercritical Fluid Extraction 20.2.6.1 Principle 20.2.6.2 Instrumentation 20.2.6.3 Applications 20.3 Cleanup Procedures 20.3.1 Precipitation of Sterols 20.3.2 Open-Column Chromatography 20.3.2.1 Magnesia 20.3.2.2 Alumina 20.3.2.3 Silica Gel 20.3.3 Solid-Phase Extraction 20.3.3.1 General Considerations 20.3.3.2 Application in Vitamin D Determinations 419 419 419 421 422 422 423 424 424 425 426 427 427 428 428 429 430 430 430 431 435 436 436 436 436 437 437 437 438 © 2006 by Taylor & Francis Group, LLC 20.4 HPLC Systems 20.4.1 Principle 20.4.2 Explanations of Chromatographic Terms 20.4.2.1 Retention 20.4.2.2 Separation 20.4.2.3 Resolution 20.4.2.4 Efficiency 20.4.3 The Column 20.4.4 Chromatographic Modes 20.4.4.1 Normal-Phase Chromatography 20.4.4.1.1 Adsorption Chromatography 20.4.4.1.2 Polar Bonded-Phase Chromatography 20.4.4.2 Reversed-Phase Chromatography 20.4.4.3 Two-Dimensional HPLC 20.4.5 Detection Systems 20.4.5.1 Introduction 20.4.5.2 Absorbance Detection 20.4.5.3 Fluorescence Detection 20.4.5.4 Electrochemical Detection 20.4.5.5 Mass Spectrometry 20.5 Applications of HPLC 20.5.1 Vitamin A 20.5.1.1 Detection 20.5.1.2 Quantification 20.5.1.3 Normal-Phase Separations 20.5.1.4 Reversed-Phase Separations 20.5.2 Provitamin A Carotenoids 20.5.2.1 Sources of Variation in the Methodology 20.5.2.2 Detection 20.5.2.3 Potential Problems with the Chromatography 20.5.2.4 Normal-Phase Separations 20.5.2.5 Reversed-Phase Separations 20.5.2.5.1 C18-Bonded Phases 20.5.2.5.2 C30-Bonded Phases 20.5.3 Vitamin D 20.5.3.1 Detection 20.5.3.2 Quantification 20.5.3.3 Cleanup Procedures 20.5.3.4 Normal-Phase Separations 20.5.3.5 Reversed-Phase Separations © 2006 by Taylor & Francis Group, LLC 439 439 440 440 440 441 442 442 444 444 444 447 448 452 453 453 454 455 456 457 457 457 457 463 465 466 469 469 469 472 474 475 475 486 489 489 489 499 500 500 20.5.4 Vitamin E 20.5.4.1 Detection 20.5.4.2 Quantification 20.5.4.3 Normal-Phase Separations 20.5.4.4 Reversed-Phase Separations 20.5.5 Vitamin K 20.5.5.1 Detection 20.5.5.2 Normal-Phase Separations 20.5.5.3 Reversed-Phase Separations 20.5.6 Simultaneous Determination of Two or Three Vitamins 20.5.6.1 Normal-Phase Separations 20.5.6.2 Reversed-Phase Separations References Determination of the Water-Soluble Vitamins by HPLC 21.1 HPLC Systems 21.1.1 The Column 21.1.2 Chromatographic Modes 21.1.2.1 Ion Exchange Chromatography 21.1.2.2 Ion Exclusion Chromatography 21.1.2.3 Reversed-Phase Chromatography 21.1.2.4 Reversed-Phase Ion-Pair Chromatography 21.1.3 Derivatization 21.2 Applications of HPLC 21.2.1 Thiamin 21.2.1.1 Detection 21.2.1.2 Methodology 21.2.2 Vitamin B2 21.2.2.1 Detection 21.2.2.2 Methodology 21.2.3 Niacin 21.2.3.1 Detection 21.2.3.2 Methodology 21.2.4 Vitamin B6 21.2.4.1 General Considerations 21.2.4.2 Detection 21.2.4.3 Methodology 21.2.5 Pantothenic Acid 21.2.5.1 Detection 21.2.5.2 Applications 505 506 510 511 526 527 528 540 541 546 549 562 567 Chapter 21 © 2006 by Taylor & Francis Group, LLC 585 585 585 585 587 588 589 591 592 592 592 594 598 598 600 612 612 612 624 624 625 626 638 638 639 21.2.6 Biotin 21.2.6.1 Detection 21.2.6.2 Application 21.2.7 Folate 21.2.7.1 General Considerations 21.2.7.2 Cleanup Procedures 21.2.7.3 Detection 21.2.7.4 Methodology 21.2.8 Vitamin B12 21.2.9 Vitamin C 21.2.9.1 Detection 21.2.9.2 Methodology 21.2.10 Multiple Vitamin Analyses 21.2.10.1 Thiamin and Riboflavin 21.2.10.2 Riboflavin and Pyridoxine 21.2.10.3 Nicotinamide and Pyridoxine 21.2.10.4 Three or More Vitamins References Chapter 22 22.1 22.2 22.3 22.4 Biospecific Methods for Some of the B-Group Vitamins Introduction Immunoassays 22.2.1 The Immunological Reaction 22.2.2 Radioimmunoassay 22.2.2.1 Principle 22.2.2.2 Determination of Pantothenic Acid 22.2.3 Enzyme-Linked Immunosorbent Assay 22.2.3.1 Principle 22.2.3.2 Determination of Pantothenic Acid 22.2.3.3 Determination of Vitamin B6 Protein-Binding Assays 22.3.1 Radiolabeled Protein-Binding Assays 22.3.1.1 Principle 22.3.1.2 Determination of Biotin 22.3.1.3 Determination of Folate 22.3.1.4 Determination of Vitamin B12 22.3.2 Enzyme-Labeled Protein-Binding Assays 22.3.2.1 General Procedure 22.3.2.2 Determination of Biotin 22.3.2.3 Determination of Folate 22.3.2.4 Determination of Vitamin B12 Biomolecular Interaction Analysis 22.4.1 Principle 645 645 646 646 646 648 650 653 676 677 677 682 701 701 715 715 716 720 © 2006 by Taylor & Francis Group, LLC 735 735 735 737 737 737 738 738 740 741 741 741 741 743 743 745 747 747 747 747 748 749 749 22.4.2 Biosensor-Based Immunoassay for Supplemental Biotin and Folate 750 22.4.3 Biosensor-Based Protein-Binding Assay for Supplemental and Endogenous Vitamin B12 751 References 752 Chapter 23 Summarized Appraisal of Analytical Techniques 23.1 Microbiological Assays 23.2 High-Performance Liquid Chromatography 23.2.1 Introduction 23.2.2 Fat-Soluble Vitamins 23.2.2.1 Vitamin A 23.2.2.2 Carotenoids 23.2.2.3 Vitamin D 23.2.2.4 Vitamin E 23.2.2.5 Vitamin K 23.2.3 Water-Soluble Vitamins 23.2.3.1 Thiamin and Flavins 23.2.3.2 Niacin 23.2.3.3 Vitamin B6 23.2.3.4 Pantothenic Acid 23.2.3.5 Biotin 23.2.3.6 Folate 23.2.3.7 Vitamin C 23.3 Supercritical Fluid Chromatography 23.4 Capillary Electrophoresis 23.5 Flow-Injection Analysis 23.6 Biospecific Methods 23.7 Evaluation of Vitamin Bioavailability From Food Analysis Data 23.7.1 Fat-Soluble Vitamins 23.7.2 Water-Soluble Vitamins 23.7.2.1 Thiamin 23.7.2.2 Vitamin B2 23.7.2.3 Niacin 23.7.2.4 Vitamin B6 23.7.2.5 Pantothenic Acid 23.7.2.6 Biotin 23.7.2.7 Folate 23.7.2.8 Vitamin B12 23.7.2.9 Vitamin C References © 2006 by Taylor & Francis Group, LLC 757 758 758 759 759 759 760 760 760 761 761 762 762 763 763 763 763 764 764 765 765 767 767 767 767 768 768 769 769 769 769 770 770 770 ... explanation without intent to infringe Library of Congress Cataloging -in- Publication Data Ball, G.F.M Vitamins in foods : analysis, bioavailability, and stability / by George F.M Ball p cm (Food science... Determination of Pantothenic Acid 22.2.3.3 Determination of Vitamin B6 Protein-Binding Assays 22.3.1 Radiolabeled Protein-Binding Assays... adequate intake of certain vitamins Knowledge about vitamin bioavailability from food is essential for the estimation of dietary requirements Equally important is knowledge of a vitamin s stability