Starch chemistry and technology (Food Science and Technology International Series)

Work towards production of the third edition of Starch: Chemistry and Technology was begun by Professor Roy L. Whistler and myself, but shortly thereafter Professor Whistler was unable to continue with the project. I was pleased to be able to see this edition through to completion. Many developments have occurred in the world of starch chemistry, genetics, biochemistry, molecular biology and applications since the second edition was published in 1984. This edition, like the previous two editions, covers the isolation processes, properties, functionalities and uses of the most commonly used starches, viz., normal maizecorn, waxy maize, highamylose maize, cassava (tapioca), potato and wheat starch, with emphases on those aspects of production, properties and uses that are unique to each; but not in single chapters. It also covers those starches that are generally available in only limited or potentially limited amounts, viz., rice (including waxy rice, but not all varieties of rice), sorghum, barley (including waxy barley), oat and rye starches. Chapters on the latter three starches are new to this edition. Not included are other starches that may be isolated from plants that are grown in limited areas and may be localized commercial products. These include amaranth, arrowroot, banana, canna, kuzu, millet, mung bean, pea (smooth and wrinkled), quinoa, sago, sweet potato and taro starch, except that some are mentioned in the chapter on starch use in foods and two are mentioned in the fi rst chapter. Where available, many of these starches are available as fl ours, rather than pure starch. There has been an interest in small granule starch that can be obtained from cattail roots, dasheen tubers, and the seeds of amaranth, canary grass, catchfl y, cow cockle, dropwort, pigweed and quinoa. None of these are covered except as noted above. However, properties and uses of small granule wheat starch are covered in the chapter on wheat starch. All chapterssubjects that were also in the previous edition have been updated. Chapters have been added on the biochemistry and molecular biology of starch biosynthesis, structural transitions and related physical properties of starch, and cyclodextrins. There are two chapters on the structural features of starch granules that present not only advances in understanding the organization of starch granules, but also advances in understanding the fi ne structures of amylose and amylopectin, both of which are based on techniques that have been developed since 1984.

STARCH: CHEMISTRY AND TECHNOLOGY Third Edition Food Science and Technology International Series Series Editor Steve L Taylor University of Nebraska – Lincoln, USA Advisory Board Ken Buckle The University of New South Wales, Australia Mary Ellen Camire University of Maine, USA Roger Clemens University of Southern California, USA Hildegarde Heymann University of California – Davis, USA Robert Hutkins University of Nebraska – Lincoln, USA Ron S Jackson Quebec, Canada Huub Lelieveld Bilthoven, The Netherlands Daryl B Lund University of Wisconsin, USA Connie Weaver Purdue University, USA Ron Wrolstad Oregon State University, USA A complete list of books in this series appears at the end of this volume Starch: Chemistry and Technology Third Edition Edited by James BeMiller and Roy Whistler AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK OXFORD • PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE SYDNEY • TOKYO Academic Press is an imprint of Elsevier Academic Press is an imprint of Elsevier 30 Corporate Drive, Suite 400, Burlington, MA 01803, USA 32 Jamestown Road, London NW1 7BY, UK 525 B Street, Suite 1900, San Diego, CA 92101-4495, USA 360 Park Avenue South, New York, NY 10010-1710, USA Second edition 1984 Third edition 2009 Copyright © 1984, 2009 Elsevier Inc Apart from Chapter 19 which is in the public domain All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (44) (0) 1865 843830; fax (44) (0) 1865 853333; email: permissions@elsevier.com Alternatively visit the Science and Technology Books website at www.elsevierdirect.com/rights for further information Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made Library of Congress Cataloging in Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-12-746275-2 For information on all Academic Press publications visit our website at www.elsevierdirect.com Typeset by Macmillan Publishing Solutions (www.macmillansolutions.com) Printed and bound in the United States of America 09 10 11 12 13 10 Contents Preface to the Third Edition xvii List of Contributors xix History and Future of Starch I History 1 Early History 1500–1900 1900–Present II Development of Specialty Starches Waxy Corn Starch High-amylose Corn Starch Chemically Modified Starches Other Naturally Modified Corn Starches III Other Products from Starch Sweeteners Ethanol Polyols Organic Acids Amino Acids IV Future of Starch Two New Starches for Industry Present American Companies V References 10 Economic Growth and Organization of the US Corn Starch Industry 11 I Introduction 11 II Extent and Directions of Market Growth 11 III High-fructose Syrup Consumption 13 IV Fuel Alcohol 15 V Technical Progress 16 VI Plant Location 16 VII Industry Organization 16 VIII Effects of Corn Price Variability 18 IX International Involvement 19 X Future Industry Prospects 20 XI References 20 vi Contents Genetics and Physiology of Starch Development 23 I Introduction 24 II Occurrence 25 General Distribution 25 Cytosolic Starch Formation 25 Starch Formed in Plastids 26 III Cellular Developmental Gradients 26 IV Non-mutant Starch Granule Polysaccharide Composition 28 Polysaccharide Components 28 Species and Cultivar Effects on Granule Composition 30 Developmental Changes in Granule Composition 31 Environmental Effects on Granule Composition 32 V Non-mutant Starch Granule and Plastid Morphology 33 Description 33 Species and Cultivar Effects on Granule Morphology 33 Developmental Changes in Average Starch Granule Size 34 Formation and Enlargement of Non-mutant Granules 34 VI Polysaccharide Biosynthesis 36 Enzymology 36 Compartmentation and Regulation of Starch Synthesis and Degradation in Chloroplasts 37 Compartmentation and Regulation of Starch Synthesis in Amyloplasts 40 VII Mutant Effects 43 Waxy 44 Amylose-extender 50 Sugary 53 Sugary-2 56 Dull 57 Amylose-extender Waxy 58 Amylose-extender Sugary 59 Amylose-extender Sugary-2 60 Amylose-extender Dull 61 10 Dull Sugary 61 11 Dull Sugary-2 62 12 Dull Waxy 62 13 Sugary Waxy 63 14 Sugary-2 Waxy 63 15 Sugary Sugary-2 64 16 Amylose-extender Dull Sugary 64 17 Amylose-extender Dull Sugary-2 65 18 Amylose-extender Dull Waxy 65 19 Amylose-extender Sugary Sugary-2 66 20 Amylose-extender Sugary Waxy 66 21 Amylose-extender Sugary-2 Waxy 67 22 Dull Sugary Sugary-2 67 23 Dull Sugary Waxy 67 24 Dull Sugary-2 Waxy 68 Contents vii 25 Sugary Sugary-2 Waxy 68 26 Amylose-extender Dull Sugary Waxy 68 VIII Conclusions 69 IX References 71 Biochemistry and Molecular Biology of Starch Biosynthesis 83 I Introduction 84 II Starch Synthesis in Plants: Localization 84 Leaf Starch 84 Starch in Storage Tissues 85 III Enzyme-catalyzed Reactions of Starch Synthesis in Plants and Algae and Glycogen Synthesis in Cyanobacteria 85 IV Properties of the Plant 1,4-α-Glucan-Synthesizing Enzymes 87 ADP-glucose Pyrophosphorylase: Kinetic Properties and Quaternary Structure 87 Relationship Between the Small and Large Subunits: Resurrection of ADPGlc PPase Catalysis in the Large Subunit 91 Phylogenetic Analysis of the Large and Small Subunits 95 Crystal Structure of Potato Tuber ADPGlc PPase 95 Supporting Data for the Physiological Importance of Regulation of ADPGlc PPase 104 Differences in Interaction Between 3PGA and Pi in Different ADPGlc PPases 105 Plant ADPGlc PPases can be Activated by Thioredoxin 107 Characterization of ADPGlc PPases from Different Sources 108 Identification of Important Amino Acid Residues Within the ADPGlc PPases 111 10 Starch Synthase 114 11 Branching Enzyme 129 12 Other Enzymes Involved in Starch Synthesis 136 V Abbreviations 138 VI References 139 Structural Features of Starch Granules I 149 I Introduction 149 II Granule Architecture 153 An Overview of Granule Structure 153 Molecular Organization of Crystalline Structures 153 Crystalline Ultrastructural Features of Starch 158 The Supramolecular Organization of Starch Granules 160 III The Granule Surface 167 Starch Granule Surface and Chemistry and Composition 168 Surface-Specific Chemical Analysis 169 IV Granule Surface Imaging 170 Granule Imaging by SEM Methods 170 Principles of AFM 171 Sample Preparation for AFM Imaging of Granular Starch 172 Surface Detail and Inner Granule Structure Revealed by AFM 173 Interpretation of AFM Images with Respect to Granule Structure 175 viii Contents V VI VII VIII IX Discussion of Granule Surface Imaging by Scanning Probe Microscopy (SPM) 177 Future Prospects of SPM of Starch 179 A Hypothesis of Starch Granule Structure: The Blocklets Concept 180 Location and State of Amylose Within Granules 184 Surface Pores and Interior Channels of Starch Granules 186 Conclusions 187 References 188 Structural Features of Starch Granules II 193 I Introduction 193 II General Characteristics of Starch Granules 194 Granule Shapes, Sizes and Distributions 194 Porous Structures of Starch Granules 195 Shapes of Gelatinized Starch Granules 200 III Molecular Compositions of Starch Granules 201 Amylopectin and Amylose 201 Intermediate Material and Phytoglycogen 202 Lipids and Phospholipids 204 Phosphate Monoesters 205 IV Structures of Amylose and Amylopectin 205 Chemical Structure of Amylose 205 Single Helical Structures (V-Complexes) of Amylose 208 Double Helical Structures of Amylose 211 Chemical Structure of Amylopectin 212 Cluster Models of Amylopectin 218 Effects of Growing Temperature and Kernel Maturity on Starch Structures 224 V Locations of Molecular Components in the Granule 225 VI References 227 Enzymes and Their Action on Starch 237 I Introduction 238 II Amylases 238 Action of Endo-Acting α-Amylases 238 Action of Exo-Acting β-Amylases 244 Amylases Producing Specific Maltodextrin Products 246 Action of Isoamylases 247 Archaebacterial Amylases 248 Action of Cyclomaltodextrin Glucanosyltransferase 250 III Relation of Structure with Action of the Enzymes 253 Relation of Structure with Action of Endo-Acting α-Amylases 253 Structure and Action of Soybean β-Amylase 257 Structure and Action of Glucoamylases 257 Specific Amino Acids at the Active-Site Involved in Catalysis and Substrate Binding 261 Structure and Function of Domains in Amylolytic Enzymes 262 IV Mechanisms for the Enzymatic Hydrolysis of the Glycosidic Bond 264 V Action of Amylases on Insoluble Starch Substrates 267 Contents ix VI VII VIII IX Action of α-Amylases on Amylose-V Complexes and Retrograded Amylose 267 Action of Amylases with Native Starch Granules 269 Inhibitors of Amylase Action 272 Action of Phosphorylase and Starch Lyase 276 Plant Phosphorylase 276 Starch Lyase 277 Enzymic Characterization of Starch Molecules 278 Determination of the Nature of the Branch Linkage in Starch 279 Identification and Structure Determination of Slightly Branched Amyloses 280 Formation of β-Amylase Limit Dextrins of Amylopectin and Determination of their Fine Structure 282 References 284 Structural Transitions and Related Physical Properties of Starch 293 I Introduction 293 II Starch Structure, Properties and Physical Methods of Analysis 295 Ordered and Amorphous Structural Domains (See Also Chapters and 6) 296 Physical Properties of Starch in Water 301 III State and Phase Transitions 310 Glass Transitions of Amorphous Structural Domains 311 Annealing and Structural Modifications by Heat–Moisture Treatments 320 Melting Transitions of Crystallites in Granular Starch 323 Gelation and Retrogradation of Starch and its Polymeric Components 332 Phase Transitions and Other Properties of V-Structures 354 IV References 359 Corn and Sorghum Starches: Production 373 I Introduction 374 II Structure, Composition and Quality of Grain 375 Structure 376 Composition 381 Grain Quality 385 III Wet-milling 391 Grain Cleaning 392 Steeping 394 Milling and Fraction Separation 408 Starch Processing 421 Product Drying, Energy Use and Pollution Control 421 Automation 423 IV The Products 423 Starch 423 Sweeteners 423 Ethanol 424 Corn Oil 425 Feed Products 426 .. .STARCH: CHEMISTRY AND TECHNOLOGY Third Edition Food Science and Technology International Series Series Editor Steve L Taylor University... Chapters have been added on the biochemistry and molecular biology of starch biosynthesis, structural transitions and related physical properties of starch, and cyclodextrins There are two chapters... small granules, the fine structures of wheat starch amylose and amylopectin, genetic and chemical modification of wheat starch, and its functionalities and uses, especially in food products The past