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Handbook of 6 Lipid Research
GlycolipidsJ PhosphoglycolipidsJ and Sulfoglycolipids
Handbook of Lipid Research
Editor: Donald J. Hanahan The University of Texas Health Science Center at San Antonio San Antonio, Texas
Volume 1
Volume 2
Volume 3
Volume 4
Volume5
Volume6
Fatty Acids and Glycerides Edited by Arnis Kuksis
The Fat-Soluble Vitamins Edited by Hector F. DeLuca
Sphingolipid Biochemistry Julian N. Kanfer and Sen-itiroh Hakomori
The Physical Chemistry of Lipids: From Alkanes to Phospholipids Donald M. Small
The Phospholipases Moseley Waite
Glycolipids, Phosphoglycolipids, and Suljoglycolipids Edited by Morris Kates
Handbook of 6 Lipid Research
Glycolipids, Phosphoglycolipids, and Sulfoglycolipids Edited by
Morris Kates University of Ottawa Ottawa, Ontario, Canada
Springer Science+Business Media, LLC
Library of Congress Catalog Card Number 88-640002
ISBN 978-1-4899-2518-3 ISBN 978-1-4899-2516-9 (eBook) DOI 10.1007/978-1-4899-2516-9
© 1990 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1990 Softcover reprint of the hardcover 1st edition 1990
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
Contributors
Werner Fischer, Institut fiir Biochemie der Medizinischen Fakultat, U niversitat Erlangen-Niirnberg, D-S520 Erlangen, Federal Republic of Germany
Jill Gigg, Laboratory of Lipid and General Chemistry, National Institute for Medical Research, London NW7 IAA, England
Roy Gigg, Laboratory of Lipid and General Chemistry, National Institute for Medical Research, London NW7 IAA, England
Mayer B. Goren, Division of Molecular and Cellular Biology, Department of Pediatrics, National Jewish Center for Immunology and Respiratory Medicine, Denver, Colorado S0206
Morris Kates, Department of Biochemistry, University of Ottawa, Ottawa, Ontario, Canada KIN 6N5
Robert K. Murray, Departments of Biochemistry and Pathology, University of Toronto, Toronto, Ontario, Canada M5S lAS
Rajagopalan Narasimhan, Departments of Biochemistry and Pathology, University of Toronto, Toronto, Ontario, Canada M5S lAS
Alexander P. Thllocht, Plant Biotechnology Institute, National Research Council of Canada, Saskatoon, Saskatchewan, Canada S7N OW9
tDeceased
v
Preface
The early history and development of the field of glycolipids was concerned mainly with the predominant glycolipids found in higher animal tissues, namely the glycosphingolipids, as has been extensively documented by J. N. Kanfer and S. Hakomori in Volume 3 of this series. The major glycolipids in organisms of the plant kingdom, however, such as bacteria, yeasts and fungi, algae, and higher plants, are glycoglycerolipids, although glycosphingolipids are also present as minor components in these organisms, except for bacteria.
It is of interest that one of the pioneers in glycosphingolipid research, Herbert E. Carter, also pioneered the discovery and structural elucidation of the plant galactosyldiacylglycerols. This class of glycolipids is present in chloroplast membranes and must surely be one of the most ubiquitous and abundant natural substances in the world, thereby deserving the attention of lipid biochemists. It is therefore surprising to learn that in contrast to the glycosphingolipids, which were discovered in the 1870s, glycoglycerolipids were not discovered until the 1950s. Since that time investigations of the structure and distribution of these glycolipids have proceeded at an exponentially increasing rate, and much information is now available for representatives of many genera of bacteria, yeasts, algae, and higher plants. Glycoglycerolipids have also been identified in animal cells, particularly in the brain, testes, and sperm. At the present time, interest in glycoglycerolipids has shifted towards an understanding of their role in membrane structure and function, and such studies are being actively pursued by several research groups.
The present volume will cover the glycoglycerolipids in bacteria (Chapters 1 and 2), plants (Chapter 3), and animals (Chapter 4). Bacteria also contain phosphoglycoglycerolipids that are associated with lipoteichoic acids, which act as a bridge between the cell wall and the plasma membrane. These anionic glycolipids will also be covered in Chapter 2. Another group of anionic glycolipids, the sulfated glycosylglycerolipids and the plant sulfoquinovosyldiacylglycerols will be covered in Chapters 1 and 3, respectively.
Apart from the glycoglycerolipids and glycosphingolipids, there are three other glycolipid classes, usually present as minor components in nonanimal organisms, that deserve attention. These are the plant glycosylsterols, reviewed in Chapter 3; the acylated carbohydrates, reviewed in Chapter 5; and the glycosylated hydroxy fatty acids, covered in Chapter 6.
In contrast to the lack of knowledge concerning the structure-function relationships of sterol glycosides in plant membranes, much effort has been devoted to investigations on the function of one group of acylated carbohy-
vii
viii Preface
drates, the diacyltrehaloses present in Mycobacteria. These acyl trehaloses and their sulfate esters are believed to be responsible for the toxicity of Mycobacteria, and the historical development of knowledge in this an~a is presented in detail in Chapter 5. The glycosylated hydroxy fatty acids, which occur in bacteria and yeasts, are also known to have a specific function: they are excreted into the growth medium where they act as detergents, enhancing the organism's ability to take up and digest lipid material, such as hydrocarbons. This is described in Chapter 6.
Establishment of the structure of these glycolipids, particularly the glycoglycerolipids has depended and still is dependent on chemical synthesis to provide pure material of known structure and stereochemical configuration for comparison with the natural substances. This synthetic material is also useful in investigations of the physical properties and structure-function relationships of the natural glycolipids. Development of procedures for the synthesis of acylated trehaloses and of glycoglycerolipids is reviewed in Chapter 5 and Chapter 7, respectively.
During the preparation of this volume one of our authors, Alexander "Pat" Tulloch, passed away on February 14, 1987, a victim of leukemia. Pat Tulloch W<!:§ ilfl outstanding carbohydrate chemist and one of the pioneers in the study of the glycosylated hydroxy fatty acids, as is clear from his contribution to this book (Chapter 6). Pat Tulloch will be remembered for his definitive investigations on the chemistry, synthesis, and metabolism of hydroxy fatty acids and their glycosylated derivatives. His premature death represents a great loss to the field of glycolipids and to science generally. For these reasons, I dedicate this volume to the memory of Dr. Alexander P. Tulloch.
There are a number of persons to whom I am indebted for their invaluable assisUince in preparing the manuscripts for Chapters 1 and 3: Helene Amyot for typing the manuscripts of Chapters 1 and 3 and the front papers, Eva Szabo for preparation of many of,the figures, Paul Brunon for photography, Clem Kazakoff for the mass spectra, and Raj Capoor for the NMR spectra. The contributors to this volume are grateful to the scientists and publishen who kindly gave permission for citation of published material and for reproduction of published figures.
Morris Kates Ottawa, Canada
Abbreviations
Abbreviations of glycolipid nomenclature (see IUPAC-IUB Lipid Nomenclature, 1978, Chem. Phys. Lipids 21:159) and other abbreviations used in this volume are as follows:
A c DAG GalAAG GalCer GalDAG Gal2DAG Gal3DAG Gal4 DAG GDAG GGro GGroL GlcDAG Gro GSL LacCer ManDAG PAPS SulfoGalAAG SulfoGalCer SulfoGalDAG
Archaeol Caldarchaeol Diacylglycerol Galactosylacylalkylglycerol Galactoceramide Galactosyldiacylglycerol Digalactosyldiacylglycerol Trigalactosyldiacylglycerol Tetragalactosyldiacylglycerol Glycosyldiacylglycerol Glycosylglycerol Glycoglycerolipid Glucosyldiacylglycerol Glycerol Glycosphingolipid Lactosylceramide Mannosyldiacylglycerol 31- Phosphoadenosine-5 1 -phosphosulfate Sulfatoxygalactosylacylalkylglycerol Sulfatoxygalactosylceramide( cerebroside sulfate) Sulfatoxygalactosyldiacylglycerol
Contents
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Chapter 1
Glyco-, Phosphoglyco-, and Sulfoglycoglycerolipids of Bacteria
Morris Kates
1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.1.1. Classification and Nomenclature of Glycoglycerolipids . . . . 1 1.1.2. Historical Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Glycosyldiacylglycerols in Eubacteria ............................ 3 1.2.1. Extraction, Isolation, and Analysis . . . . . . . . . . . . . . . . . . . . . . . 3 1.2.2. Structure Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.2.3. Distribution in Eubacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 1.2.4. Fatty Acid and Alkyl Chain Composition ................ 41
1.3. Glyco-, Sulfoglyco-, and Phosphoglycoglycerolipids of Archaebacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 1.3.1. Extraction, Isolation, and Quantitation
of Archaebacterial Lipids .............................. 47 1.3.2. Characterization of Archaebacterial Lipids . . . . . . . . . . . . . . 55 1.3.3. Structure Determination.............................. 61 1.3.4. Distribution in Archaebacteria . . . . . . . . . . . . . . . . . . . . . . . . . 72
1.4. Metabolism of Bacterial Glycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 1.4.1. Eubacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 1.4.2. Archaebacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
1.5. Physical Properties ........................................... 93 1.5.1. Glycosyldiacylglycerols of Eubacteria . . . . . . . . . . . . . . . . . . . 93 1.5.2. Glycosyl Archaeols or Caldarchaeols of Archaebacteria ... 96
1.6. Membrane Function of Glycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 1.6.1. Eubacteria.......................................... 104 1.6.2. Archaebacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
1. 7. Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
xii Contents
Chapter 2
Bacterial Phosphoglycolipids and Lipoteichoic Acids
Werner Fischer
2.1. History and Nomenclature.................................. 123 2.1.1. Lipoteichoic Acids and Related Compounds ............ 123 2.1.2. Phosphoglycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2. Occurrence and Structure................................... 126 2.2.1. Phosphoglycolipids and Poly(Glycerophosphate)
Lipoteichoic Acids................................... 126 2.2.2. Unusual Lipoteichoic Acid Structures and Related
Macroamphiphiles in Gram-Positive Bacteria........... 138 2.2.3. Taxonomic Note . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142 2.2.4. Phosphoglycolipids in Mycoplasmatales................ 143 2.2.5. Phosphoglycolipids, Lipoteichoic Acid, and
Glycerophosphate-Containing Capsular Polysaccharides in Gram-Negative Bacteria ............. 144
2.2.6. Fatty Acid Composition of Phosphoglycolipids and Lipoteichoic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
2.3. Detection, Isolation, and Purification . . . . . . . . . . . . . . . . . . . . . . . . . 151 2.3.1. Phosphoglycolipids ........... ; . . . . . . . . . . . . . . . . . . . . . . 151 2.3.2. Lipoteichoic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153 2.3.3. Behavior of Isolated Lipoteichoic Acids in Water....... 157
2.4. Structure Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 2.4.1. Phosphoglycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 2.4.2. Lipoteichoic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
2.5. Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190 2.5.1. Phosphoglycolipids.................................. 190 2.5.2. Glycerophosphoglycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . 191 2.5.3. Lipoteichoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
2.6. Metabolic Fate of Lipoteichoic Acids .......................... 201 2. 7. Cellular Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202 2.8. Biological Activities of Lipoteichoic Acids . . . . . . . . . . . . . . . . . . . . . 205
2.8.1. Bacterial Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205 2.8.2. Mammalian Organisms.............................. 211 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Chapter 3
Glycolipids of Higher Plants, Algae, Yeasts, and Fungi
Morris Kates
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 3.1.1. Nomenclature ....................................... 235 3.1.2. Historical Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.2. Lipid Extraction Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238 3.2.1. Higher Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
Contents xiii
3.2.2. Algae, Diatoms, Yeasts, and Fungi . . . . . . . . . . . . . . . . . . . . . 240 3.2.3. Seeds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
3.3. Glycolipid Isolation Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241 3.4. Characterization and Structure Analysis of Glycolipids . . . . . . . . . 242
3.4.1. Thin-Layer Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . 242 3.4.2. Spectral Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242 3.4.3. Analysis of Molecular Constituents . . . . . . . . . . . . . . . . . . . . 245 3.4.4. Molecular Species Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 245 3.4.5. Identification of Deacylated Glycolipids ................ 247 3.4.6. Identification of Carbohydrate Structure
and Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 7 3.4.7. Identification of Nonpolar Moieties of
Glycosylsterols and Glycosylceramides . . . . . . . . . . . . . . . . . 24 7 3.5. Structure Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
3.5.1. Mono- and DigalactosylDAG . . . . . . . . . . . . . . . . . . . . . . . . . . 254 3.5.2. Tri- and TetragalactosylDAG . . . . . . . . . . . . . . . . . . . . . . . . . 257 3.5.3. SulfoquinovosylDAG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258 3.5.4. Mono- and Oligoglycosylsterols . . . . . . . . . . . . . . . . . . . . . . . 258 3.5.5. Ceramide Mono- and Oligohexosides (Cerebrosides) . . . . 259 3.5.6. Phytoglycolipid ...................................... 261
3.6. Distribution of Glycolipids ................................... 261 3.6.1. Higher Plants ....................................... 261 3.6.2. Algae, Diatoms, and Cyanobacteria .................... 270 3.6.3. Yeasts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271 3.6.4. Fungi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
3. 7. Fatty Acid and Molecular Species Composition of Glycosyldiacylglycerols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 4 3.7.1. Fatty Acid Composition .............................. 274 3.7.2. Positional Distribution·of Fatty Acids and
Molecular Species of GlycosylDAGs . . . . . . . . . . . . . . . . . . . 283 3.8. Metabolism of Glycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.8.1. GlycosylDAGs .. .. . .. . .. . .. . .. . .. . .. .. . . .. .. . . .. . . .. . 286 3.8.2. Glycosylsterol and Acylglycosylsterol Biosynthesis . . . . . . . 298 3.8.3. Ceramidehexoside (Cerebroside) Biosynthesis in Fungi .. 300
3.9. Membrane Function of Plant Glycolipids ...................... 302 3.9.1. Structural Role . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302 3.9.2. Functional Role in Activity of Protein Complexes ....... 304 3.9.3. Role in Physiological Phenomena..................... 305
3.10. Summary and Conclusions.................................. 308 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Chapter 4
Glycoglycerolipids of Animal Tissues
Robert K. Murray and Rajagopalan Narasimhan
4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321 4.2. Isolation of Galactoglycerolipids .............................. 324
:riv Contents
4.3. Methods Used for Analysis of Structure...................... 326 4.4. Galactosyldiacylglycerol (GalDAG) ............................ 330 4.5. Sulfatoxygalactosyldiacylglycerol (Sulfo-GalDAG) . . . . . . . . . . . . . . 332 4.6. Digalactosyldiacylglycerol (Gal2DAG) . . . . . . . . . . . . . . . . . . . . . . . . . 334 4.7. Galactosylacylalkylglycerol (GalAAG) . . . . . . . . . . . . . . . . . . . . . . . . . 335
4.7.1. GalAAG of Brain .................................... 335 4.7.2. GalAAG of Testis and Spermatozoa ................... 335
4.8. Sulfatoxygalactosylacylalkylglycerol (Sulfo-GalAAG) . . . . . . . . . . . . 336 4.8.1. Sulfo-GalAAG of Testis and Spermatozoa . . . . . . . . . . . . . . 336 4.8.2. Sulfo-GalAAG of Brain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
4.9. Digalactosylacylalkylglycerol (Gal2AAG) ....................... 349 4.10. Glucoglycerolipids .......................................... 349 4.11. Possible Functions of GGroLs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351 4.12. Summary .................................................. 354
References................................................. 355
Chapter 5
Mycobacterial Fatty Acid Esters of Sugars and Sulfosugars
Mayer B. Goren
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363 5.2. Trehalose Mycolate Esters ........... ~....................... 364
5.2.1. History and Nomenclature........................... 364 5.2.2. History of Trehalose-6,6'-Dimycolate . . . . . . . . . . . . . . . . . . 366 5.2.3. Summary of the Early Structural Studies . . . . . . . . . . . . . . 368 5.2.4. Heterogeneity of Trehalose Dimycolates
and of Mycolic Acids................................ 370 5.2.5. Cord Factor Purification: Current Practices,
Infrared Spectrometry ............................... 374 5.2.6. Determination of Structure: Mass
and NMR Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376 5.2.7. Synthesis of Cord Factors and Cord Factor Analogues . . 377 5.2.8. Pseudo-Cord Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387 5.2.9. Biological Activities . . . .. . .. . . .. . .. . .. . .. . .. .. . . .. . . . . 391
5.2.10. Trehalose Monomycolates ............................ 408 5.3. Miscellaneous Acylated Trehalose Derivatives of Mycobacteria.. 419
5.3.1. Trehalose Phleates ................................... 419 5.3.2. Pyruvylated Glycolipids from
Mycobacterium smegmatis ............................... 420 5.3.3. Serologically Active Trehalose-Containing
Lipooligosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422 5.3.4. Trehalose Esters of Intermediate Molecular Weight . . . . . 423
5.4. Sulfatides of Mycobacterium tuberculosis ......................... 424 5.4.1. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424 5.4.2. Separation and Purification of Sulfatides . . . . . . . . . . . . . . 425 5.4.3. SL Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
Contents
5.4.4. Structural Studies on Sl.rl . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428 5.4.5. Association of Sulfatides with Virulence............... 445 5.4.6. Distribution of Mycobacterial Sulfatides............... 445 5.4. 7. Synthesis, Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446 5.4.8. Biological Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 7
5.5. Epilogue ................................................... 449 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 450
Chapter 6
Glycosides of Hydroxy Fatty Acids
Alexander P. Tulloch
6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463 6.2. Hydroxy Fatty Acid Glycosides from Bacteria................. 463
6.2.1. Characterization of Rhamnolipids from P. aeruginosa . . . . 463 6.2.2. Biosynthesis of Rhamnolipids ......................... 465 6.2.3. Function and Application of Rhamnolipids . . . . . . . . . . . . 465
6.3. Hydroxy Fatty Acid Glycosides from Fungi .................... 466 6.3.1. Characterization of Cellobiosides from Ustilago zeae . . . . . 466 6.3.2. Biosynthesis of Cellobiosides from Ustilago zeae ......... 467 6.3.3. Function and Application of Cellobiosides . . . . . . . . . . . . . 467
6.4. Hydroxy Fatty Acid Glycosides from Yeasts................... 468 6.4.1. Characterization of Sophorolipids
from Torulopsis bombicola . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468 6.4.2. Characterization of Sophorolipids
from Candida bogoriensis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 7 4 6.5. Hydroxy Fatty Acid Glycosides from Plants................... 475
6.5.1. Hydroxy Fatty Acid Glycosides from Convolvulus, Ipomoea, and Pharbitis Species .............. 475
6.5.2. Characterization of Hydroxy Fatty Acid Glycosides from Plants ............................... 476
6.5.3. Function and Application of Hydroxy Fatty Acid Glycosides from Plants . . . . . . . . . . . . . . . . . . . . . . . . . . 4 79
6.6. Determination of Structure of Hydroxy Fatty Acid Glycosides . . 480 6.6.1. Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480 6.6.2. Oxidation ........................................... 482 6.6.3. Methylation ......................... ·. . . . . . . . . . . . . . . . 482 6.6.4. Hydrolysis and Related Reactions . . . . . . . . . . . . . . . . . . . . . 483
6. 7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
Chapter 7
Synthesis of Glycoglycerolipids
Jill Gigg and Roy Gigg
7.1. Introduction............................................... 489 7.2. Monoglycosylglycerolipids................................... 489
xvi Contents
7.2.1. 1,2-trans-Monoglycosyldiacylglycerols .................. 489 7.2.2. Seminolipid ......................................... 492 7.2.3. 1,2-cis-Glycosyldiacylglycerols . . . . . . . . . . . . . . . . . . . . . . . . . 493 7.2.4. Monoglycosyldialkylglycerols . . . . . . . . . . . . . . . . . . . . . . . . . 496
7 .3. Diglycosylglycerolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496 7 .3.1. Diglycosyldiacylglycerols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496 7.3.2. Diglycosyldialkylglycerols ............................. 500
7 .4. Triglycosylglycerolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501 7 .4.1. Triglycosyldiacylglycerols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501 7 .4.2. Triglycosyldi-0-Phytanylglycerol ...................... 502 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Index .............................. : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507