gunstone the lipid handbook 3rd ed

The Lipid
Handbook
with CD-ROM
Third Edition

The Lipid
Handbook
with CD-ROM
Third Edition
Edited by
Frank D. Gunstone
John L. Harwood
Albert J. Dijkstra
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
Boca Raton London New York
CRC Press
Taylor & Francis Group
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© 2007 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
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International Standard Book Number-13: 978-0-8493-9688-5 (Hardcover)
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Library of Congress Cataloging-in-Publication Data
The lipid handbook with CD-ROM / [edited by] Frank D. Gunstone, John L. Harwood, Albert J. Dijkstra. 3rd ed.
p. ; cm.
Includes bibliographical references and index.
ISBN-13: 978-0-8493-9688-5 (alk. paper)
ISBN-10: 0-8493-9688-3 (alk. paper)
1. Lipids Handbooks, manuals, etc. I. Gunstone, F. D. II. Harwood, John L. III. Dijkstra, Albert J.
[DNLM: 1. Lipids. QU 85 L7633 2007]
OP751.L547 2007
572’57 dc22 2006052237
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v
CONTENTS
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii
1 Fatty Acid and Lipid Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
C.M. Scrimgeour and J.L. Harwood

1.1 Fatty acid structure (CMS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Lipid structure (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2 Occurrence and Characterisation of Oils and Fats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
F.D. Gunstone and J.L. Harwood
2.1 Introduction (FDG). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.2 Major oils from plant sources (FDG). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3 Minor oils from plant sources (FDG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.4 Milk fats, animal depot fats and fish oils (FDG). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2.5 Waxes (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .108
2.6 Egg lipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .115
2.7 Milk lipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .117
2.8 Liver and other tissue lipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .119
2.9 Cereal lipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .121
2.10 Leaf lipids (JLH). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .123
2.11 Algal lipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125
2.12 Fungal lipids (JLH). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .128
2.13 Bacterial lipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .134
2.14 Lipids of viruses (JLH). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .141
3 Production and Refining of Oils and Fats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .143
A.J. Dijkstra and J.C. Segers
3.1 Introduction (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .143
3.2 Production of animal oils and fats (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
3.3 Production of vegetable oils and fats (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .155
3.4 Degumming of oils and fats (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .177
3.5 Alkali refining of oils and fats (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .191
3.6 Soapstock and by-product treatments (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .204
3.7 Bleaching of oils and fats (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .212
3.8 Dewaxing of oils (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .231
3.9 Vacuum stripping of oils and fats (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .235
3.10 HACCP for oils and fats supply chains (JCS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .251

4 Modification Processes and Food Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .263
A.J. Dijkstra
4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .263
4.2 Hydrogenation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .264
Contents
vi
4.3 Interesterification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .285
4.4 Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .300
4.5 Food grade emulsifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .315
4.6 Food uses of oils and fats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .333
5 Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .355
M.S.F. Lie Ken Jie, J.L. Harwood and F.D. Gunstone (with W.H. Cheung and C.N.W. Lam)
5.1 Unsaturated fatty acid synthesis via acetylene (MSFLKJ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .355
5.2 Fatty acid synthesis by the Wittig reaction (MSFLKJ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .359
5.3 Isotopically labelled fatty acids (MSFLKJ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .363
5.4 Synthesis of acylglycerols (MSFLKJ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .368
5.5 Fullerene lipids (MSFLKJ). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .375
5.6 Glycerophospholipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .386
5.7 Sphingolipids (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
5.8 Glycosylglycerides (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .406
5.9 Bulk separation procedures (FDG). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .410
6 Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .415
A.J. Dijkstra, W.W. Christie and G.Knothe
6.1 Introduction (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .415
6.2 Requirements stemming from quality control and process investigation (AJD) . . . . . . . . . . . . . . . . . . . .420
6.3 Some selected analytical methods (AJD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .423
6.4 Chromatographic analysis of lipids (WWC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .426
6.5 Nuclear Magnetic Resonance Spectroscopy (GK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .455
7 Physical Properties: Structural and Physical Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .471
I. Foubert, K. Dewettinck, D. Van de Walle, A.J. Dijkstra and P.J. Quinn

7.1 Introduction (IF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .471
7.2 Crystallisation and melting (IF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .472
7.3 Phase behaviour (KD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .491
7.4 Lipid/water interactions (DVdW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .495
7.5 Interaction between lipids and proteins (PJQ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .503
7.6 Biological membranes (PJQ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .509
8 Chemical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .535
G. Knothe, J.A. Kenar and F.D. Gunstone
8.1 Autoxidation and photo-oxidation (GK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .535
8.2 Enzymatic oxidation (GK). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .542
8.3 Epoxidation, hydroxylation and oxidative fission (GK). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .546
8.4 Halogenation and halohydrins (GK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .551
8.5 Oxymercuration (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. .552
8.6 Metathesis (JAK). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .554
8.7 Stereomutation (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .555
8.8 Double-bond migration and cyclisation (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .557
8.9 Cyclisation (GK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .559
8.10 Dimerisation (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .564
8.11 Chain branching and extension (GK). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .566
8.12 Hydrolysis, alcoholysis, esterification and interesterification (GK). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .570
8.13 Acid Chlorides, Anhydrides and Ketene Dimers (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .576
8.14 Peroxy acids and related compounds (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .577
8.15 Nitrogen-containing compounds (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .579
8.16 Other reactions of the carboxyl group (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .583
8.17 Oleochemical carbonates (JAK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .585
8.18 Guerbet compounds (GK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .587
9 Nonfood Uses of Oils and Fats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .591
F.D. Gunstone, J. Alander, S.Z. Erhan, B.K. Sharma, T.A. McKeon and J T. Lin
9.1 Introduction (FDG). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .591

9.2 Basic oleochemicals (FDG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .592
9.3 Surfactants (FDG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .597
9.4 Cosmetics and personal care products (JA). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .604
9.5 Lubricants (SZE and BKS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .610
9.6 Biofuels (FDG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .625
9.7 Surface coatings and inks (FDG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .629
9.8 Castor oil products (TAMcK and J-TL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .632
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10 Lipid Metabolism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .637
J.L. Harwood
10.1 Fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .637
10.2 Glycerophospholipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .668
10.3 Glyceride metabolism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .680
10.4 Glycosylglycerides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .686
10.5 Sphingolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .689
10.6 Lipids as signalling molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .694
10.7 Sterol esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .698
10.8 Control mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .699
11 Medical and Agricultural Aspects of Lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .703
J.L. Harwood, M. Evans, D.P. Ramji, D.J. Murphy and P.F. Dodds
11.1 Human dietary requirements (JLH). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .703
11.2 Lipids and cardiovascular disease (ME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .710
11.3 Clinical aspects of lipids with emphasis on cardiovascular disease and dyslipaemia (DPR) . . . . . . . . . .721
11.4 Skin lipids and medical implications (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .742
11.5 Sphingolipidoses (JLH). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .746
11.6 Other disorders of lipid metabolism (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .749
11.7 Pulmonary surfactant (lung surfactant) (JLH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .751
11.8 Agricultural aspects (DJM, JLH and PFD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .756
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
Dictionary Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Name Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617

ix
PREFACE
The Lipid Handbook was first published in 1984, with a
second edition in 1994. We now present the third edition
of this successful book, with Albert Dijkstra replacing
Fred Padley as a member of the editorial team. The deci-
sion to revise this book was made late in 2004 and most
of the writing was completed during 2005. We planned
the book to take account of the many changes in lipid
science and technology that have occurred in the past 10
years, but we sought to maintain the approach and organ-
isation of material used in the earlier editions. Compared
to the second edition, some chapters have been combined —
“Fatty acid structure” with “Lipid structure” (Chapter 1),
“Separation and isolation” with “Analytical methods”
(Chapter 6), along with the two chapters on “Physical
properties” (Chapter 7). Other chapters have been divided —
The former chapter on “Processing” now appears as sep-
arate chapters devoted to “Production and refining of oils
and fats” (Chapter 3) and to “Modification processes and
food uses” (Chapter 4). One new chapter —“Nonfood
uses” (Chapter 9) has been introduced. All chapters have
been rewritten (often by a new author) and we have sought
to present information on the basis of thinking and prac-
tice in the present day. One interesting change is that the
processing sections refer to patents now easily accessible

through espacenet.com or uspto.gov.
In addition, the Dictionary section has been extended
on the basis of the latest Taylor & Francis Group data-
bases. This contains a wealth of information covering
chemical structures, physical properties, and references to
hundreds of lipid and lipid-related molecules, only some
of which can be detailed in the text. We are grateful to
Taylor & Francis for allowing us to include this informa-
tion and we thank Fiona Macdonald for assistance in
selecting and organising it.
In order to make our task manageable in the time scale
agreed between the publishers and the editors and to
present authoritative coverage of our topics, we have
secured the assistance of several contributors from Europe,
Hong Kong and the United States. Only one contributor
(P. J. Quinn) and two of the editors (F. D. Gunstone and
J. L. Harwood) were involved with the previous edition
and almost the entire text now has different authors. This
brings fresh minds to the volume.
By bringing a wide range of information into a single
volume, we hope that the book will be useful to all who
work in the lipid field as scientists or technologists, in
industrial or academic laboratories, as newcomers, or as
those who already know their way around the field. Lipid
science is of increasing interest for metabolic, nutritional,
and environmental reasons and we offer this revised and
updated volume as a contribution to that growth. For 20
years the book has provided assistance to a generation of
those working with lipids and we offer LH-3 (our acronym
for this work) to the next generation.

The third edition is also available on a CD-ROM
(included with the book). This will provide a compact
form of the so-called “Handbook” and will be easily
searchable, thereby providing easy access to material
hidden in tables and figures and in the extensive list of
references, which now come with full titles.
F. D. Gunstone
J. L. Harwood
A. J. Dijkstra

xi
EDITORS
Frank D. Gunstone, Ph.D., is professor emeritus of the
University of St. Andrews (Scotland) and holds an hon-
orary appointment at the Scottish Crop Research Institute
(Invergowrie, Dundee, Scotland). He received his Ph.D.
from the University of Liverpool (England) in 1946 for
studies with the late Professor T. P. Hilditch, and subse-
quently, there followed an academic career in two Scottish
Universities: Glasgow (1946 to 1954) and St. Andrews
(1954 to 1989). He continues to be professionally active
and has spent over 60 years studying fatty acids and lipids
with many publications to his credit. Since his retirement
in 1989, Dr. Gunstone has written or edited several books.
He has given many invited lectures and has received dis-
tinguished awards in the United States (1973, 1999, 2005,
and 2006), Britain (1962 and 1963), France (1990), Ger-
many (1998), and Malaysia (2004). For many years he has
been the editor of Lipid Technology, an activity that gives
him continued contact with lipid scientists of many differ-

ing interests.
John L. Harwood, Ph.D., is head of the School of Bio-
sciences at Cardiff University (Wales, United Kingdom).
He received his Ph.D. from the University of Birmingham
in 1969, with studies on the metabolism of inositol lipids
with Professor J. N. Hawthorne and, subsequently, learned
about plant fatty acid synthesis at the University of
California with Professor P. K. Stumpf. Following a tenure
at the University of Leeds, he moved to Cardiff where he
was promoted via reader to professor in 1984. He is
currently editor of four journals, including executive editor
of Progress in Lipid Research. Dr. Harwood has published
nearly 500 scientific papers and communications, plus
authoring three books (including Lipid Biochemistry) and
editing 14 others. He has given many plenary and named
lectures, received his D.Sc. in 1979 and is in receipt of
personal prizes. He also has awards for his publications
and those of his students. He is an honorary visiting sci-
entist at the Malaysian Palm Oil Board (Kuala Lumpur),
Centre d’Etudes Nucléaires (Grenoble), and the Hungar-
ian Academy of Sciences (Szeged).
Albert J. Dijkstra, Ph.D., specialised in gas kinetics with
Professor A. F. Trotman-Dickenson at University College
of Wales, Aberystwyth, before defending his Ph.D. thesis
at Leyden University in 1965. He joined ICI, first at the
Petrochemical & Polymer Laboratory in Runcorn,
Cheshire, then at the ICI Holland Rozenburg Works, The
Netherlands, and finally at the ICI Europa headquarters
in Everberg, Belgium. He became involved in edible oils
and fats in 1978 when he joined the Vandemoortele Group

in Izegem, Belgium, as its R&D director. Dr. Dijkstra is
the inventor in a dozen patents and has published numer-
ous articles on edible oil processing. He was the first non-
American to receive the American Oil Chemists’ Society
(AOCS) Chang Award (1997) and the first to receive the
EuroFedLipid Technology Award (2002). Although offi-
cially retired, he continues to be active in the field of edible
oils and fats as author and scientific consultant.

xiii
CONTRIBUTORS
J. Alander
AarhusKarlshamn, Sweden AB
W. W. C hrist i e
The Scottish Crop Research Institute
Invergowrie
Dundee, Scotland
K. Dewettinck
Laboratory of Food Technology and
Engineering
Ghent University
Ghent, Belgium
A. J. Dijkstra
Scientific Consultant
St. Eutrope-de-Born, France
P. F. Dodds
Department of Biology
Imperial College at Wye
Wye, Ashford, U.K.
S. Z. Erhan

USDA, ARS, NCAUR
Peoria, Illinois
USA
M. Evans
Llandough Hospital
Llandough, Cardiff, Wales
I. Foubert
Laboratory of Food Technology and
Engineering
Ghent University
Ghent, Belgium
F. D. Gunstone
The Scottish Crop Research
Institute
Invergowrie
Dundee, Scotland
J. L. Harwood
Cardiff School of Biosciences
Cardiff University
Cardiff, Wales
J. A. Kenar
USDA, ARS, NCAUR
Peoria, Illinois
USA
G. Knothe
USDA, ARS, NCAUR
Peoria, Illinois
USA
M. S. F. Lie Ken Jie
Hong Kong University

Hong Kong, China
Jiann-Tsyh Lin
USDA, ARS, WRRC
Albany, California
USA
T. A. McKeon
USDA, ARS, WRRC
Albany, California
USA
D. J. Murphy
School of Applied Sciences
University of Glamorgan
Pontypridd, Wales
P. J. Quinn
Department of Life Sciences
King’s College
London, UK
D. P. Ramji
School of Biosciences
Cardiff University
Cardiff, Wales
C. M. Scrimgeour
The Scottish Crop Research
Institute
Invergowrie
Dundee, Scotland
J. C. Segers
Jacques Segers Consultancy
Nieuwerkerk aan den IJssel,
The Netherlands

B. K. Sharma
Department of Chemical Engineering
Pennsylvania State University
University Park, Pennsylvania
USA
D. Van De Walle
Laboratory of Food Technology and
Engineering
Ghent University
Ghent, Belgium

1
1
FATTY ACID AND LIPID STRUCTURE
C. M. Scrimgeour and J. L. Harwood
1.1 Fatty acid structure
1.1.1 Introduction and nomenclature
of fatty acids
Fatty acids are aliphatic, usually straight chain, mono-
carboxylic acids. The broadest definition includes all chain
lengths, but most natural fatty acids have even chain
lengths between C
4
and C
22
, with C
18
the most common.
Natural fatty acid structures reflect their common
biosynthesis — the chain is built in two-carbon units and cis

double bonds are inserted at specific positions relative to
the carboxyl carbon. Over 1000 fatty acids are known with
different chain lengths, positions, configurations and types
of unsaturation, and a range of additional substituents
along the aliphatic chain. However, only around 20 fatty
acids occur widely in nature; of these, palmitic, oleic, and
linoleic acids make up ~80% of commodity oils and fats.
Figure 1.1 shows the basic structure of fatty acids and a
number of the functional groups found in fatty acids. A list
of many of the known structures, sources, and trivial names
is available online (Adlof and Gunstone, 2003).
Table 1.1 illustrates the naming of some commonly
encountered fatty acids (additional examples are found in
the following sections). Fatty acids are named systemati-
cally as carboxylic acid derivatives, numbering the chain
from the carboxyl carbon (IUPAC-IUB, 1976). Systematic
names for the series of saturated acids from C
1
to C
32
are
given in Table 1.2. The -anoic ending of the saturated acid
is changed to -enoic, -adienoic, -atrienoic, -atetraenoic,
-apentaenoic, and -ahexaenoic to indicate the presence of
one to six double bonds, respectively. Carbon–carbon
double bond configuration is shown systematically by Z
or E, which is assigned following priority rules for the
substituents. However, the terms cis and trans (abbreviated
c and t) are widely used to describe double bond geometry,
as with only two types of substituents there is no ambi-

guity that requires the systematic Z/E convention (Figure
1.1). However, a recent proposal for systematic naming
for use in lipidomic and bioinformatic databases requires
the use of Z or E (Fahy et al., 2005a, 2005b).
Systematic names for fatty acids are cumbersome in gen-
eral use and both shorthand alternatives and trivial names
are widely used. Trivial names seldom convey any structural
information, often reflecting a common or early source of
the acid. The shorthand names use two numbers separated
by a colon for the chain length and number of double bonds,
respectively. Octadecenoic acid with 18 carbons and 1 dou-
ble bond is, therefore, 18:1. The position of double bonds is
indicated in a number of ways — explicitly, defining the
position and configuration or locating double bonds relative
to the methyl or carboxyl ends of the chain. In the biomed-
ical literature, it is common to number the chain from the
methyl end rather than the systematic numbering from the
carboxyl end, to emphasise the biosynthetic relationship of
different double bond patterns. Numbering from the methyl
end is written n-x or ωx, where x is the double bond carbon
nearest the methyl end. If there is more than one double
bond, a cis configuration, methylene-interrupted pattern is
implied. Although the n-x notation is recommended, both
n-x and ωx are widely used in the current biomedical liter-
ature and wider nutritional contexts. The ∆ notation is used
to make it explicit that the numbering is from the carboxyl
end. Other substituents may also be included in the short-
hand notation; for example 12-OH 18:1 9c for ricinoleic acid
(12-hydroxy-9-cis-octadecenoic acid). The order and style
used for shorthand names varies widely in the literature.

1.1 Fatty acid structure
2
The following sections describe classes of naturally
occurring fatty acids, emphasising acids that are nutrition-
ally and biologically important, are components of com-
modity oils and fats, or are oleochemical precursors. The
structures of many fatty acids are contained in the dictio-
nary section of this book. Up to date information on fatty
acid occurrence in seed oils can be found online (Aitzet-
muller et al., 2003) and this is the source of much of the
data in Section 1.1.2. Further information on fatty acid
structure is available online at idli-
brary.co.uk/ and The struc-
tures of naturally occurring fatty acids are most easily
rationalised by considering their biosynthesis; a few basic
processes build and extend the chain and insert double
bonds, producing the common families of fatty acids.
We do not consider the details of these biochemical
processes here (see Section 10.1), but the reader should
be aware of the result of the various enzyme processes
that build and modify fatty acids. Saturated fatty acids
are built from two carbon units, initially derived from
acetate, added to the carboxyl end of the molecule, usu-
ally until there are 18 carbons in the chain. Double bonds
are introduced by desaturase enzymes at specific posi-
tions relative to the carboxyl group. Elongases further
FIGURE 1.1 Fatty acid structure and some functional groups found in fatty acids.
TABLE 1.1
Structure, systematic, trivial, and shorthand names of some common fatty acids
Structure Systematic Name

Trivial Name/
Abbreviation Shorthand Name
n- or ω
CH
3
(CH
2
)
l0
COOH Dodecanoic lauric 12:0
CH
3
(CH
2
)
12
COOH Tetradecanoic myristic 14:0
CH
3
(CH
2
)
14
COOH Hexadecanoic palmitic 16:0
CH
3
(CH
2
)
5

CH=CH(CH
2
)
7
COOH Z-9-hexadecenoic palmitoleic 16:1 9c 7
CH
3
(CH
2
)
16
COOH Octadecanoic stearic 18:0
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOH Z-9-octadecenoic oleic 18:1 9c 9
CH
3
(CH
2
)
5
CH=CH(CH

2
)
9
COOH Z-11-octadecenoic cis-vaccenic 18:1 11c 7
CH
3
(CH
2
)
5
CH=CH(CH
2
)
9
COOH E-11-octadecenoic vaccenic 18:1 11t 7
CH
3
(CH
2
)
3
(CH
2
CH=CH)
2
(CH
2
)
7
COOH Z,Z- 9,12-octadecadienoic linoleic (LA) 18:2 9c,12c 6

CH
3
(CH
2
CH=CH)
3
(CH
2
)
7
COOH Z,Z,Z- 9,12,15-octadecatrienoic α-linolenic (ALA) 18:3 9c,12c,15c 3
CH
3
(CH
2
)
3
(CH
2
CH=CH)
3
(CH
2
)
4
COOH Z,Z,Z- 6, 9,12-octadecatrienoic γ-linolenic (GLA) 18:3 6c,9c,12c 6
CH
3
(CH
2

)
18
COOH eicosanoic
a
arachidic 20:0
CH
3
(CH
2
)
3
(CH
2
CH=CH)
4
(CH
2
)
3
COOH Z,Z,Z,Z- 5,8,11,14-eicosatetraenoic
a
arachidonic (ARA) 20:4 5c,8c,11c,14c 6
CH
3
(CH
2
CH=CH)
5
(CH
2

)
3
COOH Z,Z,Z,Z,Z- 5,8,11,14,17-
eicosapentaenoic
a
EPA 20:5 5c,8c,11c,14c,17c 3
CH
3
(CH
2
)
20
COOH docosanoic behenic 22:0
CH
3
(CH
2
)
7
CH=CH(CH
2
)
11
COOH Z-13-docosenoic erucic 22:1 13c 9
CH
3
(CH
2
CH=CH)
6

(CH
2
)
2
COOH Z,Z,Z,Z,Z,Z- 4,7,10,13,16,19-
docosahexaenoic
DHA 22:6 4c,7c,
10c,13c,16c,19c
3
CH
3
(CH
2
)
22
COOH tetracosanoic lignoceric 24:0
CH
3
(CH
2
)
7
CH=CH(CH
2
)
13
COOH Z-15-tetracosenoic nervonic 24:1 15c 9
a
Icosa- replaced eicosa- in systematic nomenclature in 1975, but the latter is still widely used in the current literature.
CH

3
(CH
2
)
16
COOH
COOH
Fatty acid with saturated alkyl chain
R′
R
R
R′
Methylene interrupted
double bonds
Conjugated
double bonds
.
Methyl branch
OH
Allene Hydroxyl Acetylene
Epoxide
R′
trans (E)
cis (Z)
H R R R
H H
H
Cyclopropane Cyclopropene
Double bond configuration
or

O
Furan
O
Fatty Acid and Lipid Structure
3
extend the chain in two carbon units from the carboxyl
end. These processes produce most of the fatty acids
of commercial importance in commodity oils and fats,
and which are considered to be of most value in food
and nutrition.
A great diversity of fatty acid structures is produced
by variations on the basic process. The start, particularly,
of the chain elongation process may be derived from
acids other than acetate, resulting in odd or branched
chains. Enzymes closely related to the desaturases may
introduce functional groups other than double bonds,
but usually with similar positional patterns. The result
is a great variety of fatty acid structures, often restricted
to a few related plant genera in which the altered enzymes
have evolved. Additional structural variety is introduced
by subsequent modification of fatty acids, e.g., oxidation
at or near the carboxyl or methyl end. The Euphorbiacae
and Compositae (Asteracae) are particularly adept at
producing many and varied fatty acid structures. Fatty
acids may be modified further, producing other groups
of natural products, such as polyacetylenes, ecosanoids,
and oxylipins. The following sections illustrate these
various structures, but are not exhaustive.
References
Adlof, R.O. and Gunstone, F.D. (2003) Common (non-systematic)

names for fatty acids. />division/analytic/fanames.asp
Aitzetmuller, K.
et al. (2003) A new database for seed oil fatty
acids — the database SOFA, Eur. J. Lipid Sci. Technol.,
105, 92–103. />Fahy, E.
et al. (2005a) A comprehensive classification system for
lipids. J. Lipid Res., 46, 839–861.
Fahy, E.
et al. (2005b) A comprehensive classification system for
lipids. Eur. J. Lipid Sci. Technol., 107, 337–364.
IUPAC-IUB (1976) Nomenclature of Lipids, World Wide Web
version, prepared by G.P. Moss. m.
qmul.ac.uk/iupac/lipid/
1.1.2 Fatty acids
1.1.2.1 Saturated acids
Saturated fatty acids form a homologous series of mono-
carboxylic acids (C
n
H
2n+1
COOH). Table 1.2 lists the
saturated acids from C
1
to C
32
with their systematic and
trivial names and melting points. Naturally occurring
saturated acids are mainly of even chain length between C
4
TABLE 1.2 Systematic, trivial, and shorthand names and melting points of saturated fatty acids

Systematic Name Trivial Name Shorthand Name Melting Point
a
(°C)
methanoic formic 1:0 8.4
ethanoic acetic 2:0 16.6
propanoic propionic 3:0 –20.8
butanoic butyric 4:0 –5.3
pentanoic valeric 5:0 –34.5
hexanoic caproic 6:0 –3.2
heptanoic enanthic 7:0 –7.5
octanoic caprylic 8:0 16.5
nonanoic pelargonic 9:0 12.5
decanoic capric 10:0 31.6
undecanoic 11:0 29.3
dodecanoic lauric 12:0 44.8
tridecanoic 13:0 41.8
tetradecanoic myristic 14:0 54.4
pentadecanoic 15:0 52.5
hexadecanoic palmitic 16:0 62.9
heptadecanoic margaric 17:0 61.3
octadecanoic stearic 18:0 70.1
nonadecanoic 19:0 69.4
eicosanoic arachidic 20:0 76.1
heneicosanoic 21:0 75.2
docosanoic behenic 22:0 80.0
tricosanoic 23:0 79.6
tetracosanoic lignoceric 24:0 84.2
pentacosanoic 25:0 83.5
hexacosanoic cerotic 26:0 87.8
heptacosanoic carboceric 27:0 87.6

octacosanoic montanic 28:0 90.9
nonacosanoic 29:0 90.4
triacontanoic melissic 30:0 93.6
hentriacontanoic 31:0 93.2
dotriacontanoic lacceric 32:0 96.0
a
Data from The Lipid Handbook, 2
nd
Edition (1994), Chapman & Hall, London. With permission.
1.1 Fatty acid structure
4
and C
24
. Fats rich in saturated acids are high melting and
are characteristic of many tropical species. Odd chain acids
are usually minor or trace components of plant and animal
lipids, but some are more abundant in bacterial lipids.
Short chain acids, particularly butyric (4:0), are found
mainly in ruminant milk fats. Medium chain fatty acids
(8:0, 10:0, 12:0, and 14:0) occur together in coconut and
palm kernel oils, both tropical commodity oils. In both of
these oils, lauric acid (12:0) predominates (45 to 55%),
with 14:0 next most abundant. A number of Lauracae and
Myristacae species contain in excess of 80% of 12:0 or
14:0, respectively. Cuphea, a temperate genus, has species
rich in individual medium chain acids, e.g., C. pulcherrima
>90% 8:0, C. koehneana >90% 10:0, and C. calophylla ~85%
12:0. These include some of the highest levels of single
fatty acids in seed oils.
Palmitic acid (16:0) is the most abundant and wide-

spread natural saturated acid, present in plants, animals,
and microorganisms. Levels of 20 to 30% are common in
animal lipids, 10 to 40% in seed oils. Palm oil is a rich
commodity oil source and contains over 40% of palmitic
acid. Stearic acid (18:0) is also ubiquitous, usually at low
levels, but is abundant in cocoa butter (~34%) and some
animal fats, e.g., lard (5 to 24%) and beef tallow (6 to
40%). A few tropical plant species contain 50 to 60+% of
18:0, e.g., Shorea, Garcinia, Allanblackia, and Palaquium.
Arachidic acid (20:0) is 20 to 30% of the seed oils of some
tropical Sapindaceae species, but is usually a minor com-
ponent of plant and animal lipids. Groundnut oil is the
only commodity oil with significant amounts (~1%).
Saturated acids are often most easily obtained by hydro-
genation of more readily available unsaturated acids, e.g.,
docosanoic acid (22:0) could be obtained by hydrogena-
tion of erucic acid (22:1). Chain shortening and chain
extension reactions give access to odd or even chain
lengths not readily found in natural sources. Saturated
acids with 10 or more carbons are solids, and melting
points increase with chain length (see Table 1.2). Melting
points alternate between odd and even chain length, with
odd chain lengths having a lower melting point than the
preceding even chain acid. Polymorphism occurs, where
one or more lower melting, metastable forms exist.
1.1.2.2 Monoenoic acids
Straight-chain, cis-monoenoic acids with an even number
of carbons are common constituents of many lipids and
commodity oils. Trans- monoenes are rare components of
natural oils and fats (see Section 1.2.6). The cis (Z) double

bond is usually inserted by a ∆9-desaturase enzyme into
preformed saturated acids; this may be followed by two-
carbon chain extension at the carboxyl end. Starting with
16:0, this results in n-7 monoenes, while desaturation of
18:0 leads to the n-9 family. Monoenes may also result from
desaturation at the ∆4 or ∆5 positions since oils with
unsaturation at these positions occur in a few plant genera.
The most common monoene is oleic acid (18:1 9c). Oleic
acid (1) is found in most plant and animal lipids and is the
major fatty acid in olive oil (70 to 75%) and several nut oils,
e.g., macadamia, pistachio, pecan, almond, and hazelnut
(filbert) contain 50 to over 70%. High oleic varieties of
sunflower and safflower contain 75 to 80% oleic acid.
Cis-vaccenic acid (18:1 11c, n-7) is common in bacterial
lipids and a minor component of plant and animal lipids,
co-occurring with the more abundant oleic acid. Cis-vaccenic
is relatively abundant in sea buckthorn pulp, which is also
rich in its n-7 biosynthetic precursor 16:1 9c. Petroselinic
acid (18:1 6c) makes up over 50% of seed oil fatty acids of
Umbelliferae species, such as carrot, parsley, and coriander,
and is also found in the Araliaceae, Garryaceae, and Gera-
niaceae species. The biosynthesis of petroselinic acid
involves a ∆4 desaturase acting on palmitic acid (16:0) fol-
lowed by two carbon chain elongation (Cahoon et al., 1994).
Palmitoleic acid (16:1 9c, n-7) is a ubiquitous minor
component in animal lipids; somewhat more abundant in
fish oils. A few plant oils are richer sources, e.g., nuts such
as macadamia (20 to 30%) and the pulp of sea buckthorn
(25 to 40%). C
20

monoenes (11c and 13c) are present in
brassica seed oils and the 9c and 11c isomers are found
in fish oils. 20:1 5c is >60% of meadowfoam (Limnanthes
alba) seed oil fatty acids. Erucic acid (22:1 13c, n-9) is up
to 50% of Cruciferae oils, e.g. rape, mustard, crambe and
over 70% in some Tropaeolum species. Nervonic acid (24:1
15c, n-9) occurs at 15 to 20% in Lunaria annua seed oil,
along with higher levels of erucic acid.
Some monoenes are used as or have potential use as
oleochemicals. Erucic acid, as the amide, is used as an
antislip agent for polythene film. 20:1 5c from meadow-
foam oil can be used to prepare estolide lubricants and
other novel materials. ω-Olefins, such as 10-undecenoic
acid available from pyrolysis of castor oil, are useful
oleochemical intermediates.
Cis-monoenes with 18 or less carbons are liquids at
room temperature or low-melting solids; higher homo-
logues are low-melting solids. Trans-monoenes are
higher melting, closer to the corresponding saturated
acids. Double bond position also influences the melting
point; both cis- and trans-C
18
monoenes are higher melt-
ing when the double bond is at even positions than at
odd positions; a pattern most distinct for double bonds
between C
4
and C
14
. The solid acids may exist as a

number of polymorphs, with different melting points,
resulting from subtly different packing in the crystal
(Table 1.3).
1.1.2.3 Methylene-interrupted polyunsaturated acids
Most unsaturated fatty acids with two or more double
bonds show a characteristic methylene-interrupted pattern
COOH
Oleic acid
(1)
Fatty Acid and Lipid Structure
5
of unsaturation, with one CH
2
between cis double bonds.
This pattern results from the operation of a few specific
desaturases and chain-elongation enzymes. Plants generally
insert double bonds at the ∆9, ∆12, and ∆15 positions
in C
18
fatty acids, giving n-9, n-6, and n-3 compounds,
respectively. Animals can also insert double bonds at the
∆9 position, but not at ∆12 or ∆15; instead, further double
bonds are introduced between the carboxyl group and the
∆9 position by ∆5 and ∆6 desaturase enzymes and the chain
can then be extended in two carbon units at the carboxyl
end of the molecule. The resulting n-6 and n-3 polyenes are
shown in Figure 1.2. The step leading to DHA appears to
be the result of a ∆4 desaturase, but is usually the net result
of two elongations, a ∆6 desaturase and subsequent
two-carbon chain shortening. Leonard et al. (2004) have

reviewed the biosynthesis of long chain polyenes. Along
with a few saturates (mainly 16:0 and 18:0, but also 10:0 to
14:0) and oleic acid, the n-6 and n-3 polyenes make up the
fatty acids found in most plants, animals, and commodity
oils and fats.
Linoleic acid (18:2 n-6, 2) is present in most plant oils
and is abundant (>50%) in corn, sunflower, and soybean
oils, and exceeds 70% in safflower oil. γ-linolenic acid (18:3
n-6, 3) is usually a minor component of animal lipids, but
is relatively abundant in some plant oils, e.g., evening
primrose (~10%), borage (~20%), blackcurrant (~15%),
and echium (~25%). Other n-6 acids, dihomo-γ-linolenic
acid (20:3 n-6) and arachidonic acid (20:4 n-6) are present
in animal tissues, but do not usually accumulate at signif-
icant levels in storage fats. These two C
20
acids are the
precursors of the PG
1
and PG
2
prostaglandin families,
respectively. Some fungi, e.g., Mortierella species produce
up to 50% arachidonic acid in storage lipids and are a
commercial source of this acid (Ratledge, 2004).
α-linolenic acid (18:3 n-3, 4) is ubiquitous in plant leaf
lipids and is present in several commodity seed oils: 8 to
10% in soybean and canola, >50% in linseed oil, and 65
to 75% of perilla oil. The seed oils of many Labiatae
species are >50% α-linolenic acid. In plant leaves, chloro-

plast lipids contain up to 50% α-linolenic acid accompa-
nied, in some species, by its C
16
homologue, 16:3 7c, 10c,13c
(Mongrand et al., 1998). Stearidonic acid (18:4 n-3, 5) is a
minor component of animal lipids and fish oils and is
found in some seed oils, e.g., blackcurrant (up to 5%) and
echium (~7%). The n-3 long-chain, polyunsaturated fatty
TABLE 1.3 Trivial names and melting points of some
monoene fatty acids
Fatty Acid Trivial Name Melting Point
a
(°C)
16:1 9c (n-7) palmitoleic 0.5
16:1 9t (n-7) palmitelaidic 32
18:1 9c (n-9) oleic 16.2, (13.3)
18:1 9t (n-9) elaidic 45.5
18:1 6c petroselinic 31, (29)
18:1 11c (n-7) cis-vaccenic 15.5
18:1 11t (n-7) vaccenic 44.1
20:1 5c (n-16) 27
20:1 11c (n-9) gondoic 25
22:1 13c (n-9) erucic 33.5 (–52, –7, 2, 14)
24:1 15c (n-9) nervonic 45, 41
a
Data from The Lipid Handbook, 2
nd
Edition (1994), Chapman
& Hall, London. With permission. Also references in Section
1.1.3. Polymorph melting points in parentheses.

COOH
Linoleic acid
(2)
COOH
γ-linolenic acid
(3)
FIGURE 1.2 Biosynthesis of n-6 and n-3 polyenes (D = desaturase, E = elongase, -2C = two-carbon chain shortening).
n–9 n–6 n–3
18:1 9c
oleic
∆12 D
18:2 9c, 12c
linoleic
∆15 D
18:3 9c, 12c, 15c
α–linolenic
∆6 D ∆6 D
18:3 6c, 9c, 12c
γ-linolenic
18:4 6c, 9c, 12c, 15c
stearidonic
E E
20:3 8c, 11c, 14c 20:4 8c, 11c, 14c, 17c
∆5 D ∆5 D
20:4 5c, 8c, 11c, 14c
arachidonic
20:5 5c, 8c, 11c, 14c, 17c
EPA
E, E, ∆6 D,
–2C

22:6 4c, 7c, 10c, 13c, 16c, 19c
DHA
1.1 Fatty acid structure
6
acids (LC-PUFA) 20:5 (EPA, 6) and 22:6 (DHA, 7) are
important nutritionally and are mainly obtained from oily
fish and fish oils where they are present at levels from 5 to
20%. EPA is the precursor of the PG
3
prostaglandin series.
Attempts are being made to produce EPA and DHA in
plant lipids by the incorporation of appropriate enzymes
because of the desire to have new sources of these impor-
tant acids. Two types of microorganisms, a dinoflagellate
Crypthecodinium cohnii and marine protist Schizochytrium
species, are commercial single-cell oil sources of DHA
(Ratledge, 2004).
While the n-3 and n-6 polyenes are the most widely
occurring and of prime biological and nutritional interest,
a large number of other methylene-interrupted polyenes are
known, produced by the same desaturation and elongation
steps, but starting with fatty acids of different chain length
and initial unsaturation. For example, animals deprived of
linoleic or linolenic acids can use oleic acid as substrate for
the ∆6 desaturase and subsequent steps, resulting in an n-
9 polyene series. The accumulation of 20:3 n-9 (Mead’s
acid) in animals is considered to be a symptom of essential
fatty acid (i.e., linoleic acid) deficiency.
The presence of two or more cis double bonds results
in a large lowering of the melting point compared to sat-

urates of the same chain length and these polyenes are all
liquid at room temperature. Linoleic acid melts at −5°C.
1.1.2.4 Bis- and polymethylene-interrupted acids
Fatty acids with bis- or polymethylene-interrupted double
bonds, or a mixture of methylene and polymethylene
separated unsaturation, occur in some plant species and
marine organisms. Often these have a double bond inserted
at the ∆5 position in addition to one or more double bonds
in more usual positions. Bis-methylene-interrupted acids
with a ∆5c double bond are common in gymnosperms
(conifers), a typical example being pinolenic acid (18:3
5c,9c,12c) (8), occurring at levels of 25 to 30% in a number
of pine and larch species (Wolff et al. 2001). Among
angiosperms, Limnanthes alba (meadowfoam) seed oil
contains the polymethylene-interrupted 22:2 5c,13c (~20%)
and other ∆5 acids. Bis-methylene-interrupted acids with a
∆5t double bond occur in Thalictrum species (see Section
1.2.6).
Sponges and some other marine invertebrates contain
a wide range of fatty acids with 5c,9c double bonds, with
chain lengths (both odd and even) ranging from C
16
to
C
34
, known as demospongic acids. Additional double
bonds are usually n-7 or n-9 and methyl branching may
also be present (Dembitsky et al., 2003).
1.1.2.5 Conjugated acids
Fatty acids with two or more conjugated double bonds

are found in some plants and animals. Ruminant fats
contain small amounts (~1%) of “conjugated linoleic
acid” (CLA), resulting from bio-hydrogenation of
linoleic and α-linolenic acids in the rumen, which gives
mainly the 18:2 9c,11t isomer (rumenic acid, 9). The only
reported long chain, conjugated diene from a plant is 18:2
10t,12t (~10%), which occurs in Chilopsis linearis along
with the more abundant conjugated triene 18:3
9t,11t,13c. Estolides in stillingia oil (Sapium sebiferum)
and Sebastiana species contain 10:2 2t,4c linked to a short
chain allenic hydroxy acid (Spitzer et al., 1997; Figure
1.3). Conjugated dienes (and higher polyenes) are
prepared chemically from methylene-interrupted fatty
acids by alkaline isomerisation. Under controlled
conditions, linoleic acid produces a mixture containing
only the 9c11t and 10t12c CLA isomers (Sæbø, 2001).
These isomers have potential uses in modifying body
composition and as anticancer agents.
Conjugated trienes and tetraenes are found in several
plant species. They are produced biologically from methy-
lene-interrupted polyenes by a conjugase enzyme similar
to ∆12 desaturase, which shifts an existing double bond
into conjugation with a new double bond (Dyer et al.,
2002). Table 1.4 gives the structure, common name, source,
and melting point of the known conjugated trienes and
tetraenes from plants. Conjugated trienes and tetraenes
containing cis double bonds readily isomerise to the all
trans form on heating or on exposure to light. Tung oil,
containing >60% α-eleostearic acid (10), oxidises and
COOH

α-linolenic acid
(4)
COOH
Stearidonic acid
(5)
COOH
EPA
(6)
COOH
DHA
(7)
FIGURE 1.3 Estolide from stilingia oil. R, R’ 16:0, 18:0, 18:1,
18:2, 18:3.
COOH
Pinolenic acid
(8)
COOH
Rumenic acid
(9)
O
O
O
O
.
O
O
R′
O
O
R

Fatty Acid and Lipid Structure
7
polymerises readily and is used as a drying agent in paints
and varnishes. Along with CLA, there has been recent
interest in the biological and nutritional properties of
conjugated polyenes.
1.1.2.6 Trans acids
Monoenes and methylene-interrupted polyenes are pre-
dominantly cis. A few trans monoenes and dienes with
typical double bond positions are known, e.g., 18:1 9t in
Butyrospermum parkii (12.5%) and Dolichos lablab (15%),
co-occurring with 18:1 9c, and 18:2 9t12t, (~15%) in
Chilopsis linearis, associated with conjugated acids.
Thalictrum (and some other Ranunculaceae species) contain
several acids with a ∆5t bond, 16:1 5t (~2%), 18:1 5t (~20%),
18:2 5t,9c (~6%), and 18:3 5t,9c,12c (~45%). A similar
pattern with ∆3t unsaturation is seen in some Aster species.
16:1 3t occurs widely in leaves associated with chloroplast
lipids. Vaccenic acid, 18:1 11t, is the most abundant trans
monoene in ruminant lipids, which contain a complex
mixture of both cis and trans positional isomers resulting
from biohydrogenation of linoleic and linolenic acids.
Conjugated acids usually contain one or more trans double
bonds (see Section 1.2.5).
Trans isomers, mainly monoenes, are produced during
catalytic partial hydrogenation, and can be present in sub-
stantial amounts in hardened fats, generally as a mixture
of positional isomers. Heat treatment during deodorisa-
tion of commodity oils may result in low levels of trans
isomers, particularly of polyenes. The undesirable nutri-

tional properties of trans acids have led to alternative ways
of producing hardened fats, such as interesterification or
blending with fully saturated fats, and to the use of milder
deodorisation procedures.
1.1.2.7 Acetylenic and allenic acids
Fatty acids with acetylenic and allenic unsaturation are
rare. The two types of unsaturation are isomeric and can be
interconverted. In the allenic function, the double bonds
are rigidly held at right angles and introduce a twist in
the molecule, resulting in optical activity when they are
asymmetrically substituted.
The estolide oil in stillingia oil contains the allenic
hydroxy acid 8-hydroxy-5,6-octadienoic acid (Spitzer
et al., 1997; Figure 1.3). The (R,E) form of 2,4,5-tetrade-
catrienoic acid is an insect sex pheromone. Fatty acids
with a 5,6 allene are found in the seed oils of a few
Labiatae species: laballenic acid (18:2 5,6; 11) is up to
25% of Phlomis tuberosa and some Leucas species;
lamenallenic acid (18:3 5,6,16t) is up to 10% in Lamium
purpureum.
Fatty acids containing an acetylenic group are tariric
acid (18:1 6a, 12), up to 85% of some Picramnia species
and crepenynic acid (18:2 9c,12a, 13) 50 to 75% of some
COOH
α-eleostearic acid
(10)
COOH
.
Laballenic acid
(11)

TABLE 1.4 Common name, source, and melting point of some conjugated fatty acids
Fatty Acid
Common
Name Source Melting Point
a
(°C)
10:2 2t,4c Sapium sebiferum (stillingia oil) (~5 to 10%)
18:2 8t,10t CLA 56
18:2 9t,11t CLA 54
18:2 9c,11c CLA 43
18:2 9c,11t CLA ruminant fats 20
18:2 10t,12t CLA Chilopsis linearis (~10%) 56
18:2 10t,12c CLA 23
18:2 10c,12c CLA 39
18:3 8t,10t,12t β-calendic Calendula officinalis (tr) 78
18:3 8t,10t,12c calendic Calendula officinalis (60%) 40
18:3 8c,10t,12c jacaric Jacaranda mimosifolia (36%) 44
18:3 9t,11t,13t β-eleostearic Aleurites fordii (11%) 72
18:3 9c,11t,13t
b
α-eleostearic Aleurites fordii (Tung oil), Parinarium spp., Momordica sp. (>60%) 49
18:3 9t,11t,13c catalpic Catalpa spp. (~40%) 32
18:3 9c,11c,13t –– 62
18:3 9c,11t,13c punicic Punica granatum (~70%), Momordica balsamina (~60%) 45
18:4 9c,11t,13t,15c
c
α-parinaric Parinarium laurinum (>50%), Impatiens spp. (>20%) 86
18:4 9t,11t,13t,15t β-parinaric – 96
a
Data from The Lipid Handbook, 2

nd
Edition (1994), Chapman & Hall, London. With permission.
b
Occurs also as the 18-hydroxy (kamlolenic acid, Mallotus philippinensis (70%)) and 4-oxo (licanic acid, Licania rigida (80%))
derivatives.
c
Occurs also as the 4-oxo derivative (Chrysobalanus icaco (18%)).
1.1 Fatty acid structure
8
Crepis species. In C. alpina, the acetylenic bond is intro-
duced by a ∆12-desaturase-like enzyme (Lee et al., 1998).
Crepenynic acid is the starting point for the biosynthesis
of a large number of fatty acid-derived acetylenic and
polyacetylenic secondary natural products (e.g., matri-
caria ester). Stearolic acid (18:1 9a), the acetylenic
analogue of oleic acid (from which it is easily prepared),
is not often found in nature, other than as a minor com-
ponent. However, it is more abundant in some Pyrularia
species, P. edulis containing over 50%.
1.1.2.8 Branched chain acids
Straight chain fatty acids are the norm, but a wide variety
of branched chain structures are known, mainly from
bacterial and some animal sources. These acids are usually
saturated or monoenes and the alkyl branch is a methyl
group. Acids with a methyl group on the n-2 or n-3 carbon
(iso and anteiso, respectively; Figure 1.4) are common in
bacteria; their occurrence and distribution being strong
taxonomic indicators. The biosynthesis of these acids
involves the normal two-carbon chain extension, but
instead of starting with a two-carbon acetate-derived

unit, they start with 2-methyl propionic acid (from valine)
or 2-methyl butanoic acid (from leucine), respectively. The
resulting iso and anteiso acids, thus, have an even and odd
total number of carbons, but α-oxidation may subsequently
shorten the chain resulting in both odd and even carbon iso
and anteiso acids. The shorthand nomenclature for these
acids can be confusing, as the total number of carbons is
shown, while the systematic name uses the number of
carbons in the longest alkyl chain. For example, 15-methyl
hexadecanoic acid is iso-17:0.
Iso and anteiso acids found in animal fats, particularly
ruminant fats, are mostly derived from bacteria in the diet
or digestive system. However, some specific acids are of
animal origin: 18-methyleicosanoic acid is the major
thioester-bound fatty acid on the surface of wool and
mammalian hair fibres, producing a continuous hydro-
phobic layer (Jones and Rivett, 1997). Iso and anteiso acids
are rarely found in plant oils, apart from 14-methylhexa-
decanoic acid, which is found as a taxonomically useful
minor component (~1%) in the Pinacae family. These acids
are, however, abundant in the surface waxes of plant
leaves.
Fatty acids with a mid-chain methyl branch are charac-
teristic of some bacteria. For example, 10-R-methyloctade-
canoic acid (tuberculostearic acid) (14) is the major normal
chain length fatty acid in Mycobacterium tuberculosis, the
causative agent of tuberculosis, and is found in a number
of other actinomycetes. The biosynthesis involves methy-
lation of oleic acid, the methyl carbon being derived from
the C-1 pool. C

16
to C
24
mid-chain methyl branched acids
are also found in Mycobacterium species.
Polymethyl fatty acids include those of isoprenoid ori-
gin, derived from partial metabolism of the phytyl chain
from dietary chlorophyll. Phytanic (15) and pristanic acids
(16) are the most common examples and are minor
components of fish oils. A different pattern is seen in fatty
acids from bird uropygial glands where the methyl groups
are found on alternate, usually even, carbons, with two to
four methyl groups present, e.g., (17) found in the preen
gland wax of the graylag goose. Dimycocerosate esters,
found in mycobacteria, contain a range of polyketide-
derived polymethyl fatty acids. These also have the methyls
on alternate even carbons (Onwueme et al., 2005).
1.1.2.9 Cyclic fatty acids
Cyclic fatty acids, with a carbon ring along or at the end of
the alkyl chain, occur naturally in some bacteria and plants.
In addition, a variety of carbocyclic structures are formed
from methylene-interrupted polyenes during heating, for
example, during deep frying. The sources, synthesis, and
biological properties of cyclic fatty acids have been
reviewed by Sebedio and Grandgirard (1989).
Fatty acids with a mid-chain cyclopropane group are
found mainly in bacteria, with cis-9,10-methylenehexade-
canoic (9,10 cpa 17:0); cis-9,10-methyleneoctadecanoic acid
(9,10 cpa 19:0; dihydrosterculic acid); and cis-10,11-meth-
yleneoctadecanoic acid (10,11 cpa 19:0; lactobacillic acid,

18) most common. They are found in diverse bacterial spe-
cies, both aerobic and anaerobic, and in both Gram-negative
FIGURE 1.4 Iso and anteiso branched-chain structures.
COOH
Tariric acid
(12)
COOH
Crepenynic acid
(13)
iso
anteiso
COOH
CH
3
H
Tuberculostearic acid
(14)
COOH
Phytanic acid
(15)
COOH
Pristanic acid
(16)
COOH
(17)
Fatty Acid and Lipid Structure
9
and Gram-positive species. Depending on culture condi-
tions, they may be up to 35% of the membrane lipids.
Biosynthesis of the cyclopropane ring involves addition of

a methylene group, derived from S-adenosylmethione (the
“C
1
pool”), to an existing double bond, for example, lacto-
bacillic acid is derived from cis-vaccenic acid, the most abun-
dant monoene in many bacteria. The cyclopropane acids that
have been found in protozoa, slime moulds, and invertebrates
are most likely derived from bacteria in their diet. The dis-
tribution and biosynthesis of cyclopropane acids in bacteria
has been reviewed by Grogan and Cronan (1997).
Cyclopropane acids are often found at low levels (~1%)
in plant oils containing cyclopropene acids (see below).
Litchi chinensis, however, contains ~40% dihydrosterculic
acid (9,10 cpa 19:0) along with small amounts of shorter
chain homologues.
Cyclopropene acids are found in plant oils of the Malva-
laceae, Sterculiaceae, Bombacaea, Tiliaceae, and
Sapicidacaea families. These are mainly sterculic acid (9,10-
methyleneoctadec-9-enoic acid; 9,10 cpe 19:1; 19) and mal-
valic acid (8,9-methyleneheptadec-8-enoic acid; 8,9 cpe 18:0;
20). Sterculic acid is usually the more abundant (>50% in
Sterculia foetida oil) accompanied by smaller amounts of
malvalic acid. 2-hydroxysterculic acid may also occur in these
oils, probably an intermediate in the biosynthesis of malvalic
acid by α-oxidation of sterculic acid. 9,10-methyleneoctadec-
9-en-17-ynoate (sterculynic acid) occurs in Sterculia alata
(~8%). The biosynthesis of the cyclopropene ring is not fully
understood, but is thought to proceed from oleic acid to the
cyclopropane, produced by the same mechanism as in bac-
teria, followed by further desaturation. Long chain cyclopro-

pane and cyclopropylidene fatty acids have been found in
sponges, for example, (21) from the Amphimedon species
(Nemoto et al., 1997). Their biosynthesis is unknown.
Fatty acids with terminal rings are thought to be produced
by incorporating a cyclic acid rather than acetate at the start
of the chain, although the biosynthetic origin of the cyclic
acid has not always been unequivocally established. Up to
80% of the seed oils of Hydnocarpus species and other genera
of the Flacourtiaceae are terminal cyclopentenyl acids of
various chain lengths. The most abundant is usually the C
16
hydnocarpic acid (22), but in Oncoba and Caloncoba species
the C
18
chaulmoogric acid (23) predominates (~70%). Gorlic
acid (24), C
18
with a ∆6 double bond, is usually 10 to 20%
of these oils. Related homologues from C
6
to C
20
are often
found at low levels. Arum maculatum seed oil contains ~20%
of 13-phenyltridecanoic acid (25)
Bacteria isolated from the extreme environment of hot
springs produce fatty acids with a terminal cyclohexyl
group. In strains of the acidophilic and thermophilic
Bacillus acidocardarius, 11-cyclohexylundecanoic acid
and 13-cyclohexyltridecanoic acid (26) account for 70 to

over 90% of the fatty acids in the bacteria (Oshima and
Ariga, 1975). One of the most unusual fatty acid struc-
tures reported to date is a terminal concatenated cyclo-
butane or ladderane, containing up to five cis-fused four
membered rings (e.g. 27). These occur as glycerol and
methyl esters in the unusually dense membranes of anam-
mox bacteria (Damste et al., 2002).
1.1.2.10 Fatty acids with oxygen-containing
functional groups
Most fatty acids contain only double bonds, but a number
of fatty acids and their metabolites have oxygen-containing
functional groups, most commonly a hydroxyl or epoxide.
COOH
Lactobacillic acid
(18)
COOH
Sterculic acid
(19)
COOH
Malvalic acid
(20)
COOH
(21)
COOH
Hydnocarpic acid
(22)
COOH
Chaulmoorgic acid
(23)
COOH

Gorlic acid
(24)

COOH
13-phenyltridecanoic acid
(25)
COOH
13-cyclohexyltridecanoic acid
(26)
COOH
(27)
1.1 Fatty acid structure
10
Some of these are introduced by enzyme-mediated oxidation
of methylene-interrupted fatty acids, e.g., by lipoxygenase
or the initial stages of fatty acid catabolism, the latter giving
hydroxyl groups near the carboxyl or methyl end of the
chain. Autoxidation, occurring in the absence of enzymes
also gives oxygen-containing products (hydroxy, keto,
epoxy, etc.) with less positional specificity.
In a few plant oils, hydroxy and epoxy groups are intro-
duced in mid-chain positions by enzymes with the same
positional specificity as desaturases. Castor oil, rich in
ricinoleic acid (12-OH 18:1 9c), is the only commodity oil
containing a fatty acid with a functional group other than
double bonds. Oils containing vernolic acid (an epoxy
acid) have been investigated as oleochemical precursors.
Ricinoleic acid (R-12-hydroxy-9-cis-octadecenoic acid;
12-OH 18:1 9c; 28) is 80 to 90% of castor oil (from Ricinus
communis). It occurs at similar levels in Hiptage species

and is found in a number of other species. In Azima
tetracantha, Argyreia cuneata, and Anogeissus latifolia, it
occurs at levels of 10 to 25% along with lower amounts
of the cyclopropene, which contain malvalic and sterculic
acids (see Section 1.2.9). The sclerotia of the ergot fungus
(Claviceps purpurea) contain up to 50% ricinoleic acid
(see below). Isoricinoleic acid (R-9-hydroxy-12-cis-octade-
cenoic acid; 9-OH 18:1 12c) is over 70% of the Wrightia
species. Lesquerolic acid (R-14-hydroxy-11-cis-eicosenoic
acid; 29), the C
20
homologue of ricinoleic acid, occurs in
Lesquerella species (50 to 70%). It is produced from rici-
noleic acid by an elongase specific for hydroxy acids
(Moon et al., 2001). Related acids found in Lesquerella
species include densipolic acid (12-OH 18:2 9c, 15c) and
auricolic acid (14-OH 20:2 11c, 17c). Hydroxy (and keto)
acids are also found with conjugated double bonds (see
Table 1.4). These include kamlolenic acid (18-OH 18:3 9c,
11t, 13t) in Mallotus philippinensis (70%) and coriolic acid
(13-OH 18:2 9t,11c) in Coriaria species (~70%).
A hydroxyl group along the acyl chain can be esterified
to other fatty acids, forming an estolide. In castor oil,
ricinoleic acid is present only in simple triacylglycerols,
but in the ergot fungus Claviceps purpurea, ricinoleic acid
is extensively esterified with both nonhydroxy acids and
other molecules of ricinoleic acid in polyestolide groups
(Batrakov and Tolkachev, 1997). Seed oils of Lesquerella
and related species rich in lesquerolic acid contain
estolides (Hayes et al., 1995).

Cutin, a cross-linked polyester constituent of plant
cuticle, contains a number of C
16
and C
18
mono, di, and
trihydroxy fatty acids. The C
16
acids, derived from palmitic
acid contain a terminal hydroxyl group and a mid-chain
hydroxyl between C
7
and C
10
. The predominant C
18
acids,
derived from oleic acid, are 18-hydroxyoleic, 9,10,18-trihy-
droxystearic and 9,10-epoxy-18-hydroxystearic acids. The
primary hydroxyls are mainly ester linked, while the mid-
chain hydroxyls are only partially esterified. Polyhydroxy
acids are not usually found in seed oils; however, 9,10,18-
trihydroxy-12-cis-octadecenoic acid occurs as ~14% of
Chamaepeuce afra oil.
2-hydroxy or α-hydroxy acids occur in sphingolipids,
skin lipids, wool wax, bacterial cell wall lipids, and in a
few seed oils. In some Thymus species 2-hydroxylinolenic
occurs up to ~13%, along with linolenic acid and its C
17
homologue (17:3 8c,11c,14c). The hydroxy acid is proba-

bly an intermediate in the biosynthesis of the C
17
acid (see
also hydroxysterculic acid, Section 1.2.9). Salvia nilotica
oil contains α-hydroxy oleic, linoleic, and linolenic acids
along with traces of C
17
acids.
3-hydroxy or β-hydroxy fatty acids are found in bacte-
rial lipids, both medium to normal chain-length saturates
and in mycolic acids. Mycolic acids are very long chain
compounds, typically C
60
to C
90
, branched at C
2
, with
unsaturation or cyclopropane groups along the long chain
in addition to the 3-hydroxy group.
Vernolic acid (12-epoxy-9-cis-octadecenoic acid, 30) is
the most widespread epoxy acid in plant oils occurring in
a number of Compositae, Malvaceae and Euphorbiaceae
species. It makes up 60 to 80% of Vernonia oils and is over
90% of Bernardia pulchella oil. (+)-vernolic acid with the
12S,13R configuration is the most usual form, but the
other optical isomer (–)-vernolic acid, has been isolated
from some seed oils of the Malvaceae. In Crepis palaestina
and Vernonia galamensis, the epoxide group is introduced
by a ∆12-desaturase-like enzyme (Lee et al., 1998). How-

ever, in Euphorbia lagascae, the epoxygenase is a cyto-
chrome P450 acting on linoleic acid (Cahoon et al., 2002).
Other epoxy acids include coronoric acid (9,10-epoxy-
12-cis-octadecenoic acid), which occurs in a number of
mainly Compositae species and is ~15% of Chrysanthemum
coronarium oil. It is also found in sunflower and other oils
after prolonged storage of the seeds. 9,10-epoxyoctade-
canoic acid is found at low levels in Tragopogon porrifolius
oil, and alchornoic acid (14,15-epoxy-11-cis-eicosanoic
acid), the C
20
homologue of vernolic acid, occurs in Alchornea
cordifolia (~50%).
A number of oxygen-containing fatty acid derivatives are
produced from methylene-interrupted fatty acids following
COOH
OH
Ricinoleic acid
(28)
COOH
OH
Lesquerolic acid
(29)
COOH
O
Vernolic acid
(30)