Nutraceutical and Specialty Lipids and their Co-Products doc

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Nutraceutical and
Specialty Lipids
and their Co-Products
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NUTRACEUTICAL SCIENCE AND TECHNOLOGY
Series Editor
FEREIDOON SHAHIDI, PH.D., FACS, FCIC, FCIFST, FIFT, FRSC
University Research Professor
Department of Biochemistry
Memorial University of Newfoundland
St. John's, Newfoundland, Canada
1. Phytosterols as Functional Food Components and Nutraceuticals,
edited by Paresh C. Dutta
2. Bioprocesses and Biotechnology for Functional Foods and Nutraceuticals,
edited by Jean-Richard Neeser and Bruce J. German
3. Asian Functional Foods, John Shi, Chi-Tang Ho, and Fereidoon Shahidi
4. Nutraceutical Proteins and Peptides in Health and Disease,
edited by Yoshinori Mine and Fereidoon Shahidi
5. Nutraceutical and Specialty Lipids and their Co-Products,
edited by Fereidoon Shahidi
DK3305_title 2/8/06 10:07 AM Page 1
A CRC title, part of the Taylor & Francis imprint, a member of the
Taylor & Francis Group, the academic division of T&F Informa plc.
Boca Raton London New York
Nutraceutical and
Specialty Lipids
and their Co-Products
Edited by
Fereidoon Shahidi

Published in 2006 by
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2006 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group
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10987654321
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Library of Congress Cataloging-in-Publication Data
Neutraceutical lipids and co-products / edited by Fereidoon Shahidi
p. cm. (Neutraceutical science and technology ; 5)
Includes bibliographical references and index.

ISBN 1-57444-499-9
1. Functional foods. 2. Food Biotechnology. I. Series.
QP144.F85N84 2006
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Preface
Interest in food lipids has grown dramatically in recent years as a result of findings related to their
health effects. Fats and oils have often been condemned because of their high energy value and due
to potential health problems associated with certain saturated fatty acids as well as trans fats.
However, lipids are important in that they provide essential fatty acids and fat-soluble vitamins as
well as flavor, texture, and mouthfeel to foods. In addition, the beneficial health effects and essen-
tiality of long-chain omega-3 fatty acids such as eicosapentaenoic acid (EPA), and docosahexaenoic
acid (DHA) and that of omega-6 fatty acids such as arachidonic acid (AA) and γ-linolenic acid
(GLA) have been recognized. Recently, the role of EPA and/or DHA in heart health, mental health,
and brain and retina development has been well documented. In this connection, there has been a
surge in the public interest and thus inclusion of these fatty acids into foods such as spreads, bread
and cereal products, orange juice, and dairy products, among others. In addition, novel sources of
edible oils with specific characteristics such as those of fruit seed oils, nut oils, algal oils, and
medium-chain fatty acids as well as diacylglycerols have been explored. The role of minor compo-
nents in fats and oils and their effects on oil stability have been acknowledged. Minor components
such as phospholipids, tocopherols and tocotrienols, carotenoids, and sterols as well as phenolic
compounds may be procured from the oil or the leftover meal and used as nutraceuticals and
functional food ingredients.
It is the purpose of this book to present a comprehensive assessment of the current state of the

chemistry, nutrition, and health aspects of specialty fats and oils and their co-products and to
address stability issues and their potential application and delivery in functional foods and geriatric
and other formulations. This book provides valuable information for senior undergraduate and grad-
uate students as well as scientists in academia, government laboratories, and industry. I am indebted
to the participating authors for their hard work and dedication in providing a state-of-the-art con-
tribution and for their authoritative views resulting from their latest investigations on different
aspects of nutraceutical lipids and co-products.
Fereidoon Shahidi
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Editor
Fereidoon Shahidi, Ph.D., FACS, FCIC, FCIFST, FIFT, FRSC, is a University Research Professor,
the highest academic level, in the Department of Biochemistry, Memorial University of
Newfoundland (MUN), Canada. He is also cross-appointed to the Department of Biology, Ocean
Sciences Centre, and the aquaculture program at MUN. Dr. Shahidi is the author of over 550 sci-
entific papers and book chapters and has authored or edited over 40 books. He has given over 350
presentations at different scientific meetings and conferences. His research has led to a number of
industrial developments around the globe.
Dr. Shahidi’s current research interests include different areas of nutraceuticals and functional
foods and particularly work on specialty and structured lipids, lipid oxidation, food phenolics, and
natural antioxidants, among others. Dr. Shahidi is the editor-in-chief of the Journal of Food Lipids,
an editor of Food Chemistry, and a member on the editorial boards of the Journal of Food Science,
Journal of Agricultural and Food Chemistry, International Journal of Food Properties, Journal of
Food Science and Nutrition, and Current Food Science and Nutrition. He is the editor of the sixth
edition of Bailey’s Industrial Oils and Fats in six volumes. Dr. Shahidi has been the recipient of
numerous awards, the latest of which was the Stephen S. Chang Award from the Institute of Food
Technologists (IFT) in 2005, for his outstanding contributions to food lipids and flavor chemistry,
and was also recognized by IFT as a Fellow in 2005.
Dr. Shahidi is a founding member and a past chair of the Nutraceutical and Functional Food
Division of IFT and a councilor of IFT. He has also served in the past as chairs for the Agricultural

and Food Chemistry Division of the American Chemical Society (ACS) and the Lipid Oxidation
and Quality of the American Oil Chemists’ Society (AOCS). Dr. Shahidi served as a member of
the Expert Advisory Panel of Health Canada on Standards of Evidence for Health Claims for
Foods, the Standards Council of Canada on Fats and Oils, the Advisory Group of Agriculture and
Agri-Food Canada on Plant Products, and the Nutraceutical Network of Canada. He also served
as a member of the Washington-based Council of Agricultural Science and Technology on
Nutraceuticals.
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Contributors
R.O. Adlof
Food and Industrial Oil Research, National
Center for Agricultural
Utilization Research
Peoria, Illinois, USA
Scott Bloomer
Archer Daniels Midland Company
James R. Randall Research Center
Decatur, Illinois, USA
Yaakob B. Che Man
Department of Food Technology, Faculty
of Food Science and Technology
Universiti Putra Malaysia
Serdang, Selangor, Malaysia
Grace Chen
United States Department of Agriculture
Agricultural Research Service
Albany, California, USA
Hang Chen
Department of Food Science

Center for Advanced Food Technology
Rutgers University
New Brunswick, New Jersey, USA
Armand B. Christophe
Department of Internal Medicine
Ghent University Hospital
Ghent, Belgium
Yasushi Endo
Graduate School of Agricultural Science
Tohoku University
Sendai, Japan
Fang Fang
Department of Food Science
Center for Advanced Food Technology
Rutgers University
New Brunswick, New Jersey, USA
Paul Fedec
POS Pilot Plant Corporation
Saskatoon, Saskatchewan, Canada
Jaouad Fichtali
Martek Biosciences Corporation
Winchester, Kentucky, USA
Brent D. Flickinger
Archer Daniels Midland Company
Decatur, Illinois, USA
Kenshiro Fujimoto
Graduate School of Agricultural Science
Tohoku University
Sendai, Japan
Frank D. Gunstone

Scottish Crop Research Institute
Invergowrie, Dundee, Scotland, U.K.
Xiaohua He
United States Department of Agriculture
Agricultural Research Institute
Albany, California, USA
Chi-Tang Ho
Department of Food Science
Center for Advanced Food Technology
Rutgers University
New Brunswick, New Jersey, USA
Masashi Hosokawa
Laboratory of Biofunctional Material
Chemistry
Hokkaido University
Hakodate, Japan
Chung-yi Huang
Department of Food Science and Technology
University of Georgia
Athens, Georgia, USA
Yao-wen Huang
Department of Food Science and Technology
University of Georgia
Athens, Georgia, USA
DK3305_C000_FM.qxd 2/7/2006 6:37 PM Page ix
Charlotte Jacobsen
Department of Seafood Research
Danish Institute for Fisheries Research
Lyngby, Denmark
J.W. King

Food and Industrial Oil Research
National Center for Agricultural
Utilization Research
Peoria, Illinois, USA
Yong Li
Center for Enchancing Food to Protect Health
Lipid Chemistry and Molecular Biology
Laboratory
Purdue University
West Lafayette, Indiana, USA
Jiann-Tsyh Lin
United States Department of Agriculture
Agricultural Research Service
Albany, California, USA
G.R. List
Food and Industrial Oil Research
National Center for Agricultural
Utilization Research
Peoria, Illinois, USA
and
Food Science and Technology Consultants
Germantown, Tennessee, USA
Hu Liu
School of Pharmacy
Memorial University of Newfoundland
St. John’s, Newfoundland, Canada
Marina Abdul Manaf
Department of Food Technology
Faculty of Food Science and Technology
Universiti Putra Malaysia

Serdang, Selangor, Malaysia
Thomas A. McKeon
United States Department of Agriculture
Agricultural Research Service
Albany, California, USA
H. Miraliakbari
Department of Biochemistry
Memorial University of Newfoundland
St. John’s, Newfoundland, Canada
Kazur Miyashita
Laboratory of Biofunctional Material Chemistry
Hokkaido University
Hakodate, Japan
Karlene S.T. Mootoosingh
School of Nutrition
Ryerson University
Toronto, Ontario, Canada
Kumar D. Mukherjee
Institute for Lipid Research
Federal Research Centre for Nutrition and Food
Münster, Germany
Toshihiro Nagao
Osaka Municipal Technical Research Institute
Osaka, Japan
Bhaskar Narayan
Laboratory of Biofunctional Material Chemistry
Hokkaido University
Hakodate, Japan
Nina Skall Nielsen
Department of Seafood Research

Danish Institute for Fisheries Research
Lyngby, Denmark
Frank T. Orthoefer
Food Science and Technology Consultants
Germantown, Tennessee, USA
Andreas M. Papas
YASOO Health, Inc.
Johnson City, Tennessee, USA
Si-Bum Park
Graduate School of Agricultural Science
Tohoku University
Sendai, Japan
J.W. Parry
Department of Nutrition and Food Science
University of Maryland
College Park, Maryland, USA
Roman Przybylski
Department of Chemistry and Biochemistry
University of Lethbridge
Alberta, Canada
x Contributor Contact Sheet
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Robert D. Reichert
Industrial Research Assistance Program
National Research Council of Canada
Ottawa, Ontario, Canada
Robert T. Rosen
Department of Food Science
Center for Advanced Food Technology
Rutgers University

New Brunswick, New Jersey, USA
Dérick Rousseau
School of Nutrition
Ryerson University
Toronto, Ontario, Canada
Karen Schaich
Department of Food Science
Rutgers University
New Brunswick, New Jersey, USA
S.P.J.N. Senanayake
Department of Biochemistry
Memorial University of Newfoundland
St. John’s, Newfoundland, Canada
and
Martek Biosciences Corporation
Winchester, Kentucky, USA
Fereidoon Shahidi
Department of Biochemistry
Memorial University of Newfoundland
St. John’s, Newfoundland, Canada
Yuji Shimada
Osaka Municipal Technical Research Institute
Osaka, Japan
Barry G. Swanson
Food Science and Human Nutrition
Washington State University
Pullman, Washington, USA
Maike Timm-Heinrich
Department of Seafood Research
Danish Institute for Fisheries Research

Lyngby, Denmark
Charlotta Turner
United States Department of Agriculture
Agricultural Research Service
Albany, California, USA
Udaya Wanasundara
POS Pilot Plant Corporation
Saskatoon, Saskatchewan, Canada
Lili Wang
School of Pharmacy
Memorial University of Newfoundland
St. John’s, Newfoundland, Canada
Yomi Watanabe
Osaka Municipal Technical Research Institute
Osaka, Japan
Bruce A. Watkins
Center for Enhancing Food to Protect Health
Lipid Chemistry and Molecular Biology
Laboratory
Purdue University
West Lafayette, Indiana, USA
Nikolaus Weber
Institute for Lipid Research
Federal Research Centre for Nutrition and Food
Münster, Germany
Liangli Yu
Department of Nutrition and Food Science
University of Maryland,
College Park, Maryland, USA
Kequan Zhou

Department of Nutrition and Food Science
University of Maryland
College Park, Maryland, USA
Nutraceutical and Specialty Lipids xi
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Contents
1. Nutraceutical and Specialty Lipids 1
Fereidoon Shahidi and S.P.J.N. Senanayake
2. Medium-Chain Triacylglycerols 27
Yaakob B. Che Man and Marina Abdul Manaf
3. Cereal Grain Oils 57
Roman Przybylski
4. Fruit Seed Oils 73
Liangli Yu, John W. Parry, and Kequan Zhou
5. Minor Specialty Oils 91
Frank D. Gunstone
6. Sphingolipids 127
Fang Fang, Hang Chen, Chi-Tang Ho, and Robert T. Rosen
7. Modification and Purification of Sphingolipids and Gangliosides 137
Scott Bloomer
8. Hydroxy Fatty Acids 153
Thomas A. McKeon, Charlotta Turner,
Xiaohua He, Grace Chen, and Jiann-Tsyh Lin
9. Tree Nut Oils and Byproducts: Compositional Characteristics and
Nutraceutical Applications 159
Fereidoon Shahidi and H. Miraliakbari
10. Gamma-Linolenic Acid (GLA) 169
Yao-wen Huang and Chung-yi Huang
11. Diacylglycerols (DAGs) and their Mode of Action 181

Brent D. Flickinger
12. Conjugated Linoleic Acids (CLAs): Food, Nutrition, and Health 187
Bruce A. Watkins and Yong Li
13. Occurrence of Conjugated Fatty Acids in Aquatic and Terrestrial
Plants and their Physiological Effects 201
Bhaskar Narayan, Masashi Hosokawa, and Kazuo Miyashita
14. Marine Conjugated Polyunsaturated Fatty Acids 219
Yasushi Endo, Si-Bum Park, and Kenshiro Fujimoto
15. Marine Oils: Compositional Characteristics and Health Effects 227
Fereidoon Shahidi and H. Miraliakbari
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16. Single-Cell Oils as Sources of Nutraceutical and Specialty Lipids: Processing
Technologies and Applications 251
S.P.J.N. Senanayake and Jaouad Fichtali
17. Emulsions for the Delivery of Nutraceutical Lipids 281
Karlene S.T. Mootoosingh and Dérick Rousseau
18. Lipid Emulsions for Total Parenteral Nutrition (TPN) Use and
as Carriers for Lipid-Soluble Drugs 301
Hu Liu and Lili Wang
19. Modified Oils 313
Frank D. Gunstone
20. Fat Replacers: Mimetics and Substitutes 329
Barry G. Swanson
21. Application of Functional Lipids in Foods 341
Charlotte Jacobsen, Maike Timm-Heinrich, and Nina Skall Nielsen
22. Application of Multistep Reactions with Lipases to the Oil and Fat Industry 365
Yuji Shimada, Toshihiro Nagao, and Yomi Watanabe
23. Structure-Related Effects on Absorption and Metabolism
of Nutraceutical and Specialty Lipids 387
Armand B. Christophe

24. Lipid Oxidation in Specialty Oils 401
Karen Schaich
25. Trans Fatty Acids in Specialty Lipids 449
G.R. List, R.O. Adlof, and J.W. King
26. Tocopherols and Tocotrienols as Byproducts of Edible Oil Processing 469
Vitamin E: A New Perspective
Andreas M. Papas
27. Plant Sterols and Steryl Esters in Functional Foods and Nutraceuticals 483
Nikolaus Weber and Kumar D. Mukherjee
28. Phospholipids/Lecithin: A Class of Nutraceutical Lipids 509
Frank T. Orthoefer and G.R. List
29. Centrifugal Partition Chromatography (CPC) as a New Tool for
Preparative-Scale Purification of Lipid and Related Compounds 531
Udaya Wanasundara and Paul Fedec
30. Oilseed Medicinals: Applications in Drugs and Functional Foods 543
Robert D. Reichert
Index 557
xiv Contents
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CONTENTS
1.1 Introduction 2
1.2 Chemistry and Composition of Lipids 2
1.2.1 The Fatty Acids 2
1.2.2 Saturated Fatty Acids 2
1.2.3 Unsaturated Fatty Acids 3
1.2.4 Acylglycerols 4
1.2.5 Phospholipids 4
1.2.6 Fat-Soluble Vitamins and Tocopherols 7
1.2.7 Sterols 7
1.2.8 Waxes 7

1.2.9 Biochemistry and Metabolism of Short-Chain Fatty Acids (SCFAs) 8
1.2.10 Biochemistry and Metabolism of MCFAs 8
1.2.11 Biochemistry and Metabolism of Essential Fatty Acids (EFAs) 9
1.2.12 Eicosanoids 10
1.3 Major Sources of Nutraceutical and Specialty Lipids 11
1.3.1 Fish Oils 11
1.3.2 Seal Blubber Oil (SBO) 12
1.3.3 Borage, Evening Primrose, and Blackcurrant Oils 13
1.3.4 Concentration of n-3 Fatty Acids from Marine Oils 15
1.3.5 Application of Lipases in Synthesis of Specialty Lipids 16
1.3.6 Structured Lipids 16
1.3.6 Synthesis of Structured Lipids from Vegetable Oils and n-3 Fatty Acids 17
1.3.7 Synthesis of Structured Lipids from Marine Oils
and Medium-Chain Fatty Acids 18
1.3.8 Synthesis of SBO-Based Structured Lipids 19
1.3.9 Low-Calorie Structured and Specialty Lipids 19
1.4. Low-Calorie Fat Substitutes 20
1.4.1 Olestra (Sucrose Polyester) 20
1.4.2 Simplesse 21
1.4.3 Sorbestrin (Sorbitol Polyester) 21
1.4.4 Esterified Propoxylated Glycerols (EPGs) 21
1.4.5 Paselli 22
1.4.6 N-Oil 22
References 22
Nutraceutical and Specialty
Lipids
Fereidoon Shahidi and S.P.J.N. Senanayake
*
Department of Biochemistry, Memorial University of Newfoundland,
St. John’s, Newfoundland, Canada

1
*
Current address: Martek Biosciences Corporation, 555 Rolling Hills Lane, Winchester, Kentucky.
1
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1.1 INTRODUCTION
Lipids are organic substances that are insoluble or sparingly soluble in water. They are important
components in determining the sensory attributes of foods. Lipids contribute to mouthfeel and
textural properties in the foods. They have several important biological functions, which include:
(1) serving as structural components of membranes; (2) acting as storage and transport forms of
metabolic fuel; (3) serving as the protective coating on the surface of many organisms; (4) acting
as carriers of fat-soluble vitamins A, D, E, and K and helping in their absorption; and (5) being
involved as cell-surface components concerned with cell recognition, species specificity, and tissue
immunity. Ironically, overconsumption of lipids is associated with a number of diseases, namely
artherosclerosis, hypertension, and breast and colon cancer, and in the development of obesity.
There are several classes of lipids, all having similar and specific characteristics due to the pres-
ence of a major hydrocarbon portion in their molecules. Over 80 to 85% of lipids are generally in
the form of triacylglycerols (TAGs). These are esters of glycerol and fatty acids. The TAGs occur
in many different types, according to the identity and position of the three fatty acid components.
Those with a single type of fatty acid in all three positions are called simple TAGs and are named
after their fatty acid component. However, in some cases the trivial names are more commonly
used. An example of this is trioleylglycerol, which is usually referred to as triolein. The TAGs with
two or more different fatty acids are named by a more complex system.
Lipids, and particularly TAGs, are integrated components of our diet and are a major source of
caloric intake from foods. The caloric value of lipids is much higher than other food components
and about 2.25 times greater than that of proteins and carbohydrates. While a certain amount of fat
in the diet is required for growth and maintenance of the body functions, excessive intake of lipids
has its own implications. While our body can synthesize saturated and monoenoic acids, polyun-
saturated fatty acids (PUFAs) must be provided in the diet. Deficiency of linoleic acid and n-3 fatty
acids results in dermatitis and a variety of other disease conditions. The role of n-3 fatty acids in

lowering of blood cholesterol level and other benefits has been appreciated. The ratio of the intake
of linoleic to α-linolenic acid in our diet should be approximately 2 and our daily caloric intake
should have a contribution of 3.0 to 6.0% and 2.0 to 2.5% of each of these fatty acids, respectively.
1.2 CHEMISTRY AND COMPOSITION OF LIPIDS
1.2.1 T
HE FATTY ACIDS
Fatty acids are divided into saturated and unsaturated groups, the latter being further subdivided into
monounsaturated and PUFAs. The PUFAs are divided into main categories depending on the posi-
tion of the first double bond in the fatty acid carbon chain from the methyl end group of the mole-
cules and are called n-3, n-6, and n-9 families.
1.2.2 SATURATED FATTY ACIDS
Saturated fatty acids contain only single carbon–carbon bonds in the aliphatic chain and all other
available bonds are taken up by hydrogen atoms. The most abundant saturated fatty acids in animal
and plant tissues are straight-chain compounds with 14, 16, and 18 carbon atoms. In general, satu-
rated fats are solid at room temperature. They are predominantly found in butter, margarine, short-
ening, coconut and palm oils, as well as foods of animal origin
1
. The most common saturated
fatty acids in foods are lauric (12:0), myristic (14:0), palmitic (16:0), and stearic (18:0) acids
2
. The
common nomenclature for some saturated fatty acids is given in Table 1.1.
Fatty acids containing 4 to 14 carbon atoms occur in milk fat and in some vegetable oils.
For example, cow’s milk fat contains butyric acid (4:0) at a level of 4%. In addition, fatty acids
containing 6 to 12 carbon atoms are also present in small quantities. The short-chain fatty acids are
2 Nutraceutical and Specialty Lipids and their Co-Products
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usually present in butter and in other milk fat-based products. For example, the short-chain fatty
acids from butyric to capric are characteristic of ruminant milk fat.
Tropical fruit oils, such as those from coconut and palm kernel, contain very high amounts

(approximately 50%) of lauric acid (12:0). They also contain significant amounts of caprylic (8:0),
capric (10:0), and myristic (14:0) acids. Canola oil is another example of a lauric acid-rich oil.
Palmitic acid (16:0) is the most widely occurring saturated fatty acid. It is found in almost all
vegetable oils, as well as in fish oils and body fat of land animals. The common sources of palmitic
acid include palm oil, cottonseed oil, as well as lard and tallow, among others.
Stearic acid (18:0) is less common compared to palmitic acid. However, it is a major compo-
nent of cocoa butter. This fatty acid may be produced by hydrogenation of oleic, linoleic, and
linolenic acids. Palmitic and stearic acids are employed in food and nonfood (personal hygiene
products, cosmetics, surfactants, etc.) products.
1.2.3 UNSATURATED FATTY ACIDS
Unsaturated fatty acids contain carbon–carbon double bonds in the aliphatic chain. In general, these
fats are soft at room temperature. When the fatty acids contain one carbon–carbon double bond in
the molecule, it is called monounsaturated. Monounsaturated fatty acids are synthesized within the
human body
3
. Oleic acid (18:1n-9) is the most common dietary monounsaturated fatty acid and
found in most animal fats
1,2
. The common nomenclature for some unsaturated fatty acids is given
in Table 1.2.
PUFAs contain two or more carbon–carbon double bonds. The PUFAs are liquid at room
temperature. In general, they have low melting points and are susceptible to oxidation. They are
found in grains, nuts, vegetables, and seafood (Table 1.3). The PUFAs of animal origin can be
categorized into different families according to their derivation from specific biosynthetic precur-
sors. In each case, the families contain from two up to a maximum of six double bonds, separated
by methylene-interrupted groups and they have the same terminal structure. Linoleic acid (LA;
18:2n-6) is the most common fatty acid of this type. This fatty acid is found in all vegetable fats and
is required for normal growth, reproduction, and health. It is the most predominant PUFA in the
Western diet
4

. LA serves as a precursor or “parent” compound of n-6 family of fatty acids that is
formed by desaturation and chain elongation, in which the terminal (n-6) structure is retained. Thus,
LA can be metabolized into γ-linolenic acid (GLA; 18:3n-6), dihomo-γ-linolenic acid (DGLA;
20:3n-6), and arachidonic acid (AA; 20:4n-6). Of these, AA is particularly important as an essential
Nutraceutical and Specialty Lipids 3
TABLE 1.1
Nomenclature of Some Common Saturated Fatty Acids
Common name Systematic name No. of carbon atoms Shorthand notation
Acetic Ethanoic 2 2:0
Butyric Butanoic 4 4:0
Caproic Hexanoic 6 6:0
Caprylic Octanoic 8 8:0
Capric Decanoic 10 10:0
Lauric Dodecanoic 12 12:0
Myristic Tetradecanoic 14 14:0
Palmitic Hexadecanoic 16 16:0
Stearic Octadecanoic 18 18:0
Arachidic Eicosanoic 20 20:0
Behenic Docosanoic 22 22:0
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component of the membrane phospholipids and as a precursor of the eicosanoids. GLA, an important
intermediate in the biosynthesis of AA from LA, is a constituent of certain seed oils and has been
a subject of intensive study. α-Linolenic acid (ALA; 18:3n-3) is a precursor of n-3 family of fatty
acids. It is found in appreciable amounts in green leaves, stems, and roots. It is a major component
of flaxseed oil (45 to 60%) (Table 1.3). When ALA is absorbed into an animal body through the
diet, it forms long-chain PUFAs with an n-3 terminal structure. ALA can be metabolized into eicos-
apentaenoic acid (EPA; 20:5n-3) and docosahexaenoic acid (DHA; 22:6n-3). They have special
functions in the membrane phospholipids. In addition, EPA is a precursor of a series of eicosanoids.
The major sources of EPA and DHA are algal, fish, and other marine oils.
1.2.4 ACYLGLYCEROLS

Edible fats and oils are composed primarily of TAGs. Partial acylglycerols, such as mono- and dia-
cylglycerols, may also be present as minor components. The TAGs consist of a glycerol moiety,
each hydroxyl group of which is esterified to a fatty acid. These compounds are synthesized by
enzyme systems in nature. A stereospecific numbering (sn) system has been recognized to describe
various enantiomeric forms (e.g., different fatty acyl groups in each positions in the glycerol back-
bone) of TAGs. In a Fischer projection of a natural L-glycerol derivative, the secondary hydroxyl
group is shown to the left of carbon-2; the carbon atom above this becomes carbon-1 and that below
becomes carbon-3 (Figure 1.1). The prefix “sn” is placed before the stem name of the compound.
Partial acylglycerols, namely diacylglycerols (DAGs) and monoacylglycerols (MAGs), are
important intermediates in the biosynthesis and catabolism of TAGs and other classes of lipids. For
example, 1,2-DAGs are important as intermediates in the biosynthesis of TAGs and other lipids.
2-MAGs are formed as intermediates or end products of the enzymatic hydrolysis of TAGs. The
DAGs are fatty acid diesters of glycerol while the MAGs are fatty acid monoesters of glycerol. The
MAGs and DAGs are produced on a large scale for use as surface-active agents. Acyl migration may
occur with partial acylglycerols, especially on heating, in alcoholic solvents or when protonated
reagents are present.
1.2.5 PHOSPHOLIPIDS
In phospholipids, one or more of the fatty acids in the TAG is replaced by phosphoric acid or its
derivatives. Phospholipids are major constituents of cell membranes and thus regarded as structural
4 Nutraceutical and Specialty Lipids and their Co-Products
TABLE 1.2
Nomenclature of Some Common Unsaturated Fatty Acids
Common name Systematic name No. of carbon atoms Shorthand notation
Myristoleic Tetradec-9-enoic 14 14:1
Palmitoleic Hexadec-9-enoic 16 16:1
Oleic Octadec-9-enoic 18 18:1n-9
Linoleic Octadeca-9,12-dienoic 18 18:2n-6
α-Linolenic Octadeca-9,12,15-trienoic 18 18:3n-3
γ-Linolenic Octadeca-6,9, 12-trienoic 18 18:3n-6
Elaeostearic Octadeca-9,11,13-trienoic 20 20:3

Gadoleic Eicosa-9-enoic 20 20:1
Arachidonic Eicosa-5,8,11,14-tetraenoic 20 20:4n-6
EPA Eicosa-5,8,11,14,17-pentaenoic 20 20:5n-3
Erucic Docosa-13-enoic 22 22:1
DHA Docosa-4,7,10,13,16,19-hexaenoic 22 22:6n-3
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Nutraceutical and Specialty Lipids 5
TABLE 1.3
Dietary Sources of Selected Fatty Acids
Source Total fatty acid (%)
18:3n-3
Flaxseed 45–60
Green leaves 56
Rapeseed 10–11
20:5n-3
Herring 3–5
Mackerel 7–8
Sardine/pilchard 3–17
Pacific anchovy 18
Cod 17
Halibut 13
Menhaden 14
22:6n-3
Herring 2–3
Mackerel 8
Sardine/pilchard 9–13
Pacific anchovy 9–11
Cod 30
Halibut 38
Menhaden 8

18:2n-6
Borage 38
Evening primrose 70–75
Blackcurrant 44
Corn 34–62
Soybean 44–62
Sunflower seed 20–75
Safflower seed 55–81
Sesame seed 35–50
Cotton seed 33–59
Groundnut 13–45
18:3n-6
Borage 20
Evening primrose 10
Blackcurrant 17–20
FIGURE 1.1 Stereospecific numbering of triacylglycerols.
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lipids in living organisms. The acyl groups in phospholipids occur in the sn-1 and sn-2 positions of
the glycerol moiety while a polar head group involving a phosphate is present in the sn-3 position
of the molecule. There are several types of phospholipids (Figure 1.2). These are based on the phos-
phatidic acids (monoesters of the tribasic phosphoric acid), which themselves are diacyl derivatives
of 3-glycerophosphoric acid. The major types of phospholipids include phosphatidylcholine (PC),
phosphatidylethanolamine (PE), phosphatidylserine (PS), phosphatidylinositol (PI), and phos-
phatidylglycerol (PG), among others.
Phospholipids of various types are present as minor components (0.5 to 3.0%) in most crude
oils. However, these compounds are mainly removed during the refining process. They may be
recovered as a distillate byproduct during deodorization and are generally referred to as lecithin,
which is a mixture of phospholipids. The major phospholipids in crude lecithin are usually PC, PE,
PI, and phosphatidic acids. Lecithin is found in many sources of vegetable oils. Commercial lecithin
is generally produced from soybean oil during the degumming process. Lecithin is also available

from sunflower, rapeseed, and corn oils. These are important surface-active compounds used exten-
sively in the food, pharmaceutical, and cosmetic applications.
The hydrolysis of phospholipids gives rise to various products. For example, hydrolysis of PC
occurs with aqueous acids and the products are glycerol, fatty acids, phosphoric acid, and choline.
However, enzyme-assisted hydrolysis is more selective and gives rise to a variety of products.
6 Nutraceutical and Specialty Lipids and their Co-Products
FIGURE 1.2 Chemical structures of the major phospholipids.
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Phospholipase A
1
causes deacylation at the sn-1 position, liberating fatty acids from this position
and leaving behind a lysophosphatidylcholine. Phospholipase A
2
behaves in a similar manner at the
sn-2 position.
There are differences in the natural distribution of fatty acids associated with lipids such as
phospholipids and TAGs. For example, it is generally believed that phospholipids, such as lecithin
and cephalin, contain more PUFAs than do the TAGs. Lovern
5
reported that phospholipids present
in marine species are generally unsaturated and esterified mainly with EPA and DHA. Menzel and
Olcott
6
studied PC and PE constituents of menhaden oil and found that their PUFAs were located
mainly in the sn-2 position of the TAG molecules. The sn-2 position of PC in menhaden oil con-
tained 29 and 42% EPA and DHA, respectively, whereas the sn-1 position contained only 1.7 and
12.5%, respectively, of these fatty acids. However, the phospholipid content of refined, bleached,
and deodorized oils is very low
7
, due to the removal of polar compounds during the degumming

process.
Phospholipids are usually extracted with the total lipids when using the Bligh and Dyer
8
fat
extraction procedure. Silicic acid column chromatography with methanol after eluting neutral lipids
can be used to recover phospholipids. Two-dimensional thin-layer chromatography (TLC)
9
and
Iatroscan
10
provide a means for separating individual phospholipids.
1.2.6 FAT-SOLUBLE VITAMINS AND TOCOPHEROLS
Vitamins A and D are stored in large amounts in the liver of fish. Therefore, fish liver oils are
considered as exceptionally rich sources of vitamins A and D. After vitamin A was synthesized and
produced commercially, production of the liver oils for vitamins A and D became a minor industry
in North America. Vitamin E or α-tocopherols are also present in marine lipids. Though present in
lower amounts, the tocopherols and tocotrienols attract attention because of their vitamin E and
antioxidant properties. The tocopherols are a series of benzopyranols with one, two, or three methyl
groups attached to the phenolic ring. The molecules also have a 16-carbon side chain moiety on the
pyran ring. In tocopherols the side chain is saturated, whereas in tocotrienols the side chain is unsat-
urated and contains three double bonds. There are four tocopherols and tocotrienols designated α,
β, γ, and δ. The tocopherols exhibit different vitamin E activity in the order α>β>γ>δ.
However, the antioxidant activity is generally in the reverse order (δ>γ>β>α). Thus, various
oils do not follow a similar sequence of vitamin E and antioxidant activity.
1.2.7 STEROLS
Most vegetable oils contain 0.1 to 0.5% sterols. They may exist as free sterols and esters with long-
chain fatty acids. Sitosterol is generally the major phytosterol, contributing 50 to 80% to the total
content of sterols. Campesterol and stigmasterol may also be present in significant levels.
Cholesterol is generally considered to be an animal sterol. It is not present in plant systems at any
significant level. The sterol content of some fats and oils is given in Table 1.4.

1.2.8 WAXES
Waxes include a variety of long-chain compounds occurring in both plants and animals. These
are generally water-resistant materials made up of mixtures of fatty alcohols and their esters. They
differ from the long-chain fatty acids in the TAG molecules. These include compounds of higher
molecular weight (up to 60 carbon atoms and beyond) and are frequently branched with one or more
methyl groups. Even though they may be unsaturated they do not generally exhibit a methylene-
interrupted unsaturation pattern. Waxes find useful applications in the food, pharmaceutical, and
cosmetic industries.
Nutraceutical and Specialty Lipids 7
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1.2.9 BIOCHEMISTRY AND METABOLISM OF SHORT-CHAIN FATTY ACIDS (SCFAS)
Short-chain fatty acids (SCFA) are saturated fatty acids with 2 to 4 carbon atoms. This family of
fatty acids includes acetic acid (2:0), propionic acid (3:0), and butyric acid (4:0). They are com-
monly referred to as the volatile fatty acids and are produced in the human gastrointestinal tract via
bacterial fermentation of dietary carbohydrates
11
. SCFAs are present in the diet in small amounts,
for example acetic acid in vinegar and butyric acid in bovine milk and butter. They may also be pre-
sent in fermented foods. In humans, SCFAs contribute 3% of the total energy expenditure
12
. SCFAs
are more easily absorbed in the stomach and provide fewer calories than MCFAs and LCFAs.
In nutritional applications, there has been a growing interest in the use of SCFAs as an alterna-
tive or additional source of energy to the medium- (MCFA) and long-chain fatty acid (LCFA) coun-
terparts. The SCFAs, acetic, propionic, and butyric acids, are easily hydrolyzed from a single TAG
structure and are rapidly absorbed by the intestinal mucosa
13
. These fatty acids go directly into the
portal vein for transport to the liver where they are broken down to acetate via β-oxidation. The
acetate can then be metabolized for energy or use in new fatty acid synthesis.

SCFAs may be incorporated into enteral nutritional formulas. Kripke et al.
14
have shown that a
chemically synthesized diet containing 40% (w/w) of nonprotein as short-chain triacylglycerols
(1:1, triacetin and tributyrin) maintained body weight, improved nitrogen balance and liver func-
tion, and enhanced jejunal and colonic mucosal adaptation in rats after 60% distal small-intestine
resection with cecectomy, when compared to short-intestine animals receiving a diet without
supplemental lipid calories from medium-chain triacylglycerol (MCT). SCFAs affect gastrointestinal
function by stimulating pancreatic enzyme secretion
15
and increasing sodium and water absorption
in the intestine
16
.
1.2.10 BIOCHEMISTRY AND METABOLISM OF MCFAS
MCFAs are saturated fatty acids with 6 to 12 carbon atoms
17
. The sources of MCFAs include lau-
ric oils such as coconut and palm kernel oils
18
. For example, coconut oil naturally contains some
65% MCFAs
19
. MCFAs, being saturated fatty acids, are resistant to oxidation and stable at high and
low temperatures
20
. One of the first medical foods developed, as an alternative to conventional
lipids, was MCT. MCT is an excellent source of MCFAs for production of structured and specialty
lipids. Pure MCTs have a caloric value of 8.3 calories per gram. However, they do not provide
essential fatty acids

21,22
. MCFAs are more hydrophilic than their LCFA counterparts, and hence their
solubilization as micelles is not a prerequisite for absorption
23
. MCTs can also be directly incorpo-
rated into mucosal cells without hydrolysis and may readily be oxidized in the cell. MCTs pass
8 Nutraceutical and Specialty Lipids and their Co-Products
TABLE 1.4
Sterol Content of Fats and Oils
Source Sterol (%)
Soybean oil 0.7–0.9
Canola oil 0.4–0.5
Corn oil 1.0–2.3
Coconut oil 0.08
Mustard oil 0.06
Milk fat 0.3–0.35
Lard 0.12
Beef tallow 0.08–0.10
Herring 0.4
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directly into the portal vein and are readily oxidized in the liver to serve as an energy source. Thus,
they are less likely to be deposited in adipose tissues
20
and are more susceptible to oxidation in tis-
sues
24
. MCTs are metabolized as quickly as glucose and have twice the energy value of
carbohydrates
25
. Johnson et al.

26
found that MCTs were oxidized much more rapidly than LCTs,
with 90% conversion to carbon dioxide in 24 h.
MCTs are liquid or solid products at room temperature. They have a smaller molecular size,
lower melting point, and greater solubility than their LCFA counterparts. These characteristics
account for their easy absorption, transport, and metabolism compared to LCTs
27
. MCTs are
hydrolyzed by pancreatic lipase more rapidly and completely than are LCTs
18
. They may be directly
absorbed by the intestinal mucosa with minimum pancreatic or biliary function. They are trans-
ported predominantly by the portal vein to the liver for oxidation
28
rather than through the intestinal
lymphatics. In addition, MCFAs are more rapidly oxidized to produce acetyl-CoA and ketone bodies
and are independent of carnitine for entry into the mitochondria.
MCTs need to be used with LCTs to provide a balanced nutrition in enteral and parenteral prod-
ucts
29,30
. In many medical foods, a mixture of MCTs and LCTs is used to provide both rapidly
metabolized and slowly metabolized fuel as well as essential fatty acids. Clinical nutritionists have
taken advantage of MCTs’ simpler digestion to nourish individuals who cannot utilize LCTs. Any
abnormality in the numerous enzymes or processes involved in the digestion of LCTs can cause
symptoms of fat malabsorption. Thus, patients with certain diseases have shown improvement when
MCTs are included in their diet
31
. MCTs are also increasingly utilized in the feeding of critically ill
or septic patients who presumably gain benefits in the setting of associated intestinal dysfunction.
Further investigation should clarify potential roles for MCTs in patients with lipid disorders asso-

ciated with lipoprotein lipase and carnitine deficiencies. MCTs may be used in confectioneries and
in other functional foods as carriers for flavors, colors, and vitamins
20
. MCTs have clinical appli-
cations in the treatment of fat malabsorption, maldigestion, obesity, and metabolic difficulties
related to cystic fibrosis, Crohn’s disease, colitis, and enteritis
31,32
.
1.2.11 BIOCHEMISTRY AND METABOLISM OF ESSENTIAL FATTY ACIDS (EFAS)
The EFAs are PUFAs which means that they have two or more double bonds in their backbone
structure. There are two groups of EFAs, the n-3 fatty acids and the n-6 fatty acids. They are
defined by the position of the double bond in the molecule nearest to the methyl end of the chain.
In the n-3 group of fatty acids it is between the third and fourth carbon atoms and in the n-6 group
of fatty acids it is between the sixth and seventh carbon atoms. The parent compounds of the n-6
and n-3 groups of fatty acids are LA and ALA, respectively. LA and ALA are considered to be
essential fatty acids for human health because humans cannot synthesize them and must obtain
them from the diet. Within the body, these parent compounds are metabolized by a series of alter-
nating desaturations (in which an extra double bond is inserted by removing two hydrogen atoms)
and elongations (in which two carbon atoms are added) as shown in Figure 1.3. This requires a
series of special enzymes called desaturases and elongases. It is believed that the enzymes metab-
olizing both n-6 and n-3 fatty acids are identical
33
, resulting in competition between the two PUFA
families for these enzymes
3
. Chain elongation and desaturation occurs only at the carboxyl end of
the fatty acid molecule
34
.
The potential health benefits of n-3 fatty acids include reduced risk of cardiovascular disease,

inflammation, hypertension, allergies, and immune and renal disorders
35–37
. Epidemiological stud-
ies have linked the dietary intake of n-3 PUFAs in Greenland Eskimos to their lower incidence of
coronary heart disease
38,39
. Research has shown that DHA is essential for proper function of central
nervous system and visual acuity of infants
40
. The n-3 fatty acids are essential for normal growth
and development throughout the life cycle of humans and therefore should be included in the
diet. Fish and marine oils are rich sources of n-3 fatty acids, especially EPA and DHA. Cod liver,
menhaden, and sardine oils contain approximately 30% EPA and DHA.
Nutraceutical and Specialty Lipids 9
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The n-6 fatty acids exhibit various physiological functions in the human body. The main functions
of these fatty acids are related to their roles in the membrane structure and in the biosynthesis of
short-lived derivatives (eicosanoids) which regulate many aspects of cellular activity. The n-6 fatty
acids are involved in maintaining the integrity of the water impermeability barrier of the skin. They
are also involved in the regulation of cholesterol transport in the body.
GLA, a desaturation product of linoleic acid, has shown therapeutic benefits in a number of
diseases, notably atopic eczema, cyclic mastalgia, premenstrual syndrome, cardiovascular disease,
inflammation, diabetes, and cancer
33
. Arachidonic acid is found in meats, egg yolk, and human
milk. GLA is found in oats, barley, and human milk. GLA is also found in higher amounts in plant
seed oils such as those from borage, evening primrose, and blackcurrant. Algae such as Spirulina
and various species of fungi also seem to be desirable sources of GLA.
1.2.12 EICOSANOIDS
Much attention has been paid to the role of EFAs as precursors of a wide variety of short-lived

hormone-like substances called eicosanoids. They are 20-carbon endogenous biomedical media-
tors derived from EFAs, notably AA and DGLA of the n-6 family and EPA of the n-3 family
41
.
DGLA, AA, and EPA are precursors for eicosanoid series 1, 2, and 3, respectively. The members
of the eicosanoid cascade include the prostaglandins, prostacyclins, thromboxanes, leukotrienes,
and hydroxy fatty acids. They play a major role in regulating the cell-to-cell communication
involved in cardiovascular, reproductive, respiratory, renal, endocrine, skin, nervous, and immune
system actions. Arachidonic acid is derived from linoleic acid, which gives rise to series-2
prostaglandins, series-2 prostacyclins, series-2 thromboxanes, and series-4 leukotrienes. These
end products of n-6 fatty acid metabolism induce inflammation and immunosuppression.
Prostanoids (collective name for prostaglandins, prostacyclins, thromboxanes) of series-1 and
leukotrienes of series-3 are produced from DGLA. When n-3 fatty acids are processed in the
eicosanoid cascade, series-3 prostaglandins, series-3 prostacyclins, series-3 thromboxanes, and
series-5 leukotrienes are formed.
10 Nutraceutical and Specialty Lipids and their Co-Products
FIGURE 1.3 Metabolic pathways of the omega-3 and omega-6 fatty acids.
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