//img.uscri.be/pth/51ef361f13208fc872285d518fc3623c80e82653
Cette publication ne fait pas partie de la bibliothèque YouScribe
Elle est disponible uniquement à l'achat (la librairie de YouScribe)
Achetez pour : 210,16 € Lire un extrait

Téléchargement

Format(s) : PDF

avec DRM

The Chemistry of Oils and Fats

De
304 pages
The three major macronutrients are proteins, carbohydrates, and lipids (oils and fats). This book is devoted to lipids, which are an important part of life for all of us. What are these materials in molecular terms? Where do they come from? What happens to them between the harvesting of crops and the appearance of the oils and fats in different products in the supermarket? How does nature produce these molecules and can we act on nature to modify the materials to increase their beneficial properties? How important are the minor products present in the fats that we consume? Since oils and fats vary, how can we analyse them? What are their physical, chemical and nutritional properties? How do the fats that we consume affect our health and well-being in both quantitative and qualitative terms? What are their major food and non-food uses?


This book provides a broad source of reference on oils and fats chemistry for graduates entering the food and oleochemical industries, postgraduate researchers and nutritionists. It offers a point of entry to the detailed literature.

Voir plus Voir moins
Contents
Preface
Abbreviations
1
Oils and fats: sources and constituents
1.1 1.2 1.3
1.4
Introduction Specifications Major oils and fats 1.3.1 Castor oil 1.3.2 Cocoa butter 1.3.3 Coconut oil 1.3.4 Corn oil 1.3.5 Cottonseed oil 1.3.6 Groundnut oil 1.3.7 Linseed (flaxseed, linola) 1.3.8 Olive oil 1.3.9 Palm oil 1.3.10 Palmkernel oil 1.3.11 Rapeseed oil (also called canola oil) 1.3.12 Rice bran oil 1.3.13 Safflower oil 1.3.14 Sesame oil 1.3.15 Soybean oil 1.3.16 Sunflower oil 1.3.17 Tall oil 1.3.18 Oils with modified fatty acid composition Minor vegetable oils 1.4.1 Cocoa butter alternatives 1.4.2 Oils containing-linolenic acid and/or stearidonic acid 1.4.3 Avocado oil (Persea americana) 1.4.4 Chinese vegetable tallow and stillingia oil (Sapium sebiferum andStillingia sebifera) 1.4.5 Crambe (Crambe abyssinicaandC. hispanica) 1.4.6 Cuphea 1.4.7 Dimorphotheca 1.4.8 Hemp (Marijuana,Cannabis sativa) 1.4.9 Gold of Pleasure (Camelina sativa, also called false flax) 1.4.10 Hazelnut (Corylus avellana, also called filberts) 1.4.11 Honesty (Lunaria annua)
xiii
xv
1
1 1 2 3 3 3 4 5 5 5 6 6 7 7 8 9 9 9 11 11 12 12 13 13 14 14
15 15 15 15 16 16 16
vi
2
3
1.5
1.6
1.7
CONTENTS
1.4.12 Lesquerella oils 1.4.13 Marigold (Calendula officinalis) 1.4.14 Meadowfoam (Limnanthes alba) 1.4.15 Sea buckthorn (Hippophae rhamnoides) 1.4.16 Tung oil (Aleurites fordii) 1.4.17 Walnut (Juglans regia) 1.4.18 Wheatgerm (Triticum aestivum) Animal fats 1.5.1 Butter fat 1.5.2 Lard 1.5.3 Tallow 1.5.4 Fish oils Major and minor components 1.6.1 Fatty acids, glycerol esters and waxes 1.6.2 Phospholipids 1.6.3 Sterols 1.6.4 Tocols 1.6.5 Fat soluble vitamins 1.6.6 Chlorophyll 1.6.7 Hydrocarbons 1.6.7.1 Alkanes 1.6.7.2 Squalene (C30H50) 1.6.7.3 Carotenes 1.6.7.4 Polycyclic aromatic hydrocarbons Oils and fats in the market place Bibliography and references
Extraction, refining and processing
2.1 2.2
2.3
Extraction Refining 2.2.1 Degumming 2.2.2 Neutralisation 2.2.3 Bleaching 2.2.4 Deodorisation and physical refining 2.2.5 Super-refining (chromatography) Processing 2.3.1 Blending 2.3.2 Fractionation 2.3.2.1 Winterisation 2.3.2.2 Hydrophilisation 2.3.2.3 Urea fractionation 2.3.3 Hydrogenation 2.3.4 Interesterification with chemical catalysts 2.3.5 Interesterification with an enzymic catalyst Bibliography and references
Structure of fatty acids and lipids
3.1 3.2
Introduction Fatty-acid nomenclature
16 17 17 17 18 18 18 18 18 20 20 21 23 23 25 26 26 29 30 30 30 31 31 32 32 34
36
36 38 39 39 40 40 41 41 42 42 44 44 44 45 47 48 49
50
50 50
4
3.3 3.4
3.5 3.6 3.7 3.8 3.9
3.10 3.11 3.12
3.13 3.14 3.15 3.16 3.17
CONTENTS
Fatty acids ± main structural features Saturated acids 3.4.1 Short- and medium-chain acids (4:0±14:0) 3.4.2 Palmitic and stearic acid 3.4.3 Long-chain acids Monoene acids Methylene-interrupted polyene acids Other unsaturated acids Branched chain and cyclic acids Oxygenated acids 3.9.1 Hydroxy acids 3.9.2 Epoxy, furanoid and oxa acids Halogenated fatty acids Introduction to lipid structure Acylglycerols 3.12.1 Monoacylglycerols 3.12.2 Diacylglycerols 3.12.3 Triacylglycerols Wax esters Glycosyldiacylglycerols Phospholipids Ether lipids Sphingolipids Acknowledgement Bibliography and references
Chemical and biological synthesis of fatty acids and lipids
4.1
4.2
4.3 4.4 4.5
Fatty acid synthesis 4.1.1 Introduction 4.1.2 Partial synthesis by chain extension 4.1.3 Synthesis via acetylenic intermediates 4.1.4 Synthesis by the Wittig reaction 4.1.5 Other synthetic procedures 4.1.6 Synthesis of isotopically labelled acids Acylglycerol synthesis 4.2.1 Introduction 4.2.2 C3synthons 4.2.3 Acylation procedures 4.2.4 Acyl migration 4.2.5 Protecting (blocking) groups 4.2.6 Synthesis of racemic acylglycerols 4.2.7 Synthesis of enantiomeric acylglycerols 4.2.8 Structured lipids Phospholipid synthesis Sphingolipid synthesis Fatty-acid biosynthesis 4.5.1 Introduction 4.5.2De novosynthesis of saturated acids 4.5.3 Desaturation to monoene and polyene acids and elongation in plant systems
vii
52 52 53 53 54 54 56 57 59 61 61 63 64 64 66 66 66 67 68 68 69 72 73 75 75
76
76 76 76 77 78 79 80 81 81 81 81 83 83 83 86 86 87 88 88 88 89
90
Physical properties
107 108 108 109 110 110 112 112 113 116 122 122 123
124 124 126 129 129 130 130
124
CONTENTS
4.5.4 Desaturation and elongation in animal systems Lipid biosynthesis 4.6.1 Formation of triacylglycerols 4.6.2 Phospholipids 4.6.3 Sphingolipids Isolation procedures 4.7.1 Crystallisation 4.7.2 Distillation under reduced pressure 4.7.3 Chromatography including silver ion systems 4.7.4 Urea fractionation 4.7.5 Enzymic enhancement 4.7.6 Chemical methods Bibliography and references
Analytical procedures
Introduction Classical analytical procedures 5.2.1 Introduction 5.2.2 Extraction 5.2.3 Melting behaviour 5.2.4 Unsaturation 5.2.5 Acidity, saponification and unsaponifiable material 5.2.6 Measurement of oxidative deterioration and of oxidative stability Present-day analytical techniques 5.3.1 Chromatography and spectroscopy 5.3.2 Thin-layer chromatography (TLC) and related chromatographic systems 5.3.3 High performance liquid chromatography (HPLC) 5.3.4 Gas chromatography (GC) 5.3.5 NMR spectroscopy 5.3.6 Near-infrared and Fourier transform infrared spectroscopy 5.3.7 Mass spectrometry 5.3.8 Enzymatic procedures Lipid analysis 5.4.1 Fatty acids 5.4.2 Acylglycerols 5.4.3 Phospholipids 5.4.4 Minor components (sterols and tocopherols) Bibliography and references
6
5
4.6
4.7
viii
Polymorphism, crystal structure and melting point 6.1.1 Alkanoic and alkenoic acids 6.1.2 Glycerol esters Spectroscopic properties 6.2.1 Ultraviolet spectroscopy 6.2.2 Infrared spectroscopy 6.2.3 Electron spin resonance (ESR) spectroscopy
104 106 106
91 92 92 93 94 94 94 94 95 95 95 96 98
100
5.1 5.2
100 100 100 101 102 102 103
5.3
6.2
6.1
5.4
7
6.3
CONTENTS
1 6.2.4 H NMR spectroscopy 6.2.4.1 Low resolution NMR spectroscopy 6.2.4.2 High resolution NMR spectroscopy 13 6.2.5 C NMR spectroscopy 6.2.6 Mass spectrometry Other physical properties 6.3.1 Density 6.3.2 Viscosity 6.3.3 Refractive index 6.3.4 Solubility of gases in oils 6.3.5 Other physical properties Biblography and references
Chemical properties related to unsaturated centres
7.1
7.2
7.3
7.4
7.5 7.6 7.7 7.8
Hydrogenation 7.1.1 Catalytic hydrogenation 7.1.2 Other chemical reductions 7.1.3 Biohydrogenation Oxidation through reaction with oxygen 7.2.1 Introduction 7.2.2 Autoxidation 7.2.3 Photo-oxidation 7.2.4 Hydroperoxide structures 7.2.4.1 Methyl oleate 7.2.4.2 Methyl linoleate 7.2.4.3 Methyl linolenate 7.2.4.4 Cholesterol 7.2.5 Decomposition of hydroperoxides to short-chain products 7.2.6 Other secondary reaction products 7.2.7 Antioxidants ± introduction 7.2.8 Primary and secondary antioxidants 7.2.9 Synthetic and natural antioxidants Biological oxidation 7.3.1-Oxidation 7.3.2-Oxidation 7.3.3!-Oxidation 7.3.4 Lipoxygenase 7.3.5 Production and function of eicosanoids Other oxidation reactions 7.4.1 Epoxidation 7.4.1.1 Preparation of epoxides 7.4.1.2 Physical and chemical properties 7.4.1.3 Applications 7.4.2 Hydroxylation 7.4.3 Oxidative fission Halogenation Stereomutation Metathesis Double bond migration and cyclisation
ix
130 131 131 133 135 140 140 140 141 141 141 143
146
146 146 148 149 150 150 151 153 154 155 156 158 159 161 163 164 165 166 168 168 169 169 169 171 171 171 173 174 175 176 176 178 179 180 181
x
8
9
7.9
7.10 7.11
CONTENTS
Dimerisation (dimer acids, isostearic acid, estolides, Guerbet alcohols and acids) Neighbouring group participation Friedel-Crafts acylation and related reactions Bibliography and references
Chemical properties related to the carboxyl group
8.1 8.2 8.3
8.4 8.5 8.6
8.7 8.8 8.9 8.10
Introduction Hydrolysis Esterification 8.3.1 Reaction between carboxylic acids and alcohols 8.3.2 Acidolysis 8.3.3 Alcoholysis 8.3.4 Interesterification 8.3.5 Structured lipids 8.3.6 Lactones Acid chlorides, acid anhydrides and ketene dimers Peroxy acids and esters Long-chain alcohols 8.6.1 Preparation of alcohols 8.6.2 Ethoxylation and propoxylation of alcohols and esters 8.6.3 Sulfates and other alcohol esters 8.6.4 Alkyl polyglycosides 8.6.5 Guerbet alcohols and acids Acetals/ketals and orthoesters Nitrogen-containing compounds Sulfonation and other reactions at the-position Barton reaction Bibliography and references
Nutritional properties
9.1 9.2 9.3 9.4 9.5 9.6 9.7
9.8
Dietary fat ± sources and composition Digestion, absorption and transport Essential fatty acids Recommendations for dietary intake Cholesterol and phytosterols Conjugated linoleic acid (CLA) Role of fats in health and disease 9.7.1 Obesity 9.7.2 Coronary heart disease (CHD) 9.7.3 Diabetes 9.7.4 Inflammatory diseases 9.7.5 Psychiatric disorders 9.7.6 Cancer Functional foods 9.8.1 Diacylglycerols 9.8.2 Phytosterols Bibliography and references
183 185 187 188
189
189 190 191 191 192 193 195 196 198 199 200 201 201 203 204 205 205 206 207 209 210 210
211
211 214 217 222 224 225 226 227 228 231 232 233 233 233 234 235 236
10
11
Edible uses of oils and fats
10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9
CONTENTS
Spreads: butter and ghee 10.1.1 Butter 10.1.2 Ghee Spreads: margarine and vanaspati 10.2.1 Margarine 10.2.2 Vanaspati Baking fats, doughs and shortenings Frying oils and fats Salad oils, mayonnaise and salad cream and French dressings Chocolate and confectionery fats Ice cream Incorporation of vegetable oils into dairy products Edible coatings and spray processing 10.10 Emulsifying agents Bibliography and references
Non-edible uses of oils and fats
11.1 Introduction 11.2 Basic oleochemicals 11.2.1 Acids 11.2.2 Esters 11.2.3 Alcohols 11.2.4 Fatty amines 11.3 Surfactants 11.3.1 Anionic surfactants 11.3.1.1 Production from carboxylic acids 11.3.1.2 Production from alcohols 11.3.2 Nonionic surfactants 11.3.3 Ethoxylation and propoxylation of alcohols and esters 11.3.4 Alkyl polyglycosides 11.3.5 Cationic surfactants: cyanides, amines and other nitrogen-containing compounds 11.3.6 Gemini surfactants and cleavable surfactants 11.4 Personal care products 11.5 Lubricants 11.6 Biodiesel 11.7 Glycerol 11.8 Dibasic acids 11.9 Dimers, isostearic acid, estolides, Guerbet alcohols and acids 11.10 Oleochemicals from castor oil 11.11 Surface coatings and inks 11.12 Epoxides, hydroxy acids, polyurethanes Bibliography and references
Index
xi
238
238 238 240 241 241 244 245 246 247 248 252 253 253 254 255
257
257 258 258 259 261 261 261 264 264 264 265 265 266
266 267 269 269 271 274 274 275 276 277 279 280
282