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Abstract
Carotenoids are found in some food plants, flowers and animals, in free form and also esterified with fatty acids. Recent research has concentrated on the extent of carotenoid esters in these sources, how to assess their presence and the amount available for potential health effects. Focusing on the occurrence and assembly in foods, biosynthesis, analytical methods for identification and quantification, dietary intake and metabolism, the most recent research is represented and a balanced overview of what is known about carotenoid esters is provided.
As the first book to address this topic in a comprehensive way, it ensures a better understanding of the importance of carotenoid esters to both food and health, and provides one source for researchers in food science, nutrition, natural products and the food and pharmaceutical industries. Carotenoid Esters in Foods will be a valued addition to the literature, specifically for those conducting research into carotenoids and carotenoid esters in foods. It is a unique contribution and a must-have source for those in this community.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Carotenoid Esters in Foods: Physical, Chemical and Biological Properties | i | ||
| Preface | v | ||
| Contents | ix | ||
| Part I - Physical and Chemical Properties of Carotenoids | 1 | ||
| Chapter 1 - Structures, Nomenclature and General Chemistry of Carotenoids and Their Esters | 3 | ||
| 1.1 Introduction | 3 | ||
| 1.2 Fatty Acids | 4 | ||
| 1.2.1 Occurrence in Nature | 5 | ||
| 1.2.2 Chemical Structure | 5 | ||
| 1.2.2.1 Isomerism in Unsaturated FAs | 6 | ||
| 1.2.3 Nomenclature | 7 | ||
| 1.2.4 Physical–Chemical Properties | 8 | ||
| 1.2.4.1 Solubility | 8 | ||
| 1.2.4.2 Melting Point | 12 | ||
| 1.2.4.3 Susceptibility to Oxidation | 12 | ||
| 1.2.5 Overview of Biosynthesis | 13 | ||
| 1.2.6 Overview of Actions | 14 | ||
| 1.2.6.1 Sources of Energy | 14 | ||
| 1.2.6.2 Modulation of Membrane Properties | 14 | ||
| 1.2.6.3 Regulation of Gene Expression | 15 | ||
| 1.3 Isoprenoids | 15 | ||
| 1.4 Carotenoids | 15 | ||
| 1.4.1 Occurrence in Nature | 15 | ||
| 1.4.2 Chemical Structure | 17 | ||
| 1.4.2.1 Stereochemistry | 20 | ||
| 1.4.2.1.1\rGeometrical Isomers.Geometrical isomerism refers to the relative position of substituents around a planar carbon–carbon double b... | 21 | ||
| 1.4.2.1.2\rOptical Isomers.A molecule that contains carbon atoms to which four different substituents are attached (that is, asymmetric car... | 22 | ||
| 1.4.2.2 Association of Carotenoid Molecules: Carotenoid Aggregates | 25 | ||
| 1.4.2.3 Carotenoid Breakdown Derivatives | 26 | ||
| 1.4.2.3.1\rCompounds with Vitamin A Activity: Retinoids.Retinoids are diterpenes formed by four isoprene units joined in a head-to-tail man... | 27 | ||
| 1.4.2.3.2\rMammalian Apocarotenoids.Besides CCO1, mammalian genomes can also encode at least another non-haem iron oxygenase enzyme that ca... | 27 | ||
| 1.4.2.3.3\rOdorant and Sapid Compounds.Carotenoids can be cleaved at different asymmetrical locations, giving a series of carbonylic odoran... | 28 | ||
| 1.4.2.3.4\rFungal Hormones.Trisporic acid (Figure 1.2) is a carotenoid breakdown derivative that is formed from β-carotene via retinol. It ... | 29 | ||
| 1.4.2.3.5\rInsect Repellents.The grasshopper ketone (Figure 1.24) was first found in the frothy exudate of the grasshopper Romalea micropte... | 30 | ||
| 1.4.2.3.6\rPhytohormones.Abscisic acid (ABA; Figure 1.25) is a phytohormone derived from the cleavage of the (9Z)-isomers of the epoxycarot... | 30 | ||
| 1.4.3 Nomenclature | 31 | ||
| 1.4.4 General Properties and Relation to Some Actions | 32 | ||
| 1.4.4.1 Size and Shape | 32 | ||
| 1.4.4.2 Solubility | 33 | ||
| 1.4.4.3 UV–Visible Light Absorption and Colour | 33 | ||
| 1.4.4.4 Reactivity | 34 | ||
| 1.5 Association of Carotenoids with Other Molecules | 34 | ||
| 1.5.1 Carotenoid Glucosides | 34 | ||
| 1.5.2 Carotenoproteins | 36 | ||
| 1.5.3 Carotenoid Sulphates | 36 | ||
| 1.5.4 Carotenoid Acyl Esters | 36 | ||
| 1.5.4.1 Types and Occurrences of Carotenoid Esters | 36 | ||
| 1.5.4.2 Nomenclature | 38 | ||
| 1.5.5 Impact of Association with Other Molecules on the Properties of Carotenoids | 40 | ||
| 1.5.5.1 Size and Shape | 40 | ||
| 1.5.5.2 Solubility | 40 | ||
| 1.5.5.3 UV–Visible Light Absorption and Colour | 41 | ||
| 1.5.5.4 Reactivity | 41 | ||
| References | 41 | ||
| Chapter 2 - Carotenoid Assembly in Fruits and Vegetables | 51 | ||
| 2.1 Introduction | 51 | ||
| 2.2 Plastid Morphology During Fruit and Vegetable Development and Ripening | 53 | ||
| 2.3 Forms of Carotenoid Deposition in Plastids | 55 | ||
| 2.4 Chemical Structures of Carotenoids and Their Locations within Plastidal Structures | 58 | ||
| 2.5 Carotenoid Ester Deposition in Selected Plant Material | 60 | ||
| 2.5.1 Mamey Sapote (Pouteria sapota [Jacq.] H.E. Moore & Stearn) | 60 | ||
| 2.5.2 Goji (Lycium barbarum L.) | 61 | ||
| 2.5.3 Papaya (Carica papaya L.) | 62 | ||
| 2.5.4 Mango (Mangifera indica L.) | 62 | ||
| 2.6 Hypotheses on the Biological Importance of Carotenoid Esterification in Plants | 63 | ||
| References | 64 | ||
| Chapter 3 - Chemical Synthesis of Carotenoid Esters | 68 | ||
| 3.1 Introduction | 68 | ||
| 3.2 Ester Synthesis for Purification and Structure Elucidation Studies | 69 | ||
| 3.3 Synthesis of Esters to Enhance Stability and Bioavailability | 73 | ||
| 3.3.1 Carotenoid Esters of Fatty Acids, Hydroxy Acids and Bifunctional Acids | 73 | ||
| 3.3.2 Polymeric Esters | 77 | ||
| 3.4 Amphipathic Carotenoid Esters | 78 | ||
| 3.4.1 Synthesis of Ionic (Charged) Carotenoid Esters | 79 | ||
| 3.4.2 Non-charged Hydrophilic Esters | 86 | ||
| 3.5 Synthesis of Bifunctional Carotenoid Esters | 88 | ||
| 3.5.1 Combination with Other Antioxidants | 88 | ||
| 3.5.1.1 Combination with Other Carotenoids | 88 | ||
| 3.5.1.2 Combination with Other Hydrophobic Antioxidants | 91 | ||
| 3.5.1.3 Combination with Hydrophilic Antioxidants | 94 | ||
| 3.5.2 Combination with Porphyrins | 99 | ||
| 3.6 Conclusions | 103 | ||
| Abbreviations | 103 | ||
| Acknowledgements | 104 | ||
| References | 104 | ||
| Part II - Carotenoid Biosynthesis and Occurrence of Carotenoid Esters | 109 | ||
| Chapter 4 - General Overview of Carotenoid Biosynthesis | 111 | ||
| 4.1 Introduction | 111 | ||
| 4.2 Carotenoids and Isoprenoid Biosynthesis | 112 | ||
| 4.2.1 The Isoprenoid Pathway | 112 | ||
| 4.2.2 Stages of Carotenoid Biosynthesis | 112 | ||
| 4.3 Origin of the Isoprene Unit | 113 | ||
| 4.3.1 The Acetate–Mevalonate Pathway | 114 | ||
| 4.3.2 Conversion of Mevalonate into Isopentenyl Diphosphate | 114 | ||
| 4.3.3 The Mevalonate-independent Pathway to IDP | 114 | ||
| 4.4 Formation of Geranylgeranyl Diphosphate | 115 | ||
| 4.5 Formation of Phytoene | 116 | ||
| 4.6 Desaturation | 117 | ||
| 4.7 Cyclisation | 119 | ||
| 4.8 Hydroxylation | 123 | ||
| 4.8.1 Hydroxylation at C(3) | 123 | ||
| 4.8.2 Introduction of Hydroxy and Keto Groups at Other Positions | 124 | ||
| 4.9 Later Reactions | 125 | ||
| 4.9.1 Epoxidation | 125 | ||
| 4.9.2 Formation of Other End Groups | 125 | ||
| 4.9.3 Esterification | 126 | ||
| 4.10 Carotenoid Breakdown Products | 126 | ||
| 4.10.1 Apocarotenoids | 126 | ||
| 4.10.2 Carotenoid Cleavage Enzymes | 127 | ||
| 4.10.3 Saffron and Bixin | 128 | ||
| 4.11 Regulation in Higher Plants | 128 | ||
| 4.11.1 Environmental, Nutritional and Developmental Factors | 128 | ||
| 4.11.1.1 Regulation of Biosynthesis in Chloroplasts | 129 | ||
| 4.11.1.2 Regulation of Carotenoid Biosynthesis in Chromoplasts | 129 | ||
| 4.11.1.3 Environmental Stress | 130 | ||
| 4.12 Regulation in Algae | 130 | ||
| 4.13 Enzymes | 130 | ||
| 4.14 Conclusions | 132 | ||
| References | 132 | ||
| Chapter 5 - Biosynthesis and Esterification of Carotenoids During Fruit Ripening | 137 | ||
| 5.1 Fruit Classification Regarding Carotenoid Composition and Occurrence of Carotenoid Esters | 137 | ||
| 5.2 Main Pattern of Changes in Carotenoid Composition and Esterification During Fruit Ripening | 139 | ||
| 5.3 Carotenoid Pathway in Fruits and Regulation During Ripening | 143 | ||
| 5.3.1 Regulation of Carotenoid Accumulation in Fruit | 147 | ||
| 5.3.2 Localisation of Carotenoid Ester Biosynthesis | 151 | ||
| 5.4 Conclusion | 152 | ||
| Acknowledgements | 153 | ||
| References | 153 | ||
| Chapter 6 - Occurrence and Metabolism of Carotenoid Esters in Marine Organisms | 160 | ||
| 6.1 Introduction | 160 | ||
| 6.1.1 Sources of Carotenoids in Food and Food Chains | 160 | ||
| 6.1.2 Isolation and Analysis | 161 | ||
| 6.2 Carotenoids and Esters in Algae | 162 | ||
| 6.2.1 Long-chain Acyl Esters | 162 | ||
| 6.2.2 Acetate Esters | 162 | ||
| 6.2.3 Esters of C(19) Hydroxy Carotenoids | 163 | ||
| 6.3 Sulphate Esters in Bacteria | 164 | ||
| 6.4 Carotenoid Esters in Marine Animals | 165 | ||
| 6.4.1 Carotenoid Esters in Fish | 166 | ||
| 6.4.1.1 Skin | 166 | ||
| 6.4.1.2 Muscle Tissue (Flesh) | 168 | ||
| 6.4.1.3 Other Tissues and Eggs | 170 | ||
| 6.4.1.4 Physiological Changes | 170 | ||
| 6.4.2 Carotenoid Esters in Invertebrate Animals | 170 | ||
| 6.4.2.1 Crustaceans: Occurrence of Esters | 171 | ||
| 6.4.2.2 Metabolism in Crustaceans | 171 | ||
| 6.4.2.3 Crustaceans: Egg Production and Hatching | 172 | ||
| 6.4.2.4 Coelenterates | 172 | ||
| 6.4.2.5 Echinoderms | 173 | ||
| 6.4.2.6 Molluscs | 173 | ||
| 6.4.2.7 Sponges | 175 | ||
| 6.5 Conclusions | 177 | ||
| References | 178 | ||
| Chapter 7 - Occurrence of Carotenoid Esters in Foods | 182 | ||
| 7.1 Introduction | 182 | ||
| 7.2 Occurrence of Xanthophyll Esters in Food | 184 | ||
| 7.2.1 Fruits and Vegetables | 185 | ||
| 7.2.2 Wheat (Triticum spp.) and Related Cereals | 197 | ||
| 7.2.3 Flowers | 198 | ||
| 7.2.4 Animals | 201 | ||
| 7.2.4.1 Birds | 201 | ||
| 7.2.4.2 Crustaceans | 202 | ||
| 7.2.4.3 Fish | 202 | ||
| 7.2.4.4 Molluscs | 203 | ||
| 7.2.5 Human Milk | 203 | ||
| Acknowledgements | 277 | ||
| References | 277 | ||
| Part III - Analytical Methods for Determination ofCarotenoid Esters | 285 | ||
| Chapter 8 - Extraction and Cleanup of Xanthophyll Esters | 287 | ||
| 8.1 Introduction | 287 | ||
| 8.2 Extraction of Carotenoids and Carotenoid Esters | 288 | ||
| 8.2.1 Liquid Extraction at Atmospheric Pressure | 288 | ||
| 8.2.2 UAE and MAE | 290 | ||
| 8.2.3 PEF-assisted Extraction | 291 | ||
| 8.2.4 Accelerated Solvent Extraction | 291 | ||
| 8.2.5 Supercritical Fluid Extraction | 292 | ||
| 8.2.6 Enzyme-assisted Extraction | 293 | ||
| 8.2.7 Extraction Using Green Solvents | 294 | ||
| 8.3 Cleanup of Carotenoid Extracts for Carotenoid Ester Analysis | 295 | ||
| 8.4 Conclusion | 299 | ||
| Acknowledgements | 300 | ||
| References | 300 | ||
| Chapter 9 - Separation | 304 | ||
| 9.1 Introduction | 304 | ||
| 9.2 Separation of Carotenoid Esters by 1D Liquid Chromatography in Food Matrices | 305 | ||
| 9.3 Separation of Carotenoid Esters by 2D Chromatography in Food Matrices | 312 | ||
| 9.3.1 Carotenoid Ester Separation by Comprehensive Liquid Chromatography | 312 | ||
| 9.3.2 Carotenoid Ester Separation by Comprehensive Supercritical Fluid Chromatography × Liquid Chromatography | 315 | ||
| 9.3.3 Carotenoid Ester Separation by Offline Multidimensional Chromatography | 316 | ||
| 9.4 Carotenoid Ester Separation by 1D Supercritical Fluid Chromatography in Food Matrices | 317 | ||
| References | 319 | ||
| Chapter 10 - Identification of Carotenoids and Carotenoid Esters | 322 | ||
| 10.1 Introduction | 322 | ||
| 10.2 UV/Vis Spectrophotometry | 323 | ||
| 10.2.1 Relationship Between Chemical Structure and UV/Vis Characteristics | 324 | ||
| 10.2.1.1 Number of Conjugated Double Bonds | 325 | ||
| 10.2.1.2 Geometrical Isomers | 325 | ||
| 10.2.1.3 Optical Isomers | 333 | ||
| 10.2.1.4 Cyclic End Groups | 333 | ||
| 10.2.1.5 Hydroxy and Acyl Ester Groups | 334 | ||
| 10.2.1.6 Acetylenic and Allenic Groups | 334 | ||
| 10.2.1.7 Carbonyl Groups | 334 | ||
| 10.2.1.8 Epoxide Groups | 336 | ||
| 10.2.2 Effect of Solvents | 336 | ||
| 10.3 Mass Spectrometry | 337 | ||
| 10.3.1 Acquisition of Mass Data | 343 | ||
| 10.3.2 Identification by APCI(+) | 344 | ||
| 10.4 Conclusions | 347 | ||
| Acknowledgements | 347 | ||
| References | 348 | ||
| Chapter 11 - Quantification and Method Validation | 351 | ||
| 11.1 Introduction | 351 | ||
| 11.2 Sampling and Sample Preparation | 353 | ||
| 11.3 Quantification by LC-UV/Vis Detector | 355 | ||
| 11.3.1 Percentage of Area Method | 355 | ||
| 11.3.2 External Standard Method | 356 | ||
| 11.3.2.1 Calibration Using the Curve of a Xanthophyll Ester | 357 | ||
| 11.3.2.2 Calibration Using the Curve of a Free Xanthophyll or Carotene | 357 | ||
| 11.3.3 Internal Standard Method | 359 | ||
| 11.4 Quantification by Liquid Chromatography–Mass Spectrometry | 360 | ||
| 11.5 Method Validation | 361 | ||
| 11.5.1 Selectivity | 362 | ||
| 11.5.2 Trueness and Accuracy | 363 | ||
| 11.5.3 Precision | 364 | ||
| 11.5.4 Limits of Detection and Quantification | 365 | ||
| 11.5.5 Linearity | 367 | ||
| 11.5.6 Robustness | 368 | ||
| 11.6 Final Remarks | 368 | ||
| Acknowledgements | 368 | ||
| References | 369 | ||
| Part IV - Dietary Intake, Digestion, Absorption and Metabolism of Carotenoids and their Esters | 373 | ||
| Chapter 12 - Dietary Intake of Carotenoids: Nutritional Status Assessment and the Importance of Considering Free and Ester Forms in Foods | 375 | ||
| 12.1 Introduction | 375 | ||
| 12.2 Assessment of Carotenoid Dietary Intake | 377 | ||
| 12.2.1 Assessment Methods Used in Populations and Individuals | 377 | ||
| 12.2.2 Dietary Questionnaires | 379 | ||
| 12.2.3 Food Intake and Measurement of Carotenoid Intake | 380 | ||
| 12.3 Dietary Carotenoid Intake | 382 | ||
| 12.4 Interpretation of Dietary Carotenoid Intake | 385 | ||
| 12.5 Conclusions | 386 | ||
| References | 386 | ||
| Chapter 13 - Bioavailability and Metabolism of Carotenoid Esters | 390 | ||
| 13.1 Introduction | 390 | ||
| 13.2 Digestion and Absorption of Carotenoid Esters and Their Metabolites | 395 | ||
| 13.2.1 Bioavailability of Free vs. Esterified Xanthophylls | 395 | ||
| 13.2.2 Bioaccessibility of Xanthophyll Esters | 403 | ||
| 13.2.3 Intestinal Uptake, Metabolism and Absorption of Xanthophylls | 409 | ||
| 13.3 Are Xanthophylls Acylated in Human Tissues | 411 | ||
| 13.4 Final Remarks | 415 | ||
| Acknowledgements | 416 | ||
| References | 416 | ||
| Chapter 14 - In Vitro Digestion Protocols: The Benchmark for Estimation of In Vivo Data | 421 | ||
| 14.1 The Application of Good Practices in the Use of the Term ‘Bioavailability’ | 421 | ||
| 14.1.1 The Need for Splitting the Term ‘Bioavailability’ into ‘Bioaccessibility’ and ‘Bioactivity’: A Practicable Achievement vs.... | 423 | ||
| 14.1.2 Applications of the Bioaccessibility Concept in Food and Nutrition Science | 425 | ||
| 14.2 In Vitro Digestion Protocols: The Imitation Game | 425 | ||
| 14.2.1 Key Developments in the Design of In Vitro Digestion Protocols | 426 | ||
| 14.2.2 Digestion of Lipophilic Compounds or How to Cross the Water Barrier | 429 | ||
| 14.2.3 Methods Applied to Measure the Micellarisation of Carotenoids: A Practical Approach | 430 | ||
| 14.2.3.1 Critical Factors That Affect the Micellarisation of Carotenoids | 430 | ||
| 14.2.3.2 Correlation of Carotenoid In Vitro Digestion Data with the In Vivo Absorption Studies | 434 | ||
| 14.2.3.3 Description of In Vitro Digestion Protocols Applied to Measure the Micellarisation of Carotenoids | 438 | ||
| 14.2.4 The Direction of the Magnitude of In Vitro Digestion Protocols | 440 | ||
| 14.2.4.1 The Xanthophyll Esters: A Case Study | 446 | ||
| 14.3 Conclusions | 448 | ||
| Acknowledgements | 448 | ||
| References | 448 | ||
| Part V - Final Remarks | 459 | ||
| Chapter 15 - Carotenoid Esters: Opening New Perspectives and Trends | 461 | ||
| References | 464 | ||
| Subject Index | 466 |