Chemistry and Biology of Volatiles, The

The Chemistry and Biology of Volatiles......Page 5
Contents......Page 7
Foreword......Page 15
List of Contributors......Page 17
Acknowledgements......Page 19
Abbreviations......Page 21
1.1 Introduction......Page 29
1.2 Geraniol – A Typical Example......Page 30
References......Page 36
2.1 Introduction......Page 39
2.2 Plant Isoprenoids......Page 40
2.3 Two IPP-Yielding Pathways in Plants......Page 43
2.5 Compartmentation of Plant Isoprenoid Biosynthesis......Page 44
2.6 The Enzyme Steps of the Plastidic DOXP/MEP Pathway of IPP Formation......Page 45
2.7 Cross-Talk Between the Two IPP Biosynthesis Pathways......Page 47
2.8 Biosynthesis and Emission of Volatile Isoprene at High Irradiance......Page 50
2.8.1 Regulation of Isoprene Emission......Page 53
2.9.1 Fosmidomycin and 5-Ketoclomazone......Page 54
2.10 Inhibition of Carotenoid and Chlorophyll Biosynthesis by Fosmidomycin and 5-Ketoclomazone......Page 55
2.11 Biosynthesis and Emission of Methylbutenol at High Irradiance......Page 56
2.12 Source of Pyruvate for Isoprene and Methylbutenol Biosynthesis......Page 57
2.13 Branching Point of DOXP/MEP Pathway with Other Metabolic Chloroplast Pathways......Page 58
2.14 Is There a Physiological Function of Isoprene and MBO Emission?......Page 59
2.15 Biosynthesis and Emission of Monoterpenes, Sesquiterpenes and Diterpenes......Page 61
2.15.1 Monoterpenes......Page 63
2.16 Some General Remarks on the Regulation of Terpene Biosynthesis in Plants......Page 64
2.17 Volatile Terpenoids as Aroma Compounds of Wine......Page 65
2.19 Conclusion......Page 66
Acknowledgements......Page 67
References......Page 68
3.1 Introduction......Page 77
3.2 Sample Preparation......Page 78
3.2.2 Headspace Sampling......Page 79
3.2.3 Headspace–Solid Phase Microextraction......Page 80
3.2.4 In-Tube Sorptive Extraction......Page 82
3.2.5 Headspace Sorptive Extraction......Page 83
3.2.8 Headspace Liquid-Phase Microextraction......Page 84
3.3 Analysis......Page 87
3.3.1 Fast-GC and Fast-GC-qMS EO Analysis......Page 89
3.3.2 Qualitative Analysis......Page 93
3.3.3 Quantitative Analysis......Page 94
3.3.4 Enantioselective GC......Page 98
3.3.5 Multidimensional GC Techniques......Page 103
3.4 Further Developments......Page 104
3.5 Conclusion......Page 113
References......Page 115
4.1 Introduction......Page 123
4.2 The Specificity and Complexity of Herbivore-Induced VOC Production......Page 125
4.2.1 Plant Endogenous Wound Signalling......Page 127
4.2.2 Herbivore-Derived Elicitors of VOC Emission......Page 130
4.3.1 Within-Plant Defence Signalling......Page 132
4.3.2 Herbivore-Induced VOC Emission as Part of a Metabolic Reconfiguration of the Plant......Page 133
4.3.3 Herbivores Use VOCs to Select Host Plants......Page 135
4.3.4 VOCs as Indirect Defences Against Herbivores......Page 136
4.3.5 VOCs in Plant–Plant Interactions......Page 139
4.4 Conclusion......Page 140
References......Page 142
5.1.2 Classification of Pheromones......Page 151
5.2 History of Pheromone Research......Page 153
5.3.1 The Collecting of Pheromones......Page 155
5.3.3 Structure Determination and Synthesis......Page 156
5.3.5 Structure Elucidation of the Male-Produced Aggregation Pheromone of the Stink Bug Eysarcoris lewisi – A Case Study......Page 157
5.4 Structural Diversity Among Pheromones......Page 160
5.5 Complexity of Multicomponent Pheromones......Page 165
5.6.3 Only One Enantiomer is Bioactive, and its Diastereomer Inhibits the Response to the Pheromone......Page 167
5.6.4 The Natural Pheromone is a Single Enantiomer, and its Opposite Enantiomer or Diastereomer is Also Active......Page 168
5.6.8 One Enantiomer is More Active Than the Other, but an Enantiomeric or Diastereomeric Mixture is More Active Than the Enantiomer Alone......Page 169
5.7 Pheromones With Kairomonal Activities......Page 170
5.8 Mammalian Pheromones......Page 171
5.9 Invention of Pheromone Mimics......Page 173
References......Page 175
6.2 Repellents (DEET, Neem, Essential Oils)......Page 179
6.3 Volatile Synthetic Chemicals and Fumigants......Page 182
6.4 Pheromones......Page 186
6.5 Volatile Allelochemicals......Page 193
6.6 Plant Volatiles and Behavioural Modification of Beneficial Insects......Page 194
6.7 Concluding Comments......Page 195
References......Page 196
7.1 Introduction – The Art of Organic Synthesis......Page 201
7.2.1 D,L-Caryophyllene (1964)......Page 202
7.2.2 β-Vetivone (1973)......Page 203
7.3.1 (Z)-3-Hexenol......Page 204
7.3.2 Citral......Page 205
7.3.3 (—)-Menthol......Page 207
7.4 Remaining Challenges in the Large-Scale Synthesis of Natural and Non-Natural Volatiles......Page 208
7.5.1 Cassis (Blackcurrant)......Page 210
7.5.2 Patchouli......Page 212
7.5.3 Musk......Page 215
7.5.4 Sandalwood......Page 217
7.7 Conclusion......Page 221
Acknowledgements......Page 222
References......Page 223
8.1 Introduction: Flavours as Secondary Metabolites......Page 231
8.2 Sulfur in Plant Biology......Page 232
8.3 Sulfur Compounds as Flavour Volatiles......Page 233
8.4 The Alk(en)yl Cysteine Sulfoxide Flavour Precursors......Page 234
8.5 Biosynthesis of the Flavour Precursors of Allium......Page 235
8.5.1 The Biosynthesis of Allium Flavour Precursors via γ-Glutamyl Peptides......Page 236
8.5.2 The Biosynthesis of Allium Flavour Precursors via Cysteine Synthases......Page 237
8.6.1 S-Methyl-L-cysteine sulfoxide......Page 238
8.6.2 Release of the Allium CSOs......Page 239
8.7 The Allium Flavour Volatiles......Page 240
8.8 The Enzyme Alliinase......Page 241
8.9 The Enzyme Lachrymatory Factor Synthase......Page 242
8.10 The Biological Roles of the Flavour Precursors......Page 243
8.12 GS and Their Biosynthetic Pathways......Page 244
8.13 Release of Volatile GS Hydrolysis Products......Page 246
8.14 The Biological Role of Glucosinolates......Page 248
8.16.1 Complex Organic Sulfur Volatiles......Page 250
8.16.3 Hydrogen Sulfide......Page 251
References......Page 252
9.1 Introduction......Page 259
9.2 The Maillard Reaction......Page 261
9.2.1 The Amadori Rearrangement......Page 262
9.2.3 Retro-Aldolization......Page 263
9.3.1 2-Furfurylthiol......Page 265
9.3.3 Alkyl and Alkenylpyrazines......Page 267
9.4 The Strecker Degradation......Page 269
9.5 Caramelization......Page 272
9.7 Ferulic Acid Degradation......Page 274
9.8 Fat Oxidation......Page 275
References......Page 278
10.1 Introduction......Page 281
10.2 Historical Perspective on Olfactory Perception......Page 282
10.3 Human Olfactory Pathway......Page 283
10.4 Functional Studies in Human Subjects......Page 284
10.6 Single Odorants, Binary Mixtures and Complex Odour Objects......Page 287
10.7 Olfactory Versus Trigeminal Odorant Identification......Page 290
10.8 Orthonasal Versus Retronasal Odour Perception......Page 291
10.9 Specific Anosmias......Page 292
10.10 MHC-Correlated Odour Preferences in Human Subjects......Page 293
10.11 Odour Deprivation and Odour Perception......Page 294
10.12 Age-Related Decline in Olfactory Perception......Page 295
10.14 Epidemiological Studies of Human Olfaction......Page 296
10.15 Active Sampling and Olfactory Perception......Page 297
10.16 Human Olfactory Imagery......Page 298
10.17 Top-Down Influences on Olfactory Perception......Page 299
10.18 Reproductive State and Olfactory Sensitivity......Page 300
10.19 Olfaction, Hunger and Satiety......Page 301
10.20 Odour Perception Bias by Odour Names......Page 302
10.21 Olfaction and Disease States......Page 303
10.22 Prenatal and Postnatal Influences on Infant Odour/Flavour Preferences......Page 304
Acknowledgements......Page 305
References......Page 306
11.1 The Big Picture......Page 319
11.2 Wizardry No. 1: Full Holograms Create Real Emotions......Page 320
11.3 Volatiles Need a Language Wizard......Page 324
11.4 Wizardry No. 2: The Perfumer in the Jungle of Volatiles to Create Emotions......Page 326
11.5 Wizardry No. 3: End Results Are Music to the Nose......Page 331
References......Page 332
12.2 Microencapsulation in the Food Industry......Page 335
12.3.1 Spray Drying......Page 336
12.3.2 Extrusion......Page 340
12.3.3 Cyclodextrin Inclusion Complexes......Page 342
12.3.4 Helical Inclusion Complexes......Page 344
12.3.7 Bottom Spray System......Page 346
12.3.10 Coacervation......Page 348
12.3.11 Double or Multiple Emulsion with Freeze Drying......Page 349
12.3.13 Spray Chilling and Spray Cooling......Page 350
12.3.15 Other Techniques......Page 351
12.4 Conclusion and Future Trends......Page 353
References......Page 354
13.1 Introduction......Page 361
13.2.1 Enzymatic Hydrolysis......Page 363
13.2.2 Neighbouring-Group-Assisted, Non-Enzymatic Hydrolysis......Page 368
13.3.1 Oxidations......Page 374
13.3.2 Reversible Systems......Page 378
13.3.3 Retro 1,4-Additions......Page 382
13.4.1 Performance and Cost Efficiency......Page 384
13.5 Conclusion......Page 385
References......Page 386
14.1 Introduction......Page 391
14.2 The Relative Importance of Anthropogenic Versus Biogenic VOC Emissions to Atmospheric Chemistry......Page 392
14.3 Overview of BVOC Oxidation......Page 393
14.4 The Types of Emitted BVOCs and General Roles in Atmospheric Chemistry......Page 398
14.5 Gas Phase Oxidation of BVOCs......Page 400
14.6 Gas Phase Chemistry of BVOCs in Urban and Suburban Airsheds......Page 402
14.7 Gas Phase Chemistry Within and Above Forests......Page 403
14.8 BVOC Emissions and SOA Formation......Page 405
References......Page 409
Index......Page 417