An introduction to the chemistry and biology of volatiles

__"Coming to a conclusion, this wonderful, informative and very interesting book presents an excellent overview of small volatile organic compounds and their role in our life and environment. Really fascinating is the entirety of scientific disciplines which were addressed by this book."__ –Flavour and Fragrance Journal, 2011 __"... this book deserves to be a well-used reference in the library of any laboratory specialising in VOC".__ –Chemistry World, 2011 Volatile compounds are molecules with a relatively low molecular weight allowing for an efficient evaporation into the air. They are found in many areas of our everyday-life: they are responsible for the communication between species such as plants, insects or mammals; they serve as flavours or fragrances in many food products or perfumed consumer articles; and they play an important role in atmospheric chemistry. This book takes an interdisciplinary approach to volatile molecules. Review-style introductions to the main topics in volatile chemistry and biology are provided by international experts, building into a broad overview of this fascinating field.**Topics covered include:** * The structural variety of volatile compounds * Biogeneration of volatiles * Synthesis of natural and non-natural volatiles * Analysis of volatiles * Volatile compounds as semiochemicals in plant-plant or plant-insect interactions * Volatiles in pest control * Pheromones and the influence of volatiles on mammals * Olfaction and human perception * Volatiles as fragrances * The generation of flavours and food aroma compounds * Stabilisation and controlled release of volatiles * The impact of volatiles on the environment and the atmosphere Content: Chapter 1 Volatiles – An Interdisciplinary Approach (pages 1–10): Andreas HerrmannChapter 2 Biosynthesis and Emission of Isoprene, Methylbutanol and Other Volatile Plant Isoprenoids (pages 11–47): Hartmut K. LichtenthalerChapter 3 Analysis of the Plant Volatile Fraction (pages 49–93): Patrizia Rubiolo, Barbara Sgorbini, Erica Liberto, Chiara Cordero and Carlo BicchiChapter 4 Plant Volatile Signalling: Multitrophic Interactions in the Headspace (pages 95–122): Andre Kessler and Kimberly MorrellChapter 5 Pheromones in Chemical Communication (pages 123–149): Kenji MoriChapter 6 Use of Volatiles in Pest Control (pages 151–172): J. Richard M. Thacker and Margaret R. TrainChapter 7 Challenges in the Synthesis of Natural and Non?Natural Volatiles (pages 173–202): Anthony A. BirkbeckChapter 8 The Biosynthesis of Volatile Sulfur Flavour Compounds (pages 203–229): Meriel G. JonesChapter 9 Thermal Generation of Aroma?Active Volatiles in Food (pages 231–252): Christoph CernyChapter 10 Human Olfactory Perception (pages 253–289): Alan GelperinChapter 11 Perfumery – The Wizardry of Volatile Molecules (pages 291–305): Christophe LaudamielChapter 12 Microencapsulation Techniques for Food Flavour (pages 307–332): Youngjae Byun, Young Teck Kim, Kashappa Goud H. Desai and Hyun Jin ParkChapter 13 Profragrances and Properfumes (pages 333–362): Andreas HerrmannChapter 14 Reactions of Biogenic Volatile Organic Compounds in the Atmosphere (pages 363–388): Russell K. Monson 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 'Coming to a conclusion, this wonderful, informative and very interesting book presents an excellent overview of small volatile organic compounds and their role in our life and environment. Really fascinating is the entirety of scientific disciplines which were addressed by this book.'–Flavour and Fragrance Journal, 2011'... this book deserves to be a well-used reference in the library of any laboratory specialising in VOC'. –Chemistry World, 2011 Volatile compounds are molecules with a relatively low molecular weight allowing for an efficient evaporation into the air. They are found in many areas of our everyday-life: they are responsible for the communication between species such as plants, insects or mammals; they serve as flavours or fragrances in many food products or perfumed consumer articles; and they play an important role in atmospheric chemistry. This book takes an interdisciplinary approach to volatile molecules. Review-style introductions to the main topics in volatile chemistry and biology are provided by international experts, building into a broad overview of this fascinating field. Topics covered include: The structural variety of volatile compounds Biogeneration of volatiles Synthesis of natural and non-natural volatiles Analysis of volatiles Volatile compounds as semiochemicals in plant-plant or plant-insect interactions Volatiles in pest control Pheromones and the influence of volatiles on mammals Olfaction and human perception Volatiles as fragrances The generation of flavours and food aroma compounds Stabilisation and controlled release of volatiles The impact of volatiles on the environment and the atmosphere Volatile compounds are molecules with a relatively low molecular weight allowing for an efficient evaporation into the air. They are found in many areas of our everyday-life: they are responsible for the communication between species such as plants, insects or mammals; they serve as flavours or fragrances in many food products or perfumed consumer articles; and they play an important role in atmospheric chemistry.The Chemistry and Biology of Volatiles takes an interdisciplinary approach to volatile molecules. Review-style introductions to the main topics in volatile chemistry and biology are provided by international experts, building into a broad overview of this fascinating field. Topics covered include:The structural variety of volatile compoundsBiogeneration of volatilesSynthesis of natural and non-natural volatilesAnalysis of volatilesVolatile compounds as semiochemicals in plant-plant or plant-insect interactionsVolatiles in pest controlPheromones and the influence of volatiles on mammalsOlfaction and human perceptionVolatiles as fragrancesThe generation of flavours and food aroma compoundsStabilisation and controlled release of volatilesThe impact of volatiles on the environment and the atmosphereThe Chemistry and Biology of Volatiles is an essential overview of this important field for students and researchers in organic and bioorganic chemistry, biochemistry, flavour and fragrance research, pest control, and atmospheric chemistry. Volatile compounds are molecules with a relatively low molecular weight allowing for an efficient evaporation into the air. They are found in many areas of our everyday-life: they are responsible for the communication between species such as plants, insects or mammals; they serve as flavours or fragrances in many food products or perfumed consumer articles; and they play an important role in atmospheric chemistry. The Chemistry and Biology of Volatiles takes an interdisciplinary approach to volatile molecules. Review-style introductions to the main topics in volatile chemistry and biology are