Véronique Cheynier and Pascale Sarni-Manchado are based at Institut National de la Recherche Agronomique, UMR Sciences Pour l'Enologie, Montpellier, France. Stéphane Quideau is at the University of Bordeaux, Institut Européen de Chimie et Biologie, (ISM, CNRS-UMR 5255), France.

"Readers will also appreciate the text's comprehensive bibliography. Summing Up: Highly recommended. General readers, upper-division undergraduates, researchers/faculty." (Choice, 1 April 2012)

• Contributors xvPreface xix1 Plant Phenolics: A Biochemical and Physiological Perspective 1Vincenzo Lattanzio, Angela Cardinali and Vito Linsalata1.1 The general phenolic metabolism in plants 11.2 Effect of non-freezing low temperature stress on phenolic metabolism in crop plants 61.3 Plant phenolics as defence compounds 111.3.1 Phenolic-mediated induced resistance of apples against fungal pathogens 121.3.2 Contribution of vigna phenolics to plant protection against insects 161.4 Diversion of carbon skeletons from primary to phenolic-related secondary metabolism 191.4.1 Metabolic costs of adaptive responses to adverse environmental conditions 211.4.2 Transduction pathway between nutrient depletion and enhanced polyphenol content 24References 262 Polyphenols: From Plant Adaptation to Useful Chemical Resources 41Alain-Michel Boudet2.1 The emergence of phenolic metabolism and the adaptation of plants to a terrestrial environment 412.2 The shikimate pathway: a complex and subtle interface between primary metabolism and phenolic metabolism 472.2.1 Quinic acid, a specific component of higher plants 492.2.2 The postchorismate branch of the shikimate pathway leading to phenylalanine: one or two metabolic routes in plants? 532.2.2.1 Intracellular location of enzymes 542.2.2.2 Complex and new regulatory mechanisms in the shikimate pathway 552.3 Plant (poly)phenols: a diversified reservoir of useful chemicals 562.3.1 The health-promoting properties of polyphenols 572.3.2 A new time for lignocellulosics utilization through biotechnology 582.3.2.1 Biomass pretreatment and enzymatic conversion of polysaccharides 592.3.2.2 Lignins: degradation, bioconversion 602.3.2.3 The fermentation step towards the production of bioalcohols 612.3.2.4 Biorefinery pilot plants 612.3.2.5 Quality and availability of the upstream resource 612.3.2.6 Future prospects 622.3.3 Chemical and catalytic valorization of polyphenols 632.4 Concluding remarks 63Acknowledgments 64References 643 Fifty Years of Polyphenol–Protein Complexes 71Ann E. Hagerman3.1 Introduction 713.2 Precipitable complexes 743.3 Soluble complexes 763.4 Proline-rich proteins 783.5 Mechanisms of binding 793.6 Stoichiometry of binding 803.7 Protein conformation 823.8 Covalent tannin–protein complexes 833.9 Conclusions 90Acknowledgments 91References 914 Chemistry of Flavonoids in Color Development 99Kumi Yoshida, Kin-ichi Oyama and Tadao Kondo4.1 Introduction 994.2 Synthetic studies on anthocyanins toward polyacylated pigments 1034.2.1 Previously reported syntheses of anthocyanins 1034.2.2 Synthesis of anthocyanin using biomimetic oxidation 1054.2.3 Transformation of flavonol derivatives to anthocyanins via a flavenol glycoside 1074.3 Synthesis of copigments for studying blue color development 1094.3.1 Copigmentation in metalloanthocyanins 1104.3.2 Synthesis of glycosylated flavones 1124.3.3 Chiral recognition in metalloanthocyanin formation 1144.3.4 Synthesis of acylquinic acid derivatives for studies on hydrangea coloration 1184.4 Conclusion 122Abbreviations 123Acknowledgments 124References 1245 Colouring up Plant Biotechnology 131Cathie Martin, Yang Zhang, Laurence Tomlinson, Kalyani Kallam, Jie Luo, Jonathan D.G. Jones, Antonio Granell, Diego Orzaez and Eugenio Butelli5.1 Introduction 1315.2 Plant production of anthocyanins 1325.2.1 Synthesis of anthocyanins 1325.2.2 Transport of anthocyanins 1325.2.3 Decoration of anthocyanins 1325.2.4 Factors affecting the colour of anthocyanins 1345.2.5 Copigmentation 1355.2.6 Transcriptional regulation of anthocyanin biosynthesis 1355.3 Engineering anthocyanin production in plants 1375.3.1 An in vivo reporter of promoter activity 1375.3.2 Biofortified crops 1385.3.3 Visually traceable system for VIGS analysis of gene function 1385.4 Conclusions 139Acknowledgements 139References 1396 Anthocyanin Biosynthesis, Regulation, and Transport: New Insights from Model Species 143Lucille Pourcel, Andrés Bohórquez-Restrepo, Niloufer G. Irani and Erich Grotewold6.1 Anthocyanins and related pigments in model plant species 1436.1.1 General characteristics of anthocyanins 1436.1.2 Anthocyanin biosynthetic enzymes 1456.1.3 Anthocyanins in Arabidopsis 1466.2 Transcriptional regulation of anthocyanin biosynthetic genes 1476.2.1 Maize 1476.2.2 Arabidopsis 1496.2.3 Petunia 1506.2.4 Snapdragon 1506.3 Anthocyanin transport and subvacuolar localization 1516.4 Concluding remarks 154References 1547 Shedding Light on the Black Boxes of the Proanthocyanidin Pathway with Grapevine 161Yung-Fen Huang, Véronique Cheynier and Nancy Terrier7.1 Tools available on grape to study PA biosynthesis 1617.1.1 Grape PAs 1627.1.1.1 Grape PA structure 1627.1.1.2 Grape PA variations according to genotype, tissue and development 1647.1.2 Grape genetic and genomic tools 1667.2 Biosynthesis 1677.2.1 Enzymes of the pathway 1677.2.2 Transport and storage of PAs 1697.2.3 PA polymerisation 1747.2.3.1 Nature of the extension units 1747.2.3.2 Enzymatic or chemical polymerisation 1757.2.3.3 Subcellular localisation of polymerisation 1767.3 Regulation of the pathway 176References 1828 Phenolic Compounds in Plant Defense and Pathogen Counter-defense Mechanisms 191Fouad Daayf, Abdelbasset El Hadrami, Ahmed F. El-Bebany, Maria A. Henriquez, Zhen Yao, Holly Derksen, Ismaïl El-Hadrami and Lorne R. Adam8.1 Introduction 1918.2 Plant defenses and pathogen counter-defenses 1928.3 Phenolic-related plant responses to pathogens 1948.3.1 Cotton–Verticillium dahliae 1948.3.2 Cucumber—Sphaerotheca fuliginea 1958.3.3 Chickpea—Fusarium oxysporum f. sp. ciceris 1968.3.4 Potato–Verticillium dahliae 1968.3.5 Potato–Phytophthora infestans 1978.3.6 Sunflower–Verticillium dahliae 1988.3.7 Date palm–Fusarium oxysporum f. sp. albedinis 1998.3.8 Canola–Leptosphaeria maculans 1998.3.9 Saskatoons–Entomosporium mespili 2008.4 Pathogens counter-defense against plants’ phenolic-related defenses 2008.4.1 Phytophthora infestans 2018.4.2 Verticillium dahliae 2018.5 Concluding remarks 202Acknowledgments 203References 2039 Absorption and Metabolism of Dietary Chlorogenic Acids and Procyanidins 209Gary Williamson and Angelique Stalmach9.1 Introduction 2099.2 Procyanidins 2109.2.1 Gut lumen stability of procyanidins 2119.2.2 Absorption of intact procyanidins from the small intestine 2119.2.3 Mechanism of absorption across small intestine 2129.2.4 Absorption from the colon after microbial metabolism 2129.3 Chlorogenic acids and hydroxycinnamates 2149.3.1 Transport of chlorogenic acids 2149.3.2 Chlorogenic acid absorption in humans 2159.3.3 Chlorogenic acid metabolism 217References 21810 Extra-Virgin Olive Oil—Healthful Properties of Its Phenolic Constituents 223Francesco Visioli and Elena Bernardini10.1 Introduction 22310.2 Epidemiological studies 22510.3 In vitro studies on olive oil’s phenolics 22510.4 In vivo studies 22810.5 Olive oil and cancer 23110.6 Potential mechanisms of action of olive phenols—to be elucidated 23210.7 Focus on hydroxytyrosol 23310.8 Olive mill waste water as a source of olive phenols 23610.9 Conclusions 240Acknowledgments 244References 24411 Analysis and Characterisation of Flavonoid Phase II Metabolites 249Celestino Santos-Buelga, Susana González-Manzano, Montserrat Dueñas and Ana M. González-Paramás11.1 Introduction 24911.2 Flavonoid metabolism 25111.3 Preparation of metabolites 25311.3.1 Isolation from plant sources 25411.3.2 Enzymatic synthesis of metabolites 25411.3.3 Chemical synthesis 25511.3.4 Purification of metabolites 25711.4 Characterisation of flavonoid metabolites 25811.4.1 UV spectra 25811.4.2 Nuclear magnetic resonance 26011.4.3 Mass spectrometry 26111.5 Extraction and preparation 26311.5.1 Sample preparation and storage 26411.5.2 Hydrolysis 26511.5.3 Solvent extraction 26611.5.4 Solid phase extraction 26711.6 Analysis of metabolites in biological samples 26811.6.1 Quantification of total polyphenol metabolites 26911.6.2 Analysis of individual metabolites 27011.6.3 High performance liquid chromatography 27011.6.4 Detection systems 27211.6.5 Trends in the chromatographic analysis of flavonoid metabolites 276Acknowledgments 277References 27712 High-speed Countercurrent Chromatography in the Separation of Polyphenols 287Andrew Marston12.1 Foreword 28712.2 High-speed countercurrent chromatography 28812.3 Separations of polyphenols 29112.3.1 Preparative applications 29112.3.1.1 Stilbene glycosides 29112.3.1.2 Flavonolignans 29312.3.1.3 Flavonoids 29512.3.1.4 Anthocyanins 29612.3.1.5 Proanthocyanidins and tannins 29712.3.2 Analytical applications 30112.4 Extensions of the basic countercurrent chromatography method 30212.4.1 Reversed-phase operation 30212.4.2 Multiple dual-mode operation 30312.4.3 Elution–extrusion 30312.4.4 Gradient elution 30412.4.5 Hsccc/ms 30512.4.6 Complexation HSCCC 30612.4.7 High-performance ccc 307References 30713 Strategies for the Controlled Synthesis of Oligomeric Polyphenols 311Scott A. Snyder13.1 Introduction 31113.2 Serial oligomer families 31313.2.1 Overview 31313.2.2 Catechin-derived oligomers 31313.2.3 Ellagitannin-derived oligomers 31613.3 Oligomer families with diverse bond connections 31913.3.1 Overview 31913.3.2 The resveratrol family of oligomeric natural products 32013.3.2.1 Introduction 32013.3.2.2 Biomimetic approaches 32113.3.2.3 Stepwise synthesis approaches 33013.3.3 Rosmarinic-acid-derived oligomers 33713.4 Conclusion 345Acknowledgments 345References 346Index 353

Véronique Cheynier and Pascale Sarni-Manchado are based at Institut National de la Recherche Agronomique, UMR Sciences Pour l'Enologie, Montpellier, France. Stéphane Quideau is at the University of Bordeaux, Institut Européen de Chimie et Biologie, (ISM, CNRS-UMR 5255), France.

"Readers will also appreciate the text's comprehensive bibliography. Summing Up: Highly recommended. General readers, upper-division undergraduates, researchers/faculty." (Choice, 1 April 2012)

• Contributors xvPreface xix1 Plant Phenolics: A Biochemical and Physiological Perspective 1Vincenzo Lattanzio, Angela Cardinali and Vito Linsalata1.1 The general phenolic metabolism in plants 11.2 Effect of non-freezing low temperature stress on phenolic metabolism in crop plants 61.3 Plant phenolics as defence compounds 111.3.1 Phenolic-mediated induced resistance of apples against fungal pathogens 121.3.2 Contribution of vigna phenolics to plant protection against insects 161.4 Diversion of carbon skeletons from primary to phenolic-related secondary metabolism 191.4.1 Metabolic costs of adaptive responses to adverse environmental conditions 211.4.2 Transduction pathway between nutrient depletion and enhanced polyphenol content 24References 262 Polyphenols: From Plant Adaptation to Useful Chemical Resources 41Alain-Michel Boudet2.1 The emergence of phenolic metabolism and the adaptation of plants to a terrestrial environment 412.2 The shikimate pathway: a complex and subtle interface between primary metabolism and phenolic metabolism 472.2.1 Quinic acid, a specific component of higher plants 492.2.2 The postchorismate branch of the shikimate pathway leading to phenylalanine: one or two metabolic routes in plants? 532.2.2.1 Intracellular location of enzymes 542.2.2.2 Complex and new regulatory mechanisms in the shikimate pathway 552.3 Plant (poly)phenols: a diversified reservoir of useful chemicals 562.3.1 The health-promoting properties of polyphenols 572.3.2 A new time for lignocellulosics utilization through biotechnology 582.3.2.1 Biomass pretreatment and enzymatic conversion of polysaccharides 592.3.2.2 Lignins: degradation, bioconversion 602.3.2.3 The fermentation step towards the production of bioalcohols 612.3.2.4 Biorefinery pilot plants 612.3.2.5 Quality and availability of the upstream resource 612.3.2.6 Future prospects 622.3.3 Chemical and catalytic valorization of polyphenols 632.4 Concluding remarks 63Acknowledgments 64References 643 Fifty Years of Polyphenol–Protein Complexes 71Ann E. Hagerman3.1 Introduction 713.2 Precipitable complexes 743.3 Soluble complexes 763.4 Proline-rich proteins 783.5 Mechanisms of binding 793.6 Stoichiometry of binding 803.7 Protein conformation 823.8 Covalent tannin–protein complexes 833.9 Conclusions 90Acknowledgments 91References 914 Chemistry of Flavonoids in Color Development 99Kumi Yoshida, Kin-ichi Oyama and Tadao Kondo4.1 Introduction 994.2 Synthetic studies on anthocyanins toward polyacylated pigments 1034.2.1 Previously reported syntheses of anthocyanins 1034.2.2 Synthesis of anthocyanin using biomimetic oxidation 1054.2.3 Transformation of flavonol derivatives to anthocyanins via a flavenol glycoside 1074.3 Synthesis of copigments for studying blue color development 1094.3.1 Copigmentation in metalloanthocyanins 1104.3.2 Synthesis of glycosylated flavones 1124.3.3 Chiral recognition in metalloanthocyanin formation 1144.3.4 Synthesis of acylquinic acid derivatives for studies on hydrangea coloration 1184.4 Conclusion 122Abbreviations 123Acknowledgments 124References 1245 Colouring up Plant Biotechnology 131Cathie Martin, Yang Zhang, Laurence Tomlinson, Kalyani Kallam, Jie Luo, Jonathan D.G. Jones, Antonio Granell, Diego Orzaez and Eugenio Butelli5.1 Introduction 1315.2 Plant production of anthocyanins 1325.2.1 Synthesis of anthocyanins 1325.2.2 Transport of anthocyanins 1325.2.3 Decoration of anthocyanins 1325.2.4 Factors affecting the colour of anthocyanins 1345.2.5 Copigmentation 1355.2.6 Transcriptional regulation of anthocyanin biosynthesis 1355.3 Engineering anthocyanin production in plants 1375.3.1 An in vivo reporter of promoter activity 1375.3.2 Biofortified crops 1385.3.3 Visually traceable system for VIGS analysis of gene function 1385.4 Conclusions 139Acknowledgements 139References 1396 Anthocyanin Biosynthesis, Regulation, and Transport: New Insights from Model Species 143Lucille Pourcel, Andrés Bohórquez-Restrepo, Niloufer G. Irani and Erich Grotewold6.1 Anthocyanins and related pigments in model plant species 1436.1.1 General characteristics of anthocyanins 1436.1.2 Anthocyanin biosynthetic enzymes 1456.1.3 Anthocyanins in Arabidopsis 1466.2 Transcriptional regulation of anthocyanin biosynthetic genes 1476.2.1 Maize 1476.2.2 Arabidopsis 1496.2.3 Petunia 1506.2.4 Snapdragon 1506.3 Anthocyanin transport and subvacuolar localization 1516.4 Concluding remarks 154References 1547 Shedding Light on the Black Boxes of the Proanthocyanidin Pathway with Grapevine 161Yung-Fen Huang, Véronique Cheynier and Nancy Terrier7.1 Tools available on grape to study PA biosynthesis 1617.1.1 Grape PAs 1627.1.1.1 Grape PA structure 1627.1.1.2 Grape PA variations according to genotype, tissue and development 1647.1.2 Grape genetic and genomic tools 1667.2 Biosynthesis 1677.2.1 Enzymes of the pathway 1677.2.2 Transport and storage of PAs 1697.2.3 PA polymerisation 1747.2.3.1 Nature of the extension units 1747.2.3.2 Enzymatic or chemical polymerisation 1757.2.3.3 Subcellular localisation of polymerisation 1767.3 Regulation of the pathway 176References 1828 Phenolic Compounds in Plant Defense and Pathogen Counter-defense Mechanisms 191Fouad Daayf, Abdelbasset El Hadrami, Ahmed F. El-Bebany, Maria A. Henriquez, Zhen Yao, Holly Derksen, Ismaïl El-Hadrami and Lorne R. Adam8.1 Introduction 1918.2 Plant defenses and pathogen counter-defenses 1928.3 Phenolic-related plant responses to pathogens 1948.3.1 Cotton–Verticillium dahliae 1948.3.2 Cucumber—Sphaerotheca fuliginea 1958.3.3 Chickpea—Fusarium oxysporum f. sp. ciceris 1968.3.4 Potato–Verticillium dahliae 1968.3.5 Potato–Phytophthora infestans 1978.3.6 Sunflower–Verticillium dahliae 1988.3.7 Date palm–Fusarium oxysporum f. sp. albedinis 1998.3.8 Canola–Leptosphaeria maculans 1998.3.9 Saskatoons–Entomosporium mespili 2008.4 Pathogens counter-defense against plants’ phenolic-related defenses 2008.4.1 Phytophthora infestans 2018.4.2 Verticillium dahliae 2018.5 Concluding remarks 202Acknowledgments 203References 2039 Absorption and Metabolism of Dietary Chlorogenic Acids and Procyanidins 209Gary Williamson and Angelique Stalmach9.1 Introduction 2099.2 Procyanidins 2109.2.1 Gut lumen stability of procyanidins 2119.2.2 Absorption of intact procyanidins from the small intestine 2119.2.3 Mechanism of absorption across small intestine 2129.2.4 Absorption from the colon after microbial metabolism 2129.3 Chlorogenic acids and hydroxycinnamates 2149.3.1 Transport of chlorogenic acids 2149.3.2 Chlorogenic acid absorption in humans 2159.3.3 Chlorogenic acid metabolism 217References 21810 Extra-Virgin Olive Oil—Healthful Properties of Its Phenolic Constituents 223Francesco Visioli and Elena Bernardini10.1 Introduction 22310.2 Epidemiological studies 22510.3 In vitro studies on olive oil’s phenolics 22510.4 In vivo studies 22810.5 Olive oil and cancer 23110.6 Potential mechanisms of action of olive phenols—to be elucidated 23210.7 Focus on hydroxytyrosol 23310.8 Olive mill waste water as a source of olive phenols 23610.9 Conclusions 240Acknowledgments 244References 24411 Analysis and Characterisation of Flavonoid Phase II Metabolites 249Celestino Santos-Buelga, Susana González-Manzano, Montserrat Dueñas and Ana M. González-Paramás11.1 Introduction 24911.2 Flavonoid metabolism 25111.3 Preparation of metabolites 25311.3.1 Isolation from plant sources 25411.3.2 Enzymatic synthesis of metabolites 25411.3.3 Chemical synthesis 25511.3.4 Purification of metabolites 25711.4 Characterisation of flavonoid metabolites 25811.4.1 UV spectra 25811.4.2 Nuclear magnetic resonance 26011.4.3 Mass spectrometry 26111.5 Extraction and preparation 26311.5.1 Sample preparation and storage 26411.5.2 Hydrolysis 26511.5.3 Solvent extraction 26611.5.4 Solid phase extraction 26711.6 Analysis of metabolites in biological samples 26811.6.1 Quantification of total polyphenol metabolites 26911.6.2 Analysis of individual metabolites 27011.6.3 High performance liquid chromatography 27011.6.4 Detection systems 27211.6.5 Trends in the chromatographic analysis of flavonoid metabolites 276Acknowledgments 277References 27712 High-speed Countercurrent Chromatography in the Separation of Polyphenols 287Andrew Marston12.1 Foreword 28712.2 High-speed countercurrent chromatography 28812.3 Separations of polyphenols 29112.3.1 Preparative applications 29112.3.1.1 Stilbene glycosides 29112.3.1.2 Flavonolignans 29312.3.1.3 Flavonoids 29512.3.1.4 Anthocyanins 29612.3.1.5 Proanthocyanidins and tannins 29712.3.2 Analytical applications 30112.4 Extensions of the basic countercurrent chromatography method 30212.4.1 Reversed-phase operation 30212.4.2 Multiple dual-mode operation 30312.4.3 Elution–extrusion 30312.4.4 Gradient elution 30412.4.5 Hsccc/ms 30512.4.6 Complexation HSCCC 30612.4.7 High-performance ccc 307References 30713 Strategies for the Controlled Synthesis of Oligomeric Polyphenols 311Scott A. Snyder13.1 Introduction 31113.2 Serial oligomer families 31313.2.1 Overview 31313.2.2 Catechin-derived oligomers 31313.2.3 Ellagitannin-derived oligomers 31613.3 Oligomer families with diverse bond connections 31913.3.1 Overview 31913.3.2 The resveratrol family of oligomeric natural products 32013.3.2.1 Introduction 32013.3.2.2 Biomimetic approaches 32113.3.2.3 Stepwise synthesis approaches 33013.3.3 Rosmarinic-acid-derived oligomers 33713.4 Conclusion 345Acknowledgments 345References 346Index 353