Recent Advances in Polyphenol Research, Volume 3

Contributors xv

Preface xix

1 Plant Phenolics: A Biochemical and Physiological Perspective 1
Vincenzo Lattanzio, Angela Cardinali and Vito Linsalata

1.1 The general phenolic metabolism in plants 1

1.2 Effect of non-freezing low temperature stress on phenolic metabolism in crop plants 6

1.3 Plant phenolics as defence compounds 11

1.3.1 Phenolic-mediated induced resistance of apples against fungal pathogens 12

1.3.2 Contribution of vigna phenolics to plant protection against insects 16

1.4 Diversion of carbon skeletons from primary to phenolic-related secondary metabolism 19

1.4.1 Metabolic costs of adaptive responses to adverse environmental conditions 21

1.4.2 Transduction pathway between nutrient depletion and enhanced polyphenol content 24

References 26

2 Polyphenols: From Plant Adaptation to Useful Chemical Resources 41
Alain-Michel Boudet

2.1 The emergence of phenolic metabolism and the adaptation of plants to a terrestrial environment 41

2.2 The shikimate pathway: a complex and subtle interface between primary metabolism and phenolic metabolism 47

2.2.1 Quinic acid, a specific component of higher plants 49

2.2.2 The postchorismate branch of the shikimate pathway leading to phenylalanine: one or two metabolic routes in plants? 53

2.2.2.1 Intracellular location of enzymes 54

2.2.2.2 Complex and new regulatory mechanisms in the shikimate pathway 55

2.3 Plant (poly)phenols: a diversified reservoir of useful chemicals 56

2.3.1 The health-promoting properties of polyphenols 57

2.3.2 A new time for lignocellulosics utilization through biotechnology 58

2.3.2.1 Biomass pretreatment and enzymatic conversion of polysaccharides 59

2.3.2.2 Lignins: degradation, bioconversion 60

2.3.2.3 The fermentation step towards the production of bioalcohols 61

2.3.2.4 Biorefinery pilot plants 61

2.3.2.5 Quality and availability of the upstream resource 61

2.3.2.6 Future prospects 62

2.3.3 Chemical and catalytic valorization of polyphenols 63

2.4 Concluding remarks 63

Acknowledgments 64

References 64

3 Fifty Years of Polyphenol-Protein Complexes 71
Ann E. Hagerman

3.1 Introduction 71

3.2 Precipitable complexes 74

3.3 Soluble complexes 76

3.4 Proline-rich proteins 78

3.5 Mechanisms of binding 79

3.6 Stoichiometry of binding 80

3.7 Protein conformation 82

3.8 Covalent tannin-protein complexes 83

3.9 Conclusions 90

Acknowledgments 91

References 91

4 Chemistry of Flavonoids in Color Development 99
Kumi Yoshida, Kin-ichi Oyama and Tadao Kondo

4.1 Introduction 99

4.2 Synthetic studies on anthocyanins toward polyacylated pigments 103

4.2.1 Previously reported syntheses of anthocyanins 103

4.2.2 Synthesis of anthocyanin using biomimetic oxidation 105

4.2.3 Transformation of flavonol derivatives to anthocyanins via a flavenol glycoside 107

4.3 Synthesis of copigments for studying blue color development 109

4.3.1 Copigmentation in metalloanthocyanins 110

4.3.2 Synthesis of glycosylated flavones 112

4.3.3 Chiral recognition in metalloanthocyanin formation 114

4.3.4 Synthesis of acylquinic acid derivatives for studies on hydrangea coloration 118

4.4 Conclusion 122

Abbreviations 123

Acknowledgments 124

References 124

5 Colouring up Plant Biotechnology 131
Cathie Martin, Yang Zhang, Laurence Tomlinson, Kalyani Kallam, Jie Luo, Jonathan D.G. Jones, Antonio Granell, Diego Orzaez and Eugenio Butelli

5.1 Introduction 131

5.2 Plant production of anthocyanins 132

5.2.1 Synthesis of anthocyanins 132

5.2.2 Transport of anthocyanins 132

5.2.3 Decoration of anthocyanins 132

5.2.4 Factors affecting the colour of anthocyanins 134

5.2.5 Copigmentation 135

5.2.6 Transcriptional regulation of anthocyanin biosynthesis 135

5.3 Engineering anthocyanin production in plants 137

5.3.1 An in vivo reporter of promoter activity 137

5.3.2 Biofortified crops 138

5.3.3 Visually traceable system for VIGS analysis of gene function 138

5.4 Conclusions 139

Acknowledgements 139

References 139

6 Anthocyanin Biosynthesis, Regulation, and Transport: New Insights from Model Species 143
Lucille Pourcel, Andrés Bohórquez-Restrepo, Niloufer G. Irani and Erich Grotewold

6.1 Anthocyanins and related pigments in model plant species 143

6.1.1 General characteristics of anthocyanins 143

6.1.2 Anthocyanin biosynthetic enzymes 145

6.1.3 Anthocyanins in Arabidopsis 146

6.2 Transcriptional regulation of anthocyanin biosynthetic genes 147

6.2.1 Maize 147

6.2.2 Arabidopsis 149

6.2.3 Petunia 150

6.2.4 Snapdragon 150

6.3 Anthocyanin transport and subvacuolar localization 151

6.4 Concluding remarks 154

References 154

7 Shedding Light on the Black Boxes of the Proanthocyanidin Pathway with Grapevine 161
Yung-Fen Huang, Véronique Cheynier and Nancy Terrier

7.1 Tools available on grape to study PA biosynthesis 161

7.1.1 Grape PAs 162

7.1.1.1 Grape PA structure 162

7.1.1.2 Grape PA variations according to genotype, tissue and development 164

7.1.2 Grape genetic and genomic tools 166

7.2 Biosynthesis 167

7.2.1 Enzymes of the pathway 167

7.2.2 Transport and storage of PAs 169

7.2.3 PA polymerisation 174

7.2.3.1 Nature of the extension units 174

7.2.3.2 Enzymatic or chemical polymerisation 175

7.2.3.3 Subcellular localisation of polymerisation 176

7.3 Regulation of the pathway 176

References 182

8 Phenolic Compounds in Plant Defense and Pathogen Counter-defense Mechanisms 191
Fouad Daayf, Abdelbasset El Hadrami, Ahmed F. El-Bebany, Maria A. Henriquez, Zhen Yao, Holly Derksen, Ismaïl El-Hadrami and Lorne R. Adam

8.1 Introduction 191

8.2 Plant defenses and pathogen counter-defenses 192

8.3 Phenolic-related plant responses to pathogens 194

8.3.1 Cotton-Verticillium dahliae 194

8.3.2 Cucumber-Sphaerotheca fuliginea 195

8.3.3 Chickpea-Fusarium oxysporum f. sp. ciceris 196

8.3.4 Potato-Verticillium dahliae 196

8.3.5 Potato-Phytophthora infestans 197

8.3.6 Sunflower-Verticillium dahliae 198

8.3.7 Date palm-Fusarium oxysporum f. sp. albedinis 199

8.3.8 Canola-Leptosphaeria maculans 199

8.3.9 Saskatoons-Entomosporium mespili 200

8.4 Pathogens counter-defense against plants' phenolic-related defenses 200

8.4.1 Phytophthora infestans 201

8.4.2 Verticillium dahliae 201

8.5 Concluding remarks 202

Acknowledgments 203

References 203

9 Absorption and Metabolism of Dietary Chlorogenic Acids and Procyanidins 209
Gary Williamson and Angelique Stalmach

9.1 Introduction 209

9.2 Procyanidins 210

9.2.1 Gut lumen stability of procyanidins 211

9.2.2 Absorption of intact procyanidins from the small intestine 211

9.2.3 Mechanism of absorption across small intestine 212

9.2.4 Absorption from the colon after microbial metabolism 212

9.3 Chlorogenic acids and hydroxycinnamates 214

9.3.1 Transport of chlorogenic acids 214

9.3.2 Chlorogenic acid absorption in humans 215

9.3.3 Chlorogenic acid metabolism 217

References 218

10 Extra-Virgin Olive Oil-Healthful Properties of Its Phenolic Constituents 223
Francesco Visioli and Elena Bernardini

10.1 Introduction 223

10.2 Epidemiological studies 225

10.3 In vitro studies on olive oil's phenolics 225

10.4 In vivo studies 228

10.5 Olive oil and cancer 231

10.6 Potential mechanisms of action of olive phenols-to be elucidated 232

10.7 Focus on hydroxytyrosol 233

10.8 Olive mill waste water as a source of olive phenols 236

10.9 Conclusions 240

Acknowledgments 244

References 244

11 Analysis and Characterisation of Flavonoid Phase II Metabolites 249
Celestino Santos-Buelga, Susana González-Manzano, Montserrat Dueñas and Ana M. González-Paramás

11.1 Introduction 249

11.2 Flavonoid metabolism 251

11.3 Preparation of metabolites 253

11.3.1 Isolation from plant sources 254

11.3.2 Enzymatic synthesis of metabolites 254

11.3.3 Chemical synthesis 255

11.3.4 Purification of metabolites 257

11.4 Characterisation of flavonoid metabolites 258

11.4.1 UV spectra 258

11.4.2 Nuclear magnetic resonance 260

11.4.3 Mass spectrometry 261

11.5 Extraction and preparation 263

11.5.1 Sample preparation and storage 264

11.5.2 Hydrolysis 265

11.5.3 Solvent extraction 266

11.5.4 Solid phase extraction 267

11.6 Analysis of metabolites in biological samples 268

11.6.1 Quantification of total polyphenol metabolites 269

11.6.2 Analysis of individual metabolites 270

11.6.3 High performance liquid chromatography 270

11.6.4 Detection systems 272

11.6.5 Trends in the chromatographic analysis of flavonoid metabolites 276

Acknowledgments 277

References 277

12 High-speed Countercurrent Chromatography in the Separation of Polyphenols 287
Andrew Marston

12.1 Foreword 287

12.2 High-speed countercurrent chromatography 288

12.3 Separations of polyphenols 291

12.3.1 Preparative applications 291

12.3.1.1 Stilbene glycosides 291

12.3.1.2 Flavonolignans 293

12.3.1.3 Flavonoids 295

12.3.1.4 Anthocyanins 296

12.3.1.5 Proanthocyanidins and tannins 297

12.3.2 Analytical applications 301

12.4 Extensions of the basic countercurrent chromatography method 302

12.4.1 Reversed-phase operation 302

12.4.2 Multiple dual-mode operation 303

12.4.3 Elution-extrusion 303

12.4.4 Gradient elution 304

12.4.5 Hsccc/ms 305

12.4.6 Complexation HSCCC 306

12.4.7 High-performance ccc 307

References 307

13 Strategies for the Controlled Synthesis of Oligomeric Polyphenols 311
Scott A. Snyder

13.1 Introduction 311

13.2 Serial oligomer families 313

13.2.1 Overview 313

13.2.2 Catechin-derived oligomers 313

13.2.3 Ellagitannin-derived oligomers 316

13.3 Oligomer families with diverse bond connections 319

13.3.1 Overview 319

13.3.2 The resveratrol family of oligomeric natural products 320

13.3.2.1 Introduction 320

13.3.2.2 Biomimetic approaches 321

13.3.2.3 Stepwise synthesis approaches 330

13.3.3 Rosmarinic-acid-derived oligomers 337

13.4 Conclusion 345

Acknowledgments 345

References 346

Index 353