Recent Advances in Polyphenol Research, Volume 3

Plant polyphenols are secondary metabolites that constitute one ofthe most common and widespread groups of natural products. Theyexpress a large and diverse panel of biological activitiesincluding beneficial effects on both plants and humans. Manypolyphenols, from their structurally simplest representatives totheir oligo/polymeric versions (also referred to as vegetabletannins) are notably known as phytoestrogens, plant pigments,potent antioxidants, and protein interacting agents.Sponsored by Groupe Polyphénols, this publication, which isthe third volume in this highly regarded Recent Advances inPolyphenol Research series, is edited by VéroniqueCheynier, Pascale Sarni-Manchado, and Stéphane Quideau (thecurrent President of Groupe Polyphénols). Like theirpredecessors, they have once again put together an impressivecollection of cutting-edge chapters written by expert scientistsinternationally respected in their respective field of polyphenolsciences. This Volume 3 provides the latest information and opinionon the following major research topics about polyphenols:* Organic chemistry and physical chemistry* Biosynthesis, genetics and metabolic engineering* The role of polyphenols in plants and ecosystems* Health and nutrition* Analysis and metabolomicsChemists, biochemists, plant scientists, pharmacognosists andpharmacologists, biologists, ecologists, food scientists andnutritionists will all find this book an invaluable resource.Libraries in all universities and research institutions where thesedisciplines are studied and taught should have copies on theirbookshelves.

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

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

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

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

2.4 Concluding remarks 63

Acknowledgments 64

References 64

3 Fifty Years of PolyphenolProtein 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 tanninprotein 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

4.3 Synthesis of copigments for studying blue color development 109

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

5.3 Engineering anthocyanin production in plants 137

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

6.2 Transcriptional regulation of anthocyanin biosynthetic genes 147

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

7.2 Biosynthesis 167

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, Ismail 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

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

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

9.3 Chlorogenic acids and hydroxycinnamates 214

References 218

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

10.1 Introduction 223

10.2 Epidemiological studies 225

10.3In vitro studies on olive oils phenolics 225

10.4In vivo studies 228

10.5 Olive oil and cancer 231

10.6 Potential mechanisms of action of olive phenolsto 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-Paramas

11.1 Introduction 249

11.2 Flavonoid metabolism 251

11.3 Preparation of metabolites 253

11.4 Characterisation of flavonoid metabolites 258

11.5 Extraction and preparation 263

11.6 Analysis of metabolites in biological samples 268

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

12.4 Extensions of the basic countercurrent chromatography method 302

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

13.3 Oligomer families with diverse bond connections 319

13.4 Conclusion 345

Acknowledgments 345

References 346

Index 353

A color plate section is located between pages 12 and 13. 2