About the EditorsJess Dreher Reed is Professor of Animal Nutrition at the University of Wisconsin-Madison with over 30 years of postgraduate experience in research on the effects of dietary phytochemicals on the nutrition and health of animals and humans. His research includes development of phytochemical methods for characterization of tannin structure and their interactions with proteins and polysaccharides, and mechanistic studies on the effects of tannins in cell culture and animal models of disease.Victor Armando Pereira de Freitas, current President of the Groupe Polyphénols (since 2016), is Full Professor at the Faculty of Sciences of the University of Porto, Portugal. His research on polyphenols include: structural characterization, chemical transformations in plants and foods during harvest and storage, influence on the sensory properties of foods (color, astringency and bitterness), and other biological properties.Stéphane Quideau, former President of the Groupe Polyphénols (2008-2012), is Full Professor of Organic and Bioorganic Chemistry at the University of Bordeaux, France, and Senior Member of the “Institut Universitaire de France”. His laboratory is involved in research on plant polyphenol chemistry and chemical biology, with particular interests in ellagitannin chemical reactivity and synthesis, and in polyphenol-protein interactions.

• ContributorsPreface1 Achieving Complexity at the Bottom Through the Flavylium Cation-Based Multistate. A Comprehensive Kinetic and Thermodynamic StudyJohan Mendoza and Fernando Pina1.1 Introduction1.2 Flavylium cation as a metamorphosis generator1.3 Extending the multistate of anthocyanins and related compounds to the basic region1.4 The kinetic processes1.5 Conclusions and perspectives2 Proanthocyanidin Oligomers with Doubly-Linked (A-Type) Interflavan Connectivity: Structure and SynthesisKen Ohmori and Keisuke Suzuki2.1 Introduction2.2 Structure2.3 Synthetic studies2.4 Conclusion3 Answering the Call of the Wild: Polyphenols in Traditional Therapeutic PracticeMary Ann Lila and Kriya Dunlap3.1 Introduction3.2 The wildcrafting tradition3.3 How wildcrafted edible plants differ from agricultural commodities3.4 Animal mimickry/Zoopharmacognosy3.5 Probing the mechanisms behind polyphenol-rich traditional medicines bioactivity3.6 Commercialization prospects for wildcrafted polyphenol-rich plants3.7 Acknowledgements4 Causes and Consequences of Condensed Tannin Variation in Populus: A Molecules to Ecosystems PerspectiveKennedy F. Rubert-Nason and Richard L. Lindroth4.1 Introduction4.2 Condensed tannin biosynthesis4.3 Allocational tradeoffs influence CT production4.4 Causes of quantitative and qualitative variation in Populus CTs4.5 Roles of CT variation in Populus-environment interactions4.6 Importance of CTs in Populus-dominated ecosystems of the Anthropocene4.7 Conclusions and challenges5 Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) of Proanthocyanidins to Determine Authenticity of Functional Foods and Dietary SupplementsDaniel Esquivel-Alvarado, Jess D. Reed, and Christian G. Krueger5.1 Introduction5.2 Introduction to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)5.3 Mass spectrometry of proanthocyanidins5.4 Deconvolution of isotope patterns of A- to B-type interflavan bonds in proanthocyanidins5.5 Multivariate analysis of MALDI-TOF MS spectra data5.6 Conclusion6 Challenges in Analyzing Bioactive ProanthocyanidinsWayne E. Zeller and Irene Mueller-Harvey6.1 Introduction6.2 Structural diversity of proanthocyanidins6.3 Noted challenges in proanthocyanidin analysis6.4 Fate of proanthocyanidins in digestive tract and during plant fermentation6.5 Definition and possible origins of non-extractable proanthocyanidins (NEPAs)6.6 Universal problems of proanthocyanidin analysis6.7 Proanthocyanidin characterization by depolymerization6.8 Mass spectrometry6.9 Nuclear Magnetic Resonance Spectroscopy6.10 Colorimetry6.11 Infra-red spectroscopy6.12 Conclusions7 Lignin Monomers Derived from the Flavonoid and Hydroxystilbene Biosynthetic PathwaysJosé C. del Río, Jorge Rencoret, Ana Gutiérrez, Wu Lan, Hoon Kim and John Ralph7.1 Lignin monomers derived from the monolignol biosynthetic pathway7.2 Flavonoid and hydroxystilbene biosynthetic pathways7.3 Radical coupling of flavonoids and hydroxystilbenes with monolignols – flavonolignans and stilbenolignans7.4 Lignin monomers derived from the flavonoid and hydroxystilbene biosynthetic pathways7.5 Conclusions and future prospects7.6 Acknowledgements8 Complex Regulation of Proanthocyanidin Biosynthesis in Plants by R2R3 MYB Activators and RepressorsDawei Ma and C. Peter Constabel8.1 Introduction to PAs and flavan-3-ols8.2 Regulation of PA and flavonoid biosynthesis by MYB transcription factors8.3 The importance of repressor MYBs in PA and flavonoid metabolism8.4 The complex interaction of PA MYB activators, MYB repressors and bHLH transcription factors8.5 Developmental and plant hormone-mediated regulation of the PA pathway via MYBs8.6 Stress activation of PA synthesis by MYBs in poplar and other woody plants8.7 Summary and conclusions8.8 Acknowledgements9 Conservation and Divergence Between Bryophytes and Angiosperms in the Biosynthesis and Regulation of Flavonoid ProductionKevin M. Davies, Rubina Jibran, Nick W. Albert, Yanfei Zhou and Kathy E. Schwinn9.1 Introduction9.2 Flavonoid biosynthesis in basal plants9.3 Origins of the phenylpropanoid biosynthetic pathway and conservation across the embryophytes9.4 Notable phenylpropanoids of bryophytes9.5 Regulation of flavonoid production9.6 Concluding remarks9.7 Acknowledgements10 Matching Proanthocyanidin Use with Appropriate Analytical MethodJames A. Kennedy10.1 Introduction10.2 General proanthocyanidin structure and analysis10.3 Red Wine Mouthfeel10.4 Biological Activity10.5 Summary11 Imaging Polyphenolic Compounds in Plant TissuesMarisa S. Otegui11.1. Introduction11.2. The chemical nature and intrinsic fluorescence properties of polyphenols11.3. Microscopy-based methods for imaging plant phenolic compounds11.4 Polyphenols and microscopy imaging11.5 Future challenges and opportunities in imaging plant metabolitesAcknowledgmentsReferencesIndex

About the EditorsJess Dreher Reed is Professor of Animal Nutrition at the University of Wisconsin-Madison with over 30 years of postgraduate experience in research on the effects of dietary phytochemicals on the nutrition and health of animals and humans. His research includes development of phytochemical methods for characterization of tannin structure and their interactions with proteins and polysaccharides, and mechanistic studies on the effects of tannins in cell culture and animal models of disease.Victor Armando Pereira de Freitas, current President of the Groupe Polyphénols (since 2016), is Full Professor at the Faculty of Sciences of the University of Porto, Portugal. His research on polyphenols include: structural characterization, chemical transformations in plants and foods during harvest and storage, influence on the sensory properties of foods (color, astringency and bitterness), and other biological properties.Stéphane Quideau, former President of the Groupe Polyphénols (2008-2012), is Full Professor of Organic and Bioorganic Chemistry at the University of Bordeaux, France, and Senior Member of the “Institut Universitaire de France”. His laboratory is involved in research on plant polyphenol chemistry and chemical biology, with particular interests in ellagitannin chemical reactivity and synthesis, and in polyphenol-protein interactions.

• ContributorsPreface1 Achieving Complexity at the Bottom Through the Flavylium Cation-Based Multistate. A Comprehensive Kinetic and Thermodynamic StudyJohan Mendoza and Fernando Pina1.1 Introduction1.2 Flavylium cation as a metamorphosis generator1.3 Extending the multistate of anthocyanins and related compounds to the basic region1.4 The kinetic processes1.5 Conclusions and perspectives2 Proanthocyanidin Oligomers with Doubly-Linked (A-Type) Interflavan Connectivity: Structure and SynthesisKen Ohmori and Keisuke Suzuki2.1 Introduction2.2 Structure2.3 Synthetic studies2.4 Conclusion3 Answering the Call of the Wild: Polyphenols in Traditional Therapeutic PracticeMary Ann Lila and Kriya Dunlap3.1 Introduction3.2 The wildcrafting tradition3.3 How wildcrafted edible plants differ from agricultural commodities3.4 Animal mimickry/Zoopharmacognosy3.5 Probing the mechanisms behind polyphenol-rich traditional medicines bioactivity3.6 Commercialization prospects for wildcrafted polyphenol-rich plants3.7 Acknowledgements4 Causes and Consequences of Condensed Tannin Variation in Populus: A Molecules to Ecosystems PerspectiveKennedy F. Rubert-Nason and Richard L. Lindroth4.1 Introduction4.2 Condensed tannin biosynthesis4.3 Allocational tradeoffs influence CT production4.4 Causes of quantitative and qualitative variation in Populus CTs4.5 Roles of CT variation in Populus-environment interactions4.6 Importance of CTs in Populus-dominated ecosystems of the Anthropocene4.7 Conclusions and challenges5 Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) of Proanthocyanidins to Determine Authenticity of Functional Foods and Dietary SupplementsDaniel Esquivel-Alvarado, Jess D. Reed, and Christian G. Krueger5.1 Introduction5.2 Introduction to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)5.3 Mass spectrometry of proanthocyanidins5.4 Deconvolution of isotope patterns of A- to B-type interflavan bonds in proanthocyanidins5.5 Multivariate analysis of MALDI-TOF MS spectra data5.6 Conclusion6 Challenges in Analyzing Bioactive ProanthocyanidinsWayne E. Zeller and Irene Mueller-Harvey6.1 Introduction6.2 Structural diversity of proanthocyanidins6.3 Noted challenges in proanthocyanidin analysis6.4 Fate of proanthocyanidins in digestive tract and during plant fermentation6.5 Definition and possible origins of non-extractable proanthocyanidins (NEPAs)6.6 Universal problems of proanthocyanidin analysis6.7 Proanthocyanidin characterization by depolymerization6.8 Mass spectrometry6.9 Nuclear Magnetic Resonance Spectroscopy6.10 Colorimetry6.11 Infra-red spectroscopy6.12 Conclusions7 Lignin Monomers Derived from the Flavonoid and Hydroxystilbene Biosynthetic PathwaysJosé C. del Río, Jorge Rencoret, Ana Gutiérrez, Wu Lan, Hoon Kim and John Ralph7.1 Lignin monomers derived from the monolignol biosynthetic pathway7.2 Flavonoid and hydroxystilbene biosynthetic pathways7.3 Radical coupling of flavonoids and hydroxystilbenes with monolignols – flavonolignans and stilbenolignans7.4 Lignin monomers derived from the flavonoid and hydroxystilbene biosynthetic pathways7.5 Conclusions and future prospects7.6 Acknowledgements8 Complex Regulation of Proanthocyanidin Biosynthesis in Plants by R2R3 MYB Activators and RepressorsDawei Ma and C. Peter Constabel8.1 Introduction to PAs and flavan-3-ols8.2 Regulation of PA and flavonoid biosynthesis by MYB transcription factors8.3 The importance of repressor MYBs in PA and flavonoid metabolism8.4 The complex interaction of PA MYB activators, MYB repressors and bHLH transcription factors8.5 Developmental and plant hormone-mediated regulation of the PA pathway via MYBs8.6 Stress activation of PA synthesis by MYBs in poplar and other woody plants8.7 Summary and conclusions8.8 Acknowledgements9 Conservation and Divergence Between Bryophytes and Angiosperms in the Biosynthesis and Regulation of Flavonoid ProductionKevin M. Davies, Rubina Jibran, Nick W. Albert, Yanfei Zhou and Kathy E. Schwinn9.1 Introduction9.2 Flavonoid biosynthesis in basal plants9.3 Origins of the phenylpropanoid biosynthetic pathway and conservation across the embryophytes9.4 Notable phenylpropanoids of bryophytes9.5 Regulation of flavonoid production9.6 Concluding remarks9.7 Acknowledgements10 Matching Proanthocyanidin Use with Appropriate Analytical MethodJames A. Kennedy10.1 Introduction10.2 General proanthocyanidin structure and analysis10.3 Red Wine Mouthfeel10.4 Biological Activity10.5 Summary11 Imaging Polyphenolic Compounds in Plant TissuesMarisa S. Otegui11.1. Introduction11.2. The chemical nature and intrinsic fluorescence properties of polyphenols11.3. Microscopy-based methods for imaging plant phenolic compounds11.4 Polyphenols and microscopy imaging11.5 Future challenges and opportunities in imaging plant metabolitesAcknowledgmentsReferencesIndex

About the EditorsJess Dreher Reed is Professor of Animal Nutrition at the University of Wisconsin-Madison with over 30 years of postgraduate experience in research on the effects of dietary phytochemicals on the nutrition and health of animals and humans. His research includes development of phytochemical methods for characterization of tannin structure and their interactions with proteins and polysaccharides, and mechanistic studies on the effects of tannins in cell culture and animal models of disease.Victor Armando Pereira de Freitas, current President of the Groupe Polyphénols (since 2016), is Full Professor at the Faculty of Sciences of the University of Porto, Portugal. His research on polyphenols include: structural characterization, chemical transformations in plants and foods during harvest and storage, influence on the sensory properties of foods (color, astringency and bitterness), and other biological properties.Stéphane Quideau, former President of the Groupe Polyphénols (2008-2012), is Full Professor of Organic and Bioorganic Chemistry at the University of Bordeaux, France, and Senior Member of the “Institut Universitaire de France”. His laboratory is involved in research on plant polyphenol chemistry and chemical biology, with particular interests in ellagitannin chemical reactivity and synthesis, and in polyphenol-protein interactions.

• ContributorsPreface1 Achieving Complexity at the Bottom Through the Flavylium Cation-Based Multistate. A Comprehensive Kinetic and Thermodynamic StudyJohan Mendoza and Fernando Pina1.1 Introduction1.2 Flavylium cation as a metamorphosis generator1.3 Extending the multistate of anthocyanins and related compounds to the basic region1.4 The kinetic processes1.5 Conclusions and perspectives2 Proanthocyanidin Oligomers with Doubly-Linked (A-Type) Interflavan Connectivity: Structure and SynthesisKen Ohmori and Keisuke Suzuki2.1 Introduction2.2 Structure2.3 Synthetic studies2.4 Conclusion3 Answering the Call of the Wild: Polyphenols in Traditional Therapeutic PracticeMary Ann Lila and Kriya Dunlap3.1 Introduction3.2 The wildcrafting tradition3.3 How wildcrafted edible plants differ from agricultural commodities3.4 Animal mimickry/Zoopharmacognosy3.5 Probing the mechanisms behind polyphenol-rich traditional medicines bioactivity3.6 Commercialization prospects for wildcrafted polyphenol-rich plants3.7 Acknowledgements4 Causes and Consequences of Condensed Tannin Variation in Populus: A Molecules to Ecosystems PerspectiveKennedy F. Rubert-Nason and Richard L. Lindroth4.1 Introduction4.2 Condensed tannin biosynthesis4.3 Allocational tradeoffs influence CT production4.4 Causes of quantitative and qualitative variation in Populus CTs4.5 Roles of CT variation in Populus-environment interactions4.6 Importance of CTs in Populus-dominated ecosystems of the Anthropocene4.7 Conclusions and challenges5 Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) of Proanthocyanidins to Determine Authenticity of Functional Foods and Dietary SupplementsDaniel Esquivel-Alvarado, Jess D. Reed, and Christian G. Krueger5.1 Introduction5.2 Introduction to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)5.3 Mass spectrometry of proanthocyanidins5.4 Deconvolution of isotope patterns of A- to B-type interflavan bonds in proanthocyanidins5.5 Multivariate analysis of MALDI-TOF MS spectra data5.6 Conclusion6 Challenges in Analyzing Bioactive ProanthocyanidinsWayne E. Zeller and Irene Mueller-Harvey6.1 Introduction6.2 Structural diversity of proanthocyanidins6.3 Noted challenges in proanthocyanidin analysis6.4 Fate of proanthocyanidins in digestive tract and during plant fermentation6.5 Definition and possible origins of non-extractable proanthocyanidins (NEPAs)6.6 Universal problems of proanthocyanidin analysis6.7 Proanthocyanidin characterization by depolymerization6.8 Mass spectrometry6.9 Nuclear Magnetic Resonance Spectroscopy6.10 Colorimetry6.11 Infra-red spectroscopy6.12 Conclusions7 Lignin Monomers Derived from the Flavonoid and Hydroxystilbene Biosynthetic PathwaysJosé C. del Río, Jorge Rencoret, Ana Gutiérrez, Wu Lan, Hoon Kim and John Ralph7.1 Lignin monomers derived from the monolignol biosynthetic pathway7.2 Flavonoid and hydroxystilbene biosynthetic pathways7.3 Radical coupling of flavonoids and hydroxystilbenes with monolignols – flavonolignans and stilbenolignans7.4 Lignin monomers derived from the flavonoid and hydroxystilbene biosynthetic pathways7.5 Conclusions and future prospects7.6 Acknowledgements8 Complex Regulation of Proanthocyanidin Biosynthesis in Plants by R2R3 MYB Activators and RepressorsDawei Ma and C. Peter Constabel8.1 Introduction to PAs and flavan-3-ols8.2 Regulation of PA and flavonoid biosynthesis by MYB transcription factors8.3 The importance of repressor MYBs in PA and flavonoid metabolism8.4 The complex interaction of PA MYB activators, MYB repressors and bHLH transcription factors8.5 Developmental and plant hormone-mediated regulation of the PA pathway via MYBs8.6 Stress activation of PA synthesis by MYBs in poplar and other woody plants8.7 Summary and conclusions8.8 Acknowledgements9 Conservation and Divergence Between Bryophytes and Angiosperms in the Biosynthesis and Regulation of Flavonoid ProductionKevin M. Davies, Rubina Jibran, Nick W. Albert, Yanfei Zhou and Kathy E. Schwinn9.1 Introduction9.2 Flavonoid biosynthesis in basal plants9.3 Origins of the phenylpropanoid biosynthetic pathway and conservation across the embryophytes9.4 Notable phenylpropanoids of bryophytes9.5 Regulation of flavonoid production9.6 Concluding remarks9.7 Acknowledgements10 Matching Proanthocyanidin Use with Appropriate Analytical MethodJames A. Kennedy10.1 Introduction10.2 General proanthocyanidin structure and analysis10.3 Red Wine Mouthfeel10.4 Biological Activity10.5 Summary11 Imaging Polyphenolic Compounds in Plant TissuesMarisa S. Otegui11.1. Introduction11.2. The chemical nature and intrinsic fluorescence properties of polyphenols11.3. Microscopy-based methods for imaging plant phenolic compounds11.4 Polyphenols and microscopy imaging11.5 Future challenges and opportunities in imaging plant metabolitesAcknowledgmentsReferencesIndex