Polyphenols in Plants: Isolation, Purification and Extract Preparation

Polyphenols in Plants

Isolation, Purification and Extract Preparation

Second Edition

Ronald Ross Watson

Table of Contents

Cover image

Title page

Copyright

Contributors

Preface

Acknowledgments

Section A: Polyphenols in Agriculture, Plant Growth Economics and Delivery

Chapter 1: Not Only What Is Food Is Good—Polyphenols From Edible and Nonedible Vegetable Waste

Abstract

Acknowledgments

1 Introduction

2 Behind a Common Meal: Polyphenols in Food Byproducts

3 Something to Drink: Polyphenols in Most Common Beverage Byproducts

4 Other Off-the-Menu Miscellaneous

5 Conclusive Remarks

Chapter 2: Polyphenols in Agricultural Byproducts and Food Waste

Abstract

1 Introduction

2 Byproducts Rich in Phenolic Compounds

3 Methods for Recovery of Polyphenolic Compounds From Byproducts

4 Stabilization of Phenolic Extracts

5 Addition of Phenolic Extracts in Foods

6 Conclusions

Chapter 3: Phenolic Natural Compounds and Their Influence on Physiological Processes in Plants

Abstract

1 Introduction

2 Natural Sources of Phenolic Compounds

3 Influence of Some Phenolic Natural Products on Plant's Development

4 Conclusions

Chapter 4: Improving Bioavailability of Polyphenols Using Nanodelivery Systems Based on Food Polymers

Abstract

1 Introduction

2 Health Benefits of Polyphenols Phytochemicals

3 Nanoparticles

4 Food Derived Polymers for Polyphenol Nanodelivery Systems

5 Final Remarks

Chapter 5: Polyphenols Resources in Indonesia From Economic Perspective

Abstract

1 Introduction

2 Tannins From Mangrove Forest

3 Cocoa

4 Tea

5 Coffee

6 Gambier

7 Mangosteen

8 Conclusion

Section B: Isolation and Analysis of Polyphenol Structure

Chapter 6: Structure and Antioxidant Efficiency of Beech (Fagus sylvatica L.) Bark Polyphenols Unraveled by High-Performance Liquid Chromatography/Photodiode Array Detection/Multistage Electrospray Mass Spectrometry and Chemometrics

Abstract

Acknowledgments

1 Introduction

2 Sample Preparation and Extraction

3 Determination of Antioxidant Capacities

4 The HPLC-PDA-ESI-MS/MS Identification of Beech (Fagus sylvatica L.) Bark Polyphenols

5 Mass Spectrometric Evaluation of Relative Quantities of the Compounds by MRM Peak Areas

6 Study of the Antioxidant Efficiency of Compounds Using Chemometrics

7 Conclusions

Chapter 7: Characterization and Quantification of Polyphenols in Fruits

Abstract

1 Introduction

2 Sample Preparation

3 Analytical Methods

4 Preparative Methods

Chapter 8: Phenotypic Diversity of Colored Phytochemicals in Sorghum Accessions With Various Pericarp Pigments

Abstract

Acknowledgments

1 Introduction

2 Pericarp Pigments

3 Phytochemicals

4 Anthocyanins

5 Carotenoids

6 Health Benefits of Colored Phytochemicals

7 Discussion

8 Conclusion

Chapter 9: Relevance and Analysis of Citrus Flavonoids

Abstract

1 Generalities

2 Natural Occurrence of Citrus Flavonoids

3 Analysis of Flavonoids

4 Sampling Methodology

5 Sample Pretreatment

6 Experimental Designs Used in Citrus Studies

7 Extraction Methods: Effect of the Auxiliary Energies

8 Identification and Quantitation of Citrus Flavonoids

9 Foreseeable Applications of Citrus Flavonoids

Chapter 10: Extraction Methods of Polyphenol From Grapes: Extractions of Grape Polyphenols

Abstract

1 Introduction

2 Sampling

3 Sample Preparation

4 Extraction Techniques

5 Conclusion

Chapter 11: Total Polyphenols Content and Antioxidant DPPH Assays on Biological Samples

Abstract

1 Introduction

2 The Folin-Ciocalteu Method or the Assessment of Total Polyphenols Content

3 DPPH Test

4 Total Polyphenols and Antioxidant Activity Relationship

5 Conclusions

Chapter 12: Extraction of Phenolic Compounds From Coriandrum sativum L. and Amaranthus hybridus L. by Microwave Technology

Abstract

Acknowledgments

1 Introduction

2 Material and Methods

3 Results and Discussion

4 Conclusions

Chapter 13: Anthocyanins and Other Polyphenols in Citrus Genus: Biosynthesis, Chemical Profile, and Biological Activity

Abstract

1 Introduction

2 Anthocyanin Compounds

3 Biosynthesis of Anthocyanins and Phenolic Compounds

4 Anthocyanins in Citrus Species

5 Biological Activity of Citrus Flavonoids and Other Phenolic Compounds

6 Conclusion

Chapter 14: Rice Phenolics: Extraction, Characterization, and Utilization in Foods

Abstract

1 Introduction

2 Extraction of Phenolic Compounds From Rice

3 Characterization of Phenolics in Rice

4 Utilization of Rice Phenolics in foods

5 Conclusions

Chapter 15: Extraction of Polyphenols From Aromatic and Medicinal Plants: An Overview of the Methods and the Effect of Extraction Parameters

Abstract

1 Introduction

2 An Overview of Extraction Techniques

3 Effect of Extraction Parameters

Section C: Analysis Techniques for Polyphenols

Chapter 16: Classification of Phenolic Compounds in Plants

Abstract

1 Introduction

2 C6 Phenolic Compounds

3 C6-Cn (1 ≤ n ≤ 4) Phenolic Compounds

4 C6-Cn-C6 (1 ≤ n ≤ 3, or n = 7) Phenolic Compounds

5 Phenolic Dimers and Condensation Oligomeric Products

6 Polymeric Phenols (C6)n, (C6-C3)n, and (C6-C3-C6)n (n > 12)

7 Hybrid Phenolics

Chapter 17: Gas Chromatography: Mass Spectrometry Analysis of Polyphenols in Foods

Abstract

1 Polyphenolic Compounds

2 Polyphenolic Compounds in Foods

3 Methods for Determining Polyphenols

4 Determination of Polyphenols by Gas Chromatography-Mass Spectrometry (GC-MS). Derivatization Reactions

5 Sample Preparation Techniques

6 Miniaturized Techniques for Sample Preparation In GC-MS

Chapter 18: Reaction of Hemoglobin With the Schiff Base Intermediate of the Glucose/Asparagine Reaction: Formation of a Hemichrome

Abstract

1 Introduction

2 Materials and Methods

3 Results and Discussion

4 Conclusions

Chapter 19: Adsorption and Ion Exchange for the Recovery and Fractionation of Polyphenols: Principles and Applications

Abstract

1 Adsorption and Ion Exchange Technology: Historic Overview of Its Application Potential

2 Adsorbent and Ion Exchange Materials

3 Principles of Adsorption and Ion Exchange

4 Kinetics and Equilibria of Sorption and Ion Exchange Processes

5 Practical Implementation of Sorption and Ion Exchange Processes

6 Application of Adsorption and Ion Exchange Technology

7 Application of Adsorbent Resins and Ion Exchangers for the Recovery of Bio- and Technofunctional Phenolic Compounds from Byproducts of Food Processing

Chapter 20: HILIC Chromatography: Powerful Technique in the Analysis of Polyphenols

Abstract

1 Introduction

2 Conclusions

Chapter 21: Chromatographic Analysis of Polyphenols

Abstract

1 Introduction

2 Sample Preparation

3 Chromatographic Analysis

4 Hydrophilic Interaction Chromatography

5 Multidimensional Chromatography

6 HPLC With Online Antioxidant Activity Assays

7 Conclusions

Chapter 22: Sweet Potato Leaf Polyphenols: Preparation, Individual Phenolic Compound Composition and Antioxidant Activity

Abstract

1 Overview of Polyphenols in Sweet Potato Leaves

2 Extraction and Purification of Polyphenols From Sweet Potato Leaves

3 Individual Phenolic Compound Composition and Antioxidant Activity of Sweet Potato Leaf Polyphenols

4 Conclusion and Prospect

Chapter 23: Evaluation of the Phytochemistry and Biological Activity of Grape (Vitis vinifera L.) Stems: Toward a Sustainable Winery Industry

Abstract

Acknowledgments

1 Introduction

2 Conclusions

Chapter 24: The Phenolic Gingerols and Gingerol-Derived Shogaols: Features and Properties Related to the Prevention and Treatment of Cancer and Chronic Inflammation

Abstract

1 Introduction

2 Toxicity

3 Pharmacokinetics

4 Effects on Other Drugs

5 Chemoprevention

6 Antiproliferative and Cytotoxic Effects on Cancer Cells

7 Effects on Cancer Metastasis

8 Antiinflammatory and Immune-modulating Effects

9 Conclusions

Chapter 25: Polyphenols Present in Campomanesia Genus: Pharmacological and Nutraceutical Approach

Abstract

1 Introduction

2 Bioactivities of Campomanesia Genus

3 Nutraceutical and Pharmacological Perspectives of Polyphenols

4 Conclusion

Index

Copyright

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Contributors

Numbers in parentheses indicate the pages on which the authors' contributions begin.

Suminar Setiati Achmadi 67      Department of Chemistry, Bogor Agricultural University, Bogor, Indonesia

Cristóbal N. Aguilar 185      Laboratory of Bioprocesses and Natural Products, Food Research Department, School of Chemistry, Autonomous University of Coahuila, Unidad Saltillo, Coahuila, México

A. Aguirre 59      Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba (UNC), ICYTAC (Instituto de Ciencia y Tecnología de Alimentos), CONICET-UNC, Córdoba, Argentina

Margherita Amenta 191      Council for Agricultural Research and Economics (CREA), Research Centre for Olive, Citrus and Tree Fruit, Acireale, Italy

Željko Andabaka 151      Faculty of Agriculture, Department of Viticulture and Enology, University of Zagreb, Zagreb, Croatia

Fadi Aramouni 123      Food Science Institute, Kansas State University, Manhattan, KS, United States

Danijela Ašperger 151      Faculty of Chemical Engineering and Technology, Department of Analytical Chemistry, University of Zagreb, Zagreb, Croatia

Gabriele Ballistreri 191      Council for Agricultural Research and Economics (CREA), Research Centre for Olive, Citrus and Tree Fruit, Acireale, Italy

Ana I.R.N.A. Barros 381      Centre for the Research and Technology of Agro-Environmental and Biological Sciences, University of Trás-os-Montes and Alto Douro (CITAB-UTAD), Vila Real, Portugal

R. Borneo 59      Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba (UNC), ICYTAC (Instituto de Ciencia y Tecnología de Alimentos), CONICET-UNC, Córdoba, Argentina

Oana-Crina Bujor 45      University of Agronomic Sciences and Veterinary Medicine of Bucharest, Research Center for Studies of Food and Agricultural Products Quality, Bucharest, Romania

Anderson Rodrigues Lima Caires 407      Institute of Physics, Federal University of Mato Grosso do Sul, Campo Grande, Brazil

Natalia Campillo 285      Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, Murcia, Spain

Reinhold Carle 327      Institute of Food Science and Biotechnology, Hohenheim University, Stuttgart, Germany

Veronica Sanda Chedea 169      Laboratory of Animal Biology, National Research and Development Institute for Biology and Animal Nutrition, Baloteşti (INCDBNA-IBNA), Baloteşti, Romania

Nopparat Cheetangdee 217      Department of Product Development, Faculty of Agro-Industry, Kasetsart University, Bangkok, Thailand

Juan C. Contreras-Esquivel 185      Laboratory of Bioprocesses and Natural Products, Food Research Department, School of Chemistry, Autonomous University of Coahuila, Unidad Saltillo, Coahuila, México

Haley Davis 123      Department of Food Nutrition Dietetics & Health, Kansas State University, Manhattan, KS, United States

Ivan Pires de Oliveira 407      Institute of Biomedical Sciences, University of São Paulo, São Paulo, Brazil

Simona Fabroni 191      Council for Agricultural Research and Economics (CREA), Research Centre for Olive, Citrus and Tree Fruit, Acireale, Italy

Fernando Freitas de Lima 407      School of Chemical Engineering, University of Campinas, Campinas, Brazil

Athanasia Goula 23      Department of Food Science & Technology, School of Agriculture, Forestry and Natural Environment, Aristotle University, Thessaloniki, Greece

Irene Gouvinhas 381      Centre for the Research and Technology of Agro-Environmental and Biological Sciences, University of Trás-os-Montes and Alto Douro (CITAB-UTAD), Vila Real, Portugal

Tamás Hofmann 83      University of Sopron, Faculty of Forestry, Institute of Chemistry, Sopron, Hungary

David W. Hoskin 395

Department of Pathology

Department of Microbiology and Immunology

Department of Surgery, Dalhousie University, Halifax, NS, Canada

Nera Huzanić 151      Faculty of Agriculture, Department of Viticulture and Enology, University of Zagreb, Zagreb, Croatia

Aristodimos Ioannou 317      Department of Environmental Science and Technology, Cyprus University of Technology, Limassol, Cyprus

Dietmar Rolf Kammerer 327      WALA Heilmittel GmbH, Bad Boll, Germany

Judith Kammerer 327      lege artis Pharma GmbH + Co. KG, Dettenhausen, Germany

Jasminka Karoglan Kontić 151

Faculty of Agriculture, Department of Viticulture and Enology

Faculty of Agriculture, Centre of Excellence for Biodiversity and Molecular Plant Breeding, University of Zagreb, Zagreb, Croatia

Carlos A. Ledesma-Escobar 133

Department of Analytical Chemistry, University of Córdoba; University of Córdoba Agroalimentary Excellence Campus, Córdoba, Spain

Technological Institute of Veracruz, Food Research and Development Unit, Veracruz, Mexico

Caroline Honaiser Lescano 407      Department of Pharmacology, School of Medical Sciences, University of Campinas, Campinas, Brazil

Chao-Yu Loung 395      Department of Pathology, Dalhousie University, Halifax, NS, Canada

María D. Luque de Castro 133

Department of Analytical Chemistry, University of Córdoba; University of Córdoba Agroalimentary Excellence Campus

Maimónides Institute of Biomedical Research (IMIBIC), Reina Sofía Hospital, University of Córdoba, Córdoba, Spain

Edi Maletić 151

Faculty of Agriculture, Department of Viticulture and Enology

Faculty of Agriculture, Centre of Excellence for Biodiversity and Molecular Plant Breeding, University of Zagreb, Zagreb, Croatia

Ioannis Mourtzinos 23      Department of Food Science & Technology, School of Agriculture, Forestry and Natural Environment, Aristotle University, Thessaloniki, Greece

Tai-Hua Mu 365      Institute of Food Science and Technology, Chinese Academy of Agricultural Sciences; Key Laboratory of Agro-Products Processing, Ministry of Agriculture, Beijing, China

Diana B. Muñiz-Márquez 185      Laboratory of Bioprocesses and Natural Products, Food Research Department, School of Chemistry, Autonomous University of Coahuila, Unidad Saltillo, Coahuila, México

Antigoni Oreopoulou 243      Laboratory of Food Chemistry and Technology, School of Chemical Engineering, National Technical University of Athens (NTUA), Athens, Greece

Vassiliki Oreopoulou 243,263      Laboratory of Food Chemistry and Technology, School of Chemical Engineering, National Technical University of Athens (NTUA), Athens, Greece

Maike Passon 111      Institute of Nutritional and Food Sciences, Chair of Molecular Food Technology, University of Bonn, Bonn, Germany

Raluca Maria Pop 169      Department of Pharmacology, Toxicology and Clinical Pharmacology, University of Medicine and Pharmacy Iuliu Hatieganu, Cluj-Napoca, Romania

Valentin I. Popa 45      Gheorghe Asachi Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, Iasi, Romania

Darko Preiner 151

Faculty of Agriculture, Department of Viticulture and Enology

Faculty of Agriculture, Centre of Excellence for Biodiversity and Molecular Plant Breeding, University of Zagreb, Zagreb, Croatia

Feliciano Priego-Capote 133

Department of Analytical Chemistry, University of Córdoba; University of Córdoba Agroalimentary Excellence Campus

Maimónides Institute of Biomedical Research (IMIBIC), Reina Sofía Hospital, University of Córdoba, Córdoba, Spain

Krystyna Pyrzynska 341,353      Department of Chemistry, University of Warsaw, Warsaw, Poland

Marcelo Queiroz 381      Centre for the Research and Technology of Agro-Environmental and Biological Sciences, University of Trás-os-Montes and Alto Douro (CITAB-UTAD), Vila Real, Portugal

Paolo Rapisarda 191      Council for Agricultural Research and Economics (CREA), Research Centre for Olive, Citrus and Tree Fruit, Acireale, Italy

Andrea N. Rasmussen 395      Department of Pathology, Dalhousie University, Halifax, NS, Canada

Miguel Rodrigues 381      Centre for the Research and Technology of Agro-Environmental and Biological Sciences, University of Trás-os-Montes and Alto Douro (CITAB-UTAD), Vila Real, Portugal

Raúl Rodriguez-Herrera 185      Laboratory of Bioprocesses and Natural Products, Food Research Department, School of Chemistry, Autonomous University of Coahuila, Unidad Saltillo, Coahuila, México

Flora Valeria Romeo 191      Council for Agricultural Research and Economics (CREA), Research Centre for Olive, Citrus and Tree Fruit, Acireale, Italy

Giuseppe Ruberto 3      Istituto del CNR di Chimica Biomolecolare, Catania, Italy

J. Scott Smith 123      Food Science Institute, Kansas State University, Manhattan, KS, United States

Aleksandra Sentkowska 341,353      Heavy Ion Laboratory, University of Warsaw, Warsaw, Poland

Yanting Shen 123      Department of Food Nutrition Dietetics & Health, Kansas State University, Manhattan, KS, United States

Laura Siracusa 3      Istituto del CNR di Chimica Biomolecolare, Catania, Italy

Domagoj Stupić 151      Faculty of Agriculture, Department of Viticulture and Enology, University of Zagreb, Zagreb, Croatia

Xiaoyu Su 123      Department of Food Nutrition Dietetics & Health, Kansas State University, Manhattan, KS, United States

Hong-Nan Sun 365      Institute of Food Science and Technology, Chinese Academy of Agricultural Sciences; Key Laboratory of Agro-Products Processing, Ministry of Agriculture, Beijing, China

Corneliu Tanase 45      University of Medicine and Pharmacy of Tirgu Mureș, Faculty of Pharmacy, Botanical Pharmaceutic Department, Tirgu Mures, Romania

Nicolina Timpanaro 191      Council for Agricultural Research and Economics (CREA), Research Centre for Olive, Citrus and Tree Fruit, Acireale, Italy

Ivana Tomaz 151      Faculty of Agriculture, Department of Viticulture and Enology, University of Zagreb, Zagreb, Croatia

Dimitrios Tsimogiannis 243,263      Laboratory of Food Chemistry and Technology, School of Chemical Engineering, National Technical University of Athens (NTUA), Athens, Greece

Constantinos Varotsis 317      Department of Environmental Science and Technology, Cyprus University of Technology, Limassol, Cyprus

Pilar Viñas 285      Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, Murcia, Spain

Donghai Wang 123      Department of Biological & Agricultural Engineering, Kansas State University, Manhattan, KS, United States

Weiqun Wang 123      Department of Food Nutrition Dietetics & Health, Kansas State University, Manhattan, KS, United States

Fabian Weber 111      Institute of Nutritional and Food Sciences, Chair of Molecular Food Technology, University of Bonn, Bonn, Germany

Jorge E. Wong-Paz 185      Laboratory of Bioprocesses and Natural Products, Food Research Department, School of Chemistry, Autonomous University of Coahuila, Unidad Saltillo, Coahuila, México

Jingwen Xu 123      Department of Food Nutrition Dietetics & Health, Kansas State University, Manhattan, KS, United States

Preface

There is a growing community of researchers interested in the identification and isolation of polyphenols. Therefore, in this second edition, 92% of the topics are new additions to those that appeared in the first edition, making this book novel. The role of polyphenols in agriculture is covered in the first expanded new section. Siracusa reviews polyphenols in vegetable waste, and there is a chapter by Mourtzinos about their presence in agricultural byproducts. Tanase then describes polyphenol influence on physiological processes in plants. To improve the use of polyphenols, Aguirre discusses nanodelivery in food. Achnadi, as expected, outlines the economic perspective of polyphenols.

Section B focuses on an analysis of polyphenol structure. Hofmann describes HPLC in purification and identification. Weber completes this review with characterization of polyphenols in fruit, and Davis uses phenotypic diversity to define pigments in plants. Ledesma-Escobar analyses citrus flavonoids as an example of defining polyphenols in a fruit, and Tomaz reviews extraction from grapes as a model of understanding polyphenols. Several chapters then examine other extractions of phenolics, including using microwave technology, describing rice phenolics, and defining biosynthesis, chemical profiles, and biological activity in citrus. Oreopoulou concludes with a review of extraction and an overview of methods.

The final section centers on analysis techniques for polyphenols, a major component of the book. This comprises two chapters on classification, including the use of gas chromatography-mass spectrometry analysis, and consists of revised chapters from the first edition. Kammerer reviews methods using adsorption and ion exchange to increase polyphenol recovery, and Sentkowska supports this review with HILIC chromatography to improve analysis. Mu uses sweet potato leaf polyphenols to define composition and antioxidant activity, a special detailed example of analysis of a single plant. Gouvinhas then applies the methods in phytochemistry to understand the wine industry, a significant activity. Loung uses isolation techniques in the development of new compounds and their use in cancer therapy, followed by Lescano who concludes the book with her chapter defining polyphenols using pharmacological and nutraceutical approaches.

Acknowledgments

The work of Dr. Watson’s editorial assistant, Bethany L. Stevens, in communicating with authors and working on the manuscripts was critical to the successful completion of the book. The support of Michelle Fisher and Nancy Maragioglio was very helpful. Their assistance is very much appreciated. Support for Ms. Stevens’ and Dr. Watson’s work was graciously provided by the Natural Health Research Institute, www.naturalhealthresearch.org. It is an independent, non-profit organization that supports science-based research on natural health and wellness set up by Elwood Richard and managed by Dr. Richard Sharpe and Antonella Matuszewski. It is committed to informing about scientific evidence on the usefulness and cost-effectiveness of diet, supplements, and a healthy lifestyle to improve health and wellness and reduce disease. Finally, the work of the librarian of the Arizona Health Science Library assigned to the Public Health School, Mari Stoddard, was vital and very helpful in identifying key researchers who participated in the book.

Section A

Polyphenols in Agriculture, Plant Growth Economics and Delivery

Chapter 1

Not Only What Is Food Is Good—Polyphenols From Edible and Nonedible Vegetable Waste

Laura Siracusa; Giuseppe Ruberto    Istituto del CNR di Chimica Biomolecolare, Catania, Italy

Abstract

The current transition from a linear (open-ended) to a circular economy is mainly with regard in the way waste is considered, passing from a valueless material to a precious resource. This has prompted researchers to study waste composition, in particular that coming from food industry and market, and exploit it as a source of nutrients/bioactive molecules, particularly polyphenols. These compounds, unlike the other secondary metabolites and notwithstanding their lower number, can be considered ubiquitous in plants in which they extert a protective and defensive role. Phenolic compounds are widespread in all parts of fruits, vegetables, seeds, legumes, cereals, etc. Most of these products are consumed as fresh material but are also sometimes submitted to transformations that normally produces some waste depending on the typology of the product. Therefore, this enormous amount of material can be used as an economic source of phenolic compounds, contributing to their partial ecological disposal. In this chapter, an ordinary 100% vegetable-based meal is presented, along with a list of the corresponding byproducts, with the aim of underlining the need of re-evaluating and recycling, and to show how everyday food waste can be considered as a further source of nutrients, according to the circular economy concept.

Keywords

Circular economy; Re-evaluation; Recycling; Secondary metabolism; Polyphenols; Vegetable waste; Processing; Ready-to-eat; High added-value byproducts

Chapter Outline

1Introduction

1.1Why to Re-Evaluate: The Importance of Vegetable Wastes in the Circular Economy Era

1.2The Tight Biochemical Connection Between Vegetables and Their Byproducts

2Behind a Common Meal: Polyphenols in Food Byproducts

2.1Introducing the Concept of This Section

2.2First Course: Pasta With Tomato Sauce (Polyphenols in Wheat Bran and Tomato Byproducts)

2.3A Fresh Side Dish: Mixed Salad (Polyphenols From Fennel, Carrot, Lettuce Leaves, Artichoke, Lemon Juice, and Olive Oil Byproducts)

2.4Fruits (Polyphenols From Apple, Pomegranate, Banana, and Berry Byproducts)

3Something to Drink: Polyphenols in Most Common Beverage Byproducts

3.1Orange Juice (Polyphenols From Orange Byproducts)

3.2Wine (Polyphenols From Grape and Wine Byproducts)

4Other Off-the-Menu Miscellaneous

5Conclusive Remarks

Acknowledgments

References

Further Reading

Acknowledgments

We wish to thank Consiglio Nazionale delle Ricerche (CNR, Rome, Italy) for financial support. The authors also express their thanks to the numerous colleagues of other Italian and international institutions, quoted in the reference list, for their continued and efficacious collaboration in this field. A particular mention goes to Antonio Greco (ICB-CNR-CT) for his precious help in the graphics of this chapter.

1 Introduction

1.1 Why to Re-evaluate: The Importance of Vegetable Wastes in the Circular Economy Era

The primary challenge for all kinds of industries in terms of green processes is the transition from a fossil resource-based economy to one based on renewable raw materials processing. The food and beverage industry is undoubtedly the largest manufacturing sector in the European Union (EU); byproduct management in the food industry is hence a great concern in the areas of environmental protection and sustainability. Because agrifood industry waste is almost entirely of biological origin, the two general ways to reuse it have been either as animal feed (not always adequate due to difficulties in properly balancing the nutritional requirements) or as combustion feedstock or fertilizers, sometimes causing major environmental issues [1,2]. Furthermore, among all known sustainable resources (solar, wind, geothermal), only biomass coming from food and feed crops, dedicated energy crops, trees, agriculture residues, et similia currently represents an accessible source for chemicals and products with high added value [3]. For example, these materials usually contain high levels of cellulose, hemicellulose, lignin, and proteins, which can be used as renewable natural resources either for inexpensive, ecofriendly materials (such as low-cost adsorbents) [2] or destined to supplement food products and ready meals [4]. As a matter of fact, the number of food products enriched with dietary fibers coming from agronomic byproducts introduced to the market has increased due to several beneficial effects mainly on the digestive system [5]. In a recent paper, Naziri and coworkers [6] critically discussed the possibility of waste recycling in three of the primary traditional productions in Macedonia, that is, olive oil, wine, and rice. They reported high-value nutrient recovery animal feed, thermal energy production, alcohol production, and composting as the currently available ways for waste utilization in Greece. These processes, once optimized, can be practical examples of the so-called circular economy, whose concept was introduced by Pearce and Turner [7], which is defined as a regenerative system in which resource input and waste, emission, and energy leakage are minimized by slowing, closing, and narrowing material and energy loops. This can be achieved through long-lasting design, maintenance, repair, reuse, remanufacturing, refurbishing, and recycling [8]. In other words, circular economy promotes resource minimization and the adoption of cleaner technologies [9]. A painless transition from the conventional, open-ended economy to the circular economy has been, and still is, one of the primary strategies of the European Commission [10].

Apart from the previously mentioned dietary fibers, food and agroindustrial residues are known to constitute a good natural source of bioactive molecules such as vitamins, minerals, pigments, and antioxidants to be used as food additives and/or nutraceuticals; in fact, other than contributing to the overall process sustainability, natural ingredients used in daily life products have greater acceptability for most people over their synthetic counterparts [11].

1.2 The Tight Biochemical Connection Between Vegetables and Their Byproducts

Compositional studies of agrifood industry waste suggest the presence of a wide range of bioactive compounds, mainly primary and secondary metabolites of plants. German physiologist Albrecht Kossel [12] was the first to adopt this subdivision. The primary components are considered vital for all living organisms, from the simplest unicellular organism to the multicellular and very complex ones such as plants and animals, accounting for their growth, development, reproduction, etc. From a chemical point of view, these substances belong to the classes of carbohydrates, proteins, and lipids, and are very similar in all living organisms. The secondary components were initially considered void of any vital function, as a sort of metabolic waste product. Unlike the primary substances, these components are not uniformly present in all living organisms, and one of their main peculiarities is a large chemical diversity. In the last decade, nearly 1000 phytochemical studies have shown that the presence of the secondary metabolites is strictly connected with the relationship of a given organism within its enviroment, assuming, therefore, a vital and not secondary role for these compounds [13,14].

The large number of secondary metabolites—today estimated at around 200,000—are best classified into three categories of substances: terpenes and terpenoids, alkaloids, and phenolic compounds [15–17]. The previously discussed subdivision arises from the biosynthetic route of their formation: (a) mevalonic acid pathway and (b) methyl-erythritol phosphate/deoxy xylulose phosphate (MEP/DOXP) pathway, which regulate the biosynthesis of terpenes and terpenoids, and (c) shikimic acid and malonic acid pathways, which govern the biosynthesis of phenolics. Alkaloids come from aromatic and aliphatic amino acids. However, the previously mentioned pathway often intercross producing the so-called mixed-biogenesis metabolites.

Phenolics, unlike the other secondary metabolites and notwithstanding their lower number, can be considered ubiquitous in plants developing a protective and defensive role. They can be divided in different chemical classes, namely flavonoids, benzoic and cinnamic acids, gallotannins, proanthocyanidins, stilbenoids, and lignans. Flavonoids, with more than 4000 substances, are largely the most represented phenolic compounds [18,19], which in turn are classified as anthocyanins, flavones, isoflavones, flavanones, flavonols, and flavanols [20].

A further aspect related to the secondary metabolites is that most of these substances show many biological activities when assumed by the diet. Their role is mainly protective, in other words, these components act as preventive agents that help fight the onset of several pathologies such as cardiovascular and neurodegenative diseases, cancer, diabetes, etc., as ascribed to the Mediterranean Diet, recently defined as an intangible cultural heritage of humanity by the United Nations Educational, Scientific and Cultural Organization (UNESCO). The term nutraceutic has been coined for these compounds to indicate a simulatenous nutritional and pharmaceutic value [21,22]. Moreover, these substances are responsible for the therapeutic properties of many medicinal plants present in ethnobotanic and ethnopharmaceutic fields of many countries [23–25]. Finally, due to their peculiar and unusual chemical structures, these compounds still represent lead compounds able to be used to produce and project new drugs [26,27].

As previously mentioned, polyphenols are present in many plant materials, such as fruits, vegetables, seeds, legumes, cereals, etc. Most of these products are consumed as fresh material but often are submitted to some transformations that normally produce an amount of waste depending on the typology of the product. Of course, if these transformations are carried out at room temperature and/or with minimal treatments, which is true in most cases, the obtained waste shares a similar secondary metabolic pool with the original plant material [17]. Therefore, this enormous amount of material (for example, waste derived from the production of juices and essential oils from citrus fruits, the grape pomace from wine production, and residual products from olive and seed oil production) can be used as an economic source of phenolics, contributing to their partial ecological disposal [28].

2 Behind a Common Meal: Polyphenols in Food Byproducts

2.1 Introducing the Concept of This Section

The implications of the transition from a linear economy to a circular economy primarily regards the way in which waste is considered, passing from a valueless material to a high added-value resource [29]. This has prompted researchers to exhaustively study waste composition, in particular that coming from the food industry and market, to exploit it as a source of nutrients, in particular polyphenols. In the last decade (2008–18), 939 papers (of which 51 were reviews) have been published on the topic polyphenols from waste; 338 publications (of which 31 were reviews) are present in the literature when restricting the research to polyphenols from food waste (source: Scopus). With an aim to again underline the need of re-evaluating and recycling, we have built the concept of this section on a common ordinary meal to show how everyday food waste can be considered as a further source of nutrients (Fig. 1).

Fig. 1 A list of foods and beverages normally present in a daily diet discussed in this chapter for their content in secondary metabolites and, in particular, polyphenols.

Starting with a traditional, known-worldwide, Italian first course, namely pasta with tomato sauce, we will talk about recovery of polyphenols in two strategic food industry byproducts: wheat bran and tomato paste residues. Regarding a vegetarian side dish, a typical mixed salad, the phenolic composition of waste from artichoke, fennel, carrots, and lettuce leaves will be discussed, together with the composition and potential reuse of byproducts from lemon juice and olive oil-producing chain. Polyphenols-rich mixed fruit (apple, banana, berries, and pomegranate) residue exploitation will follow, finally ending with a discussion on the nutrient composition and possible exploitation of polyphenols from wine and orange juice byproducts.

2.2 First Course: Pasta With Tomato Sauce (Polyphenols in Wheat Bran and Tomato Byproducts)

Wheat is a wild grass native to arid countries of western Asia. Almost 600 genera of wheat have evolved and a number of classifications are available [30]. Nowadays, wheat is one of the major crops cultivated worldwide, representing a primary component of the human diet; its flour is in fact the basic ingredient of bread, pasta, and other bakery products [31]. The wheat preferred for making pasta products is durum wheat (Triticum turgidum L. subsp. turgidum conv. durum, Desf. MacKey); this is due to its unique features including its hardness, intense yellow color, and taste. Durum wheat-derived pasta products have an excellent cooking quality and stability to overcooking, with unmatched eating quality. Italian law n. 580 [32] decreed that dried pasta can be produced only from durum wheat and that the use of other cereals can be regarded as fraud [33]. Wheat is also a good source of bioactive compounds, including fiber (both soluble and insoluble) and a wide range of phenolic compounds such as benzoic and cinnamic acids, anthocyanidins, quinones, flavonols, chalcones, flavanones, and amino phenolics [34]. Polyphenol content in wheat as well as is its main byproduct, namely bran, is highly variable and depends on wheat genotype, growing area, interaction with environmental factors, and milling procedure [35,36]. Wheat polyphenols may be present in free or esterified/etherified soluble form as well as in an insoluble form bound to cell wall constituents such as polysaccharides, protein, lignin, cutin, or suberin. Insoluble polyphenols are considered the major contributors to the total antioxidant capacity of wheat, as in other cereals [37]. Numerous papers in the literature report that whole grain products have an antioxidant activity that is almost double that of white ones; these data indicate the fundamental contribution of bran and germ to the whole cereal antioxidant activity and is explained by the fact that phenol compounds are associated with the outer layers, particularly the aleurone layer [38]. Recent literature also reports the content of phenolics in different varieties of wheat grains and in their different fractions (bran, break flour, reduction flour, and shorts), among which wheat bran has the highest concentration ([39,40] and references therein). Several phenolic acids have been detected in wheat bran; ferulic acid is the predominate compound along with significant levels of syringic, p-hydroxybenzoic, vanillic, and coumaric acids [36]. In the bran, ferulic acid is largely located as a structural component of the cell walls of aleurone and pericarp. Most of the ferulic acid is covalently bound to complex polysaccharides in the cell walls, mainly arabinoxylans. The potential health effect of such a molecule has been partly attributed to its antioxidant properties. It was also identified as the major contributor to the antioxidant capacity of aleurone, which is a fraction of the highest antioxidant capacity in wheat grain [41]. Wheat milling byproducts are mainly used in all-bran breakfast extruded products, which contain almost exclusively insoluble dietary fibers. The last decade trend was, and still is, that of recovering valuable nutrients from this matrix (as the aforementioned ferulic acid) with the aim of improving the technological performance and/or integration of foods with healthy compounds [38] via optimization of the extraction method [42], by biotransformation [41], or through acid and/or alkaline hydrolysis. The hydrolysis method in particular can affect the yield and profile of phenolic acids in wheat bran because phenolic acids exist in esterified forms in the cell walls [35,43].

Tomato is the second-most important vegetable crop worldwide and a key component in the so-called Mediterranean diet. Tomato and its products are an important source of phenolic compounds; it is known that the phenolic constituents of tomato such as flavanones, flavonols, hydroxycinnamates, and conjugated structures (caffeoylquinic acids) are involved in the prevention of cancer and cardiovascular diseases [44,45]. With regard to the tomato-processing industry, processed tomato products include canned and sundried tomatoes, juices, ketchup, pastes, purees, salads, sauces, and soups [46]. During tomato processing, a considerable amount of waste is generated. Tomato waste consists mainly of peel and seeds, which contain fiber as a major compound, but also fatty acids, sitosterol, and phenolics such as quercetin, myricetin, and others. Kalogeropoulos and others [47] found comparable results when analyzing the total phenolic content and antioxidant activity of industrial tomatoes compared with their processing byproducts. Valdez-Morales and coworkers [48] studied the detailed composition of peel and seeds from four different tomato cultivars; they reported gallic acid, hydroxycinnamic acids (including hydroxycinnamoylquinic acids such as chlorogenic acid), quercetin along with its derivatives, isorhamnetin, narigenin, apigenin, and kaempferol as metabolites present in these byproducts. The same authors also found tomato peel is nearly three times richer in organic and cinnamic acids and four times richer in flavonoids with respect to tomato seeds. Similar results have been reported by Toor and Savage [49] and Ćetković et al. [50]. Therefore, data available in the literature seem to conform the fact that tomato byproducts contain significant amounts of bioactive phytochemicals. Therefore, in line with the trend for sustainability and recycling/reusing, these constituents could be either isolated from the wastes to be used for the formulation of functional foods or serve as additives in food systems to elongate their shelf life. With regard to ferulic acid, the main constituent of wheat bran, the new trend is to use it as a substrate for the biological production of vanillin, one of the 71 most widely used aromatic molecules in the food, pharmaceutical, and cosmetic industries [51,52].

Some typical polyphenol components from grains and tomato are reported in Fig. 2.

Fig. 2 Some typical polyphenol components from grain and tomato.

2.3 A Fresh Side Dish: Mixed Salad (Polyphenols From Fennel, Carrot, Lettuce Leaves, Artichoke, Lemon Juice, and Olive Oil Byproducts)

Consumption of fresh mixed vegetables has always been and still is highly recommended as they are considered essential components of the human diet, providing considerable health and nutritional benefits due to the presence of high levels of micronutrients and fibers [53].

Substantial changes in modern lifestyles have resulted in an increase of consumption of ready-to-eat foodstuff, including minimally processed vegetables, defined as raw fresh vegetables that have been washed then peeled, sliced, chopped, or shredded prior to being packaged for sale, and are intended to be consumed raw and not intended for further processing; with the possible exception of the addition of dressing or croutons by the end user, these products do not require further preparation (cooking, washing, etc.) before consumption [54].

This means that the main sources of fruit and vegetable waste production from commercialization and industrial transformation originate in the packing houses, where external leaves and low-quality products are discarded; in the fresh cut industries, where peels and external tissues are removed; and in the extraction industries, where the press cake residues (pomaces) constitute the main byproduct. The full minimally processed product chain includes selection, cleaning, washing, trimming, peeling, cutting and shredding, sanitizing, and packing [53]. The packing houses dealing with vegetables therefore produce large amounts of waste and residues, sometimes reaching up to 50% of the vegetable's initial weight, as in lettuce or fennel [55].

Fennel (Foeniculum vulgare Mill.) is a widespread perennial umbellifer (Apiaceae) herb, traditionally used for medicinal purposes and human consumption. Different fennel parts are widely used in many of the culinary traditions of the world. Shoots, tender leaves, and stems are chewed and sucked due to its peculiar aniseed flavor. All these parts are also stable ingredients in many dishes such as salads, soups, and herbal teas. Outer leaves, stems, and inflorescences from fennel, which are considered as waste in the food industry, are shown to possess high nutritional value due to the presence of sugars, unsaturated fatty acids, and phenolics [56]. Among the flavonoids present in F. vulgare, the most abundant are the flavonols quercetin 3-O-glucuronide, quercetin 3-O-glucoside (isoquercitrin), quercetin 3-O-arabinoside, kaempferol 3-O-glucuronide, kaempferol 3-O-arabinoside, and isorhamnetin glucoside. Quercetin 3-O-galactoside, kaempferol 3-O-rutinoside, and kaempferol 3-O-glucoside have also been reported to occur in the aqueous extract of fennel [57]. Parejo et al. [58] studied the detailed phenolic composition in fennel waste from essential oil distillation using the LC-ESI-/MS/MS technique; nearly 50 polyphenols were identified in this byproduct, ranging from simple phenolic acids to hydroxycinnamoylquinic acids and various flavonoids. Other authors investigated the phenolic profile and content from the leaves of F. vulgare, identifying more than 20 different metabolites again belonging to the subclasses of flavonols and hydroxycinnamoylquinic acids [59]. With regard to lettuce leaves and carrots, these vegetables can be used raw or as minimally processed products. As already mentioned, production and commercialization of ready-to-eat vegetables include the discharge of outer/damaged leaves, as in lettuce, and substantial portions of the edible root, as in carrots, to obtain chopped, sliced, or whole minimally processed products. In this case, nearly 50% of the raw material is discarded as byproduct in the packing houses.

Lettuce (Lactuca sativa L.) is an annual herbaceous plant belonging to the Compositae (Asteraceae) family, one of the most diverse families of flowering plants. Today, lettuce is an important crop species and a broadly consumed vegetable, as well as a good source of different classes of phenolic compounds. Lettuce is also consumed worldwide as a minimally processed food product, and its use has continued to increase in salad bars and fast foods [60]. As in many vegetable species, the abundance of phenolic compounds in lettuce tissues can be affected by genetic, agronomical, and environmental factors [61] as well as the cultivation method (greenhouses or open field) and tissue type (red, green, or white) [60]. Several authors ([62,63] and references therein) reported the presence of flavonols in lettuce such as quercetin and kaempferol derivatives (quercetin 3-O-glucoside, quercetin 3-O-rutinoside, quercetin 3-O-glucuronide, quercetin 3-O-(6″-O-malonyl)-glucoside, kaempferol 3-O-glucuronide, kaempferol 3-O-(6″-O-malonyl)-glucoside) together with several derivatives of the flavone luteolin (luteolin 7-O-glucuronide, luteolin 7-O-glucoside, luteolin 7-O-rutinoside). However, the subclass of hydroxycinnamic acids represents undoubtedly the largest phenolic group in this matrix, where they are present principally as esters with tartaric, malic, and quinic acid. For example, in 10 samples of Romaine variety lettuce, Ribas-Agustí and coworkers [61] found that caffeoyl derivatives covered nearly 90% of total polyphenols, whereas quercetin derivatives were present in a lesser extent (5%). Crozier et al. [63] reported a study on the red-leaved lettuce Lollo Rosso, which contained the anthocyanin cyanidin 3-O-(6″-O-malonyl) glucoside and several flavonols. The levels of flavonols measured in the outer leaves were around double the amount found in the inner leaves of this variety.

The edible roots of Daucus carota L., commonly known as carrots, are a stable vegetable included in most diets. As these plants are seasonal, they are usually processed in many forms, such as chopped, frozen, or canned. As a fresh vegetable, carrots are used in many cooking recipes such as soups, sauces, and dinner meals. Carrot juice is also utilized as a natural source of antioxidants in drink production [64]. All of these uses initially begin with the peeling and removal of the top and bottom of the carrot. Although the carrot is widely recognized as a source of carotenoids, primarily β-carotene, it is also a rich source of polyphenols and dietary fiber, and so are its byproducts. Unlike other vegetables, phenolic compounds contribute to some of the physical characteristics of the carrot. For instance, anthocyanins and carotenoids are responsible for the color, aroma, and bitterness of carrots. The two main phenolic classes present in carrots are para-hydroxybenzoic acids and hydroxycinnamic acids (caffeic and ferulic acid derivatives, mainly quinic acid esters), as reported by O'Shea et al. [65] and Gonçalves et al. [66]. Among them, chlorogenic acid (3-caffeoylquinic acid) was detected as the main compound, representing nearly half of the total phenolic compounds present in carrot [67]. The flavanols catechin and epicatechin have also been detected in this matrix [68]. With regard to the content of polyphenols in different D. carota root tissues, Zhang and Hamauzu [67] reported carrot peel as the richest part; in fact, although this tissue accounts for only 11% of root's fresh weight, it contributes more than 50% of the total carrot phenolics. Therefore, the higher level of phenolic compounds and antioxidant properties in carrot peel treated as waste in the processing industry could be considered for value-added utilization [69].

Artichoke (Cynara cardunculus L. subsp. scolymus (L.) Hayek, formerly Cynara scolymus L.) is an herbaceous perennial plant typical of the Mediterranean area and today widely cultivated all over the world. The edible parts of the plant are the large immature inflorescences (heads or capitula), harvested in the early stages of their development, which represent about 30% to 50% of its fresh weight depending on the variety and harvesting time [70]. Artichoke is a rich source of fibers, minerals, inulin, and bioactive phenolic compounds. Caffeic acid derivatives are the main phenolic compounds found in artichoke, with a wide range of mono- and di-caffeoylquinic acid derivatives and chlorogenic acid (3-O-caffeoylquinic acid) as the prevalent polyphenol. However, cynarin (1,3-di-caffeoylquinic acid) is the most well-known caffeoylquinic acid derivative identified in artichoke extracts (heads and leaves), even though it is not the most abundant. Other phenolics, such as the flavones apigenin and luteolin (both present as glucosides and rutinosides) as well as different cyanidin caffeoylglucoside derivatives, have been identified in artichoke tissues; from a quantitative point of view, these compounds are considered minor constituents, counting for about 10% or less of the total artichoke polyphenols [71]. Artichoke heads are usually commercialized as raw products, sliced, or as frozen hearts. As already stated, the packing houses and food-processing industries dealing with vegetables produce large amounts of wastes and residues; sometimes, these byproducts can reach up to 60% of harvested vegetal as in the case of the industrial manipulation of artichokes. Byproducts of artichoke processing (leaves, stems, outer and intermediate bracts) have been investigated as animal feedstuff, for fiber production, and for the recovery of functional food ingredients [72]. In a detailed compositional study on different parts of artichoke heads (outer, intermediate and inner bracts, and receptacle), Fratianni and coworkers [73] reported that, on the whole, hydroxycinnamic acids were uniformly represented; also, the content of cynarin was found not to vary significantly in the different parts of the head. When the same authors analyzed the luteolin content, it was found to be low in receptacles and inner bracts, yet the highest levels were observed in intermediate bracts; the quantitative analysis of apigenin on the other hand showed a constantly low level for receptacles and inner bracts. Schütz et al. [74] analyzed the content of phenolic compounds from artichoke heads, juice, and pomace; they detected 22 major compounds, among which were 11 caffeoylquinic acids and 8 flavonoids. Apigenin 7-O-glucuronide was found to be the major flavonoid in all samples investigated, whereas 1,5-di-caffeoylquinic acid represented the major hydroxycinnamic acid. Total phenolic contents of 12 g/kg on a dry matter basis revealed that artichoke pomace is a promising source of phenolic compounds that might be recovered and used as natural antioxidants or functional food ingredients. Blanched (thermally treated) artichokes and artichoke blanching waters, which represent a huge amount of discarded material in some industries, were also studied for their polyphenol content by Llorach et al. [72]; according to the encouraging results reported by the authors, the use of these byproducts as possible ingredients to functionalize foodstuffs (to decrease lipid peroxidation and to increase health-promoting properties) is suggested. Artichoke leaves and floral stems were also investigated; a high content of flavones was present in the leaf, and floral stems proved to be rich in caffeoylquinic acids [75].

A very common and simple salad dressing used in the Mediterranean area is a mixture of lemon juice and extra virgin olive oil; particularly, ready-to-use lemon juice is nowadays present in the global market chain worldwide.

Lemon (Citrus limon L.) is considered the third-most important citrus species after orange and mandarin, with a strong commercial value. The worldwide production of lemons in 2010 was more than 4 million tons. Half of that production is destined to be processed, mainly in the juice industry. This industry thus generates a large amount of agrifood waste material, which is mostly used as a source of cattle feed or as fertilizer. Current studies have found other uses for this abundant agrifood waste, for example, using it as a source of biomass to produce bioethanol. However, the most valuable option would be to obtain high added-value products such as polyphenols [76]. Lemon fruits are significant sources of flavonoids, principally flavanones, which are considered a sort of marker of the genus Citrus and are present in both the juice and the tissues ingested when fruit segments are consumed [63,67]. Lemon peel represents the main component of lemon waste (pomace), which accounts for 50% to 65% of the whole fruit weight [77]. Just like lemon pulp, lemon peel contains bioactive compounds such as vitamin C (ascorbic acid) and other organic acids like tartaric, malic, and citric acid [78]; flavonoids (flavanones, flavonols, flavones); and cinnamic acids (ferulic, p-coumaric, and sinapic acids). Cinnamic acids are often linked to various plant components through ester, ether, or acetal bonds, whereas lemon flavonoids can be present in the aglycone or glycoside forms [79–81]. The liberation of phenolic compounds of Citrus peels may result in extracts with increased antioxidant activity and could be achieved by different treatments [82].

Olive oil, obtained from the fruits of Olea europaea L., is almost totally produced in the Mediterranean region. During the production process, several wastes and byproducts are generated; the most important are olive wood and leaves, cake, pomace, kernel, paste, and olive mill wastewater [83]. As the demand of olive oil rapidly increases worldwide, the olive oil producing countries have faced a serious challenge to find an environmentally sound and economically viable solution in handling and disposal of olive mill wastes [84]. However, they are also an important source of nutritionally valuable compounds including polyphenols, fatty acids, chlorophylls, carotenoids, tocopherols, phytosterols, squalene, and aromatic compounds. Polyphenol composition of olive mill wastes may vary according to many factors, the most important of which are cultivar, climatic conditions, stage of crop cycle, and agricultural practices [85]. Uncommon phenols include oleuropein, dimethyloleuropein, oleuropein aglycone, ligstroside, ligstroside aglycone, oleoside, tyrosol, and hydroxytyrosolare typical of O. europaea and its byproducts, which also contain flavonoid glycosides including luteolin 7-O-glucoside, apigenin 7-O-glucoside, rutin (quercetin 3-rutinoside), apigenin 7-O-rutinoside, luteolin 7-O-rutinoside, and luteolin 4-O-glucoside. Flavonoids aglycones such as apigenin, quercetin, kaempferol, hesperidin, luteolin, and several phenolic acids (ferulic, caffeic, chlorogenic, p-coumaric, homovanillic, and vanillic) were also found to be present in olive leaves [86,87], pomace [88,89], cake ([90] and references therein), paste [91,92], kernel [93], and wastewater [94]. The recovery of polyphenols from olive byproducts is one of the objectives that is increasingly generating an incredible amount of interest by food researchers and industries. Until now, this goal has been accomplished by the use of different nonconventional methods such as supercritical fluid extraction (SFC), pressurized water extraction (PWE), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE) [83]. Biotechnological approaches have also been studied for both the recovery of phenols and the improvement of bioactivity of olive mill wastes [95]. Fig. 3A and B lists some characteristics of the polyphenols present in the vegetables described in this section.

Fig. 3 Some characteristics polyphenols present in (A) fennel, lettuce, and carrot and (B) artichoke, olive oil, and lemon.

2.4 Fruits (Polyphenols From Apple, Pomegranate, Banana, and Berry Byproducts)

Fruit-processing industries contribute more than 0.5 billion tons of global waste worldwide. The availability of this feedstock and its potential has encouraged researchers to perform detailed compositional studies on fruit-processing wastes, which have been found to be selective and concentrated in nature; peels, pomace, and seed fractions of fruits could be a good source of bioactive compounds such as pectin, lipids, dietary fibers, and polyphenols, whose concentration in fruit-processing wastes is often greater compared with the fruit pulp [17]. Therefore, use of the waste as a source of polyphenols may be of considerable economic benefit to food processors. Fruit waste and byproducts can range from pomace (leftovers after pressing) to cut-offs and whole fruits and vegetables [96].

Apples (Malus pumila Miller) are available all year round and represent one of the main sources of phenolic compounds in the Western diet. Apples contain as much as 2 g of phenols per kilogram wet weight, or about 400 mg total phenols per apple [97]. Apple peel as well as apple seeds also contribute to the quality of the whole fruit and have been recognized as a valuable source of phytochemicals. The main classes of polyphenols in apples are flavonoids, such as flavonols (quercetin and its glycosides); flavan-3-ols ([−]-epicatechin, [+]-catechin, and their oligomers, procyanidins); and anthocyanins. Phloretin derivatives (phloridzin and phloretin) have been generally thought to be specific constituents of this fruit, but a recent study revealed that phloridzin is also present in strawberry fruits [98]. Cinamoylquinic acids such as chlorogenic acid are also present in apples. The occurrence of these polyphenols depends on many factors such as variety, stage of maturity, growing region, and rural practices [99]. The industrial processing of apples is based primarily on the production of apple juice, jelly, and pulp. Fruits that are not suitable for raw consumption are processed, generating large amounts of residues. Apple pomace, the solid residue from juice production, represents around 30% of the original fruit. Many researchers, looking for high added-value products, have proposed the use of apple pomace for the production of enzymes, organic acids, protein-enriched feeds, edible mushrooms, bioethanol, aroma compounds, natural antioxidants, and edible fibers [100]. Apple pomace is also the prevalent byproduct in the cider-making industry [101]. Very similar to apple pulp, apple pomace has been reported as a source of polyphenols: protocatechuic acid, hydroxycinnamic acids esters (mainly chlorogenic acid), flavan-3-ols, dihydrochalcones, and flavonols (rutin, isoquecitrin, quercitrin) [101,102].

Pomegranate (Punica granatum L.) is a small tree originating from the Middle East, now extending throughout the Mediterranean, China, India, South Africa, and America [103]. Pomegranate fruit is one of the oldest edible fruits, known for its pleasant taste and excellent health-benefiting properties, which has been used extensively in the folk medicine of many cultures [104]. The beneficial properties attributed to pomegranate are not limited to the edible part of fruit, in fact, the nonedible parts of the fruit and tree (peel, seeds, flowers, bark, buds, and leaves), although considered waste, contain even higher amounts of specific nutritionally valuable and biologically active components [105]. More than 100 different phytochemicals can be found in pomegranate fruit; among these are high molecular weight polyphenols ellagitannins and the pomegranate-peculiar punicalagin [106]. On the other hand, nearly 50 phenolic compounds have been identified in pomegranate peels and other anatomical parts of the fruit. Pomegranate peels constitute ~ 40% of the whole fruit and are rich in ellagic acid derivatives such as ellagitannins, punicalagin, and punicalin. Some simple ellagic acid derivatives (ellagic acid-hexoside, ellagic acid-pentoside, etc.) are also present, although in lesser amounts. Interestingly, pomegranate peels contain the most promising pool of phenolics (predominantly those from hydrolysable tannins) compared with their concentration in any other anatomical part of the fruit. For these reasons, great attention has been given to this waste product, and conventional and nonconventional methods to recover bioactive molecules from this matrix have been studied [104,107]. Novel methodologies to stabilize phenolics in complex matrices, such as microencapsulation, have also been applied to pomegranate peels [108].

Banana (Musa cavendishii) is the second-largest produced fruit after citrus, contributing for about 16% of the total fruit production worldwide [109]. The original bananas grew in Southeast Asia but contained many bitter black seeds so they were almost inedible. Cultivation of bananas commenced in the West Indies in the 17th century. There are both sweet and cooking bananas, the latter sometimes called plantains [63]. In terms of use and consumption, bananas are a basic foodstuff, consumed fresh or cooked. Bananas are also raw materials in a variety of domestic and regional products (fritters, jams, wines, beer); domestic and artisanal flour; purees; regional beers; wine; vinegar; nectar; chunks; and as ingredients in culinary preparations (pastries, desserts, ice creams, sorbets, and cream products). Unpeeled green bananas are used as an animal feed, especially for pigs. The majority of these uses generate large amounts of byproducts, primarily banana peels [110]. Bananas are reported to contain lutein, α-carotene, β-carotene, and high concentrations of the catecholamine dopamine, which is a strong antioxidant, together with norepinephrine (noradrenaline). Bananas are also rich in phenolic compounds, which causes the astringent taste of unripe fruits [109]. Among banana polyphenols, the organic acids gallic and protocatechuic are the most represented, together with the hydroxycinnamic acids caffeic and ferulic. Flavan-3-ols and flavonols are also present in bananas [111–113]. The flavan-3-ol (+)-gallocatechin was found in commercial bananas by Someya et al. [114]; the authors also found this phenol was more abundant in peel (158 mg/100 g dry wt.) than in pulp (29.6 mg/100 g dry wt.). As a general trend, higher levels of polyphenols are found in banana peel than the pulp; for example, Faller and Fialho [115] found that the levels of both soluble and insoluble polyphenols tended to be nearly two times higher in banana peels with respect to the pulp.

Berries (cranberry, strawberry, blueberry, raspberry), commonly referred to as colored fruits, can be consumed fresh but are also generally available as frozen product or processed into juice, jam, ice cream, and wine [116]. The processing of berries generally results in ~ 20% to 30% of byproduct. Berries are commonly squeezed, treated with pectinases, and heated prior to juice extraction; the residue from berry processing (seeds, skins, and stems) is commonly denoted as pomace. Berry pomace is usually recycled as animal feed, composted, used for biogas production, or simply discarded [117]. The berry fruits are rich in phenolic compounds such as phenolic acids, flavonoids (mainly highly hydroxylated flavonols such as glycosides and other derivatives of quercetin, myricetin, and kaempferol), and anthocyanins. Glucosides, galactosides, and arabinosides of cyanidin, peonidin, and other minor anthocyanins (malvidin, petunidin, delphinidin, and pelargonidin) impart the dark red or blue color to these fruits, and are also powerful antioxidants. Ellagic acid and ellagitannins are also present in berries [118,119]. Variation in the content of phenolic compounds is mainly due to the differences in the berry species, varieties, and growth conditions. Also, methodological differences may contribute to the variability in the reported flavonoid and phenolic acid concentrations. In raspberries and strawberries, the content of ellagic acid is reported to be high but not higher than that of anthocyanins [120]. With regard to berry byproducts, it has been reported that many phenolic compounds located in the skins and seeds of the berries are retained in pomace, which therefore constitutes a valuable plant-based source of phytochemicals and a precious ingredient for processed foods [117,121]. Fig. 4 shows some peculiar polyphenol components from the fruits previously described.

Fig. 4 Some characteristics polyphenols present in selected fruits: apple, pomegranate, banana, and berries.

3 Something to Drink: Polyphenols in Most Common Beverage Byproducts

3.1 Orange Juice (Polyphenols From Orange Byproducts)

As previously discussed, the citrus industry (oranges, lemons, and grapefruits) is of capital importance in tropical and subtropical zones of the world. In contrast with other types of fruits, citrus fruits have a small edible portion and large amounts of waste material such as peels and seeds. Therefore, citrus processing produces a considerable amount of byproducts, which could be used as functional ingredients when designing healthy foods (functional foods), especially nondigestible carbohydrates (dietary fiber) and bioactive compounds (ascorbic acid and polyphenols) [122].

Oranges (C. sinensis L.) represent by far the most important class of commercial citrus fruits. Approximately 40% of the oranges produced globally are used in processing to make different commercial products, such as dehydrated products or marmalades, jams, fresh juice, and flavoring agents for beverages [123,124]. The domestic and industrial use of large quantities of orange fruits, especially for the production of juice, results in the accumulation of high amounts of byproducts such as peel, seed, cell, and membrane residues, which account for about half of the fresh fruit weight. These byproducts can be used for the production of molasses, pectins, essential oils, limonene, and cattle feed [125]. Compositionally speaking, they represent a source of fat (oleic, linoleic, linolenic, palmitic, stearic, glycerin, and phytosterols), sugars (glucose, fructose, sucrose), acids (especially citric and malic acid, tartaric, but also benzoic, oxalic, and succinic acids), insoluble carbohydrates (cellulose, pectin), enzymes (pectinesterase, phosphatase, peroxidase), essential oils (d-limonene), pectins, and pigments (carotenoids, xanthophylls). Flavanones (especially the characteristic glycosides such as naringin, hesperidin, narirutin, and neohesperidin) and polymethoxy flavones, which are responsible for the antiinflammatory activity of this matrix, are also present [126,127]. All of these components are found in different amounts depending on the fraction of the fruit (juice, albedo, flavedo, rag and pulp, and seeds), and therefore their proportion in orange juice residues