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SCIENCE AND ENGINEERING OF POLYPHENOLS A groundbreaking synthesis of rich and varied polyphenol research Polyphenols are a class of compounds, found naturally in fruits and vegetables, whose flexibility and ubiquity give them a vast range of applications in pharmaceutical, environmental, and biological research and development. They play a role in diagnosing and preventing diseases from diabetes to Parkinson's to Alzheimer's and have been integral in food preservation. The field of polyphenols research has the potential to touch virtually every area of organic production. Science and Engineering of Polyphenols provides a current and comprehensive overview of this field of research and its latest developments. Long overdue as a 'state of the field' synthesis for an area of study that has seen rapid development in recent years, this book promises to be a milestone. Science and Engineering of Polyphenols readers will also find: * Treatment of both natural and synthetic polyphenols * Detailed discussion of topics including synthesis and characterization of polyphenols, electronic and molecular structure of polyphenols, and many more * Supplementary material including websites of interest and updates on the latest research and development Science and Engineering of Polyphenols is ideal for scholars, industrialists, and policymakers in any of the myriad areas of academia and industry touched by polyphenol research.
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Edited byChandrabhan VermaDepartment of Chemical EngineeringKhalifa University of Science and TechnologyAbu Dhabi,United Arab Emirates
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Names: Verma, Chandrabhan, editor.Title: Science and engineering of polyphenols : fundamentals and industrial scale applications / edited by Chandrabhan Verma, Khalifa University of Science and Technology, Abu Dhabi, United Arab Emirates.Description: Hoboken, New Jersey : Wiley, [2024] | Includes bibliographical references and index.Identifiers: LCCN 2023053751 (print) | LCCN 2023053752 (ebook) | ISBN 9781394203901 (hardback) | ISBN 9781394203918 (adobe pdf) | ISBN 9781394203925 (epub)Subjects: LCSH: Polyphenols. | Polyphenols—Industrial applications. | Polyphenols—Therapeutic use.Classification: LCC QK898.P764 S35 2024 (print) | LCC QK898.P764 (ebook) | DDC 547/.632—dc23/eng/20231221LC record available at https://lccn.loc.gov/2023053751LC ebook record available at https://lccn.loc.gov/2023053752
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Polyphenols are a class of micronutrients that are naturally present in plants, and they are of interest due to their potential for technological advancement and therapeutic effects. They are present in many supplements and readily available in various foods, including fruits, vegetables, teas, and spices. There are more than 8000 different varieties of polyphenols. The majority of the antioxidants in our diets are polyphenols. The two primary types of polyphenols, accounting for one‐third and two‐thirds, are phenolic acids (mostly caffeic acid) and flavonoids, respectively. The chemical structure of polyphenols is related to their biological characteristics, bioavailability, antioxidant activity, and specific interactions with cell receptors and enzymes. Polyphenols substantially impact diagnosing and preventing many diseases, including diabetes, obesity, Parkinson's, Alzheimer's, and others. They are connected to several significant properties, making them candidates for pharmacological, biological, and industrial applications.
The book, Science and Engineering of Polyphenols: Fundamentals and Industrial Scale Applications, describes polyphenols' science and engineering, including their fundamentals and industrial‐scale applications. The book is divided into three sections. Part I is related to the overview of polyphenols and contains four chapters. Chapters 1 and 2 describe the fundamentals of polyphenols and their nomenclature, classification, properties, synthesis, characterization, and chemical reactivities. Chapters 3 and 4 account for the extraction, purification, and characterization of plant‐derived polyphenols and the degradation and fermentation of the polyphenols, respectively. Part II describes the different industrial applications of polyphenols. Part II has eight chapters (Chapters 5–12), each reporting a specific industrial application of polyphenols. Chapters 5–10 describe wastewater treatment, corrosion protection, dyes, packaging, textile, and sensing/biosensing applications of polyphenols. Chapter 11 reports the fundamental properties and industrial applications of polyphenol‐based hydrogels and nanocomplexes. Lastly, Chapter 12 describes the chemo‐ and bio‐sensing applications of polyphenol‐based materials.
Part III discusses the biological uses of polyphenols. It is divided into 11 chapters (Chapters 13–23), each discussing a different biological use. Chapters 13 and 14 discuss the applications of polyphenols in COVID‐19 control and dietary applications, respectively. Chapter 15 reports the use of polyphenols in health management and disease control. Chapters 16 and 17 report polyphenols' antimicrobial and antioxidant uses, respectively. Chapter 18 describes the polyphenols derived from marine organisms and their biofunctional properties. Chapters 19–22 describe the different applications of polyphenols, including dietary, food additives, and pharmaceuticals (Diagnosis, Therapies, and Prevention of Diseases). The last chapter (Chapter 23) discusses the phenolic compounds (polyphenols) isolated from marine organisms and their biofunctional properties.
I, Dr. Chandrabhan Verma (the editor), thank all contributors for their outstanding efforts. On behalf of John Wiley & Sons, Inc. (Wiley Publications), I am very thankful to the authors of all chapters for their outstanding and passionate efforts in making this book. Special thanks to Dr. Michael Leventhal (commissioning editor) and Dr. Dorairaj Vijayan (Editorial Assistant) for their dedicated support and help during this project. In the end, all thanks to John Wiley & Sons, Inc. (Wiley Publications) for publishing the book.
Chandrabhan Verma, PhD
(Editor)
15 JanuaryAbu Dhabi, United Arab Emirates
Name: Chandrabhan Verma
Affiliation: Department of Chemical Engineering, Khalifa University of Science and Technology, Abu Dhabi, United Arab Emirates
Email: [email protected]
Chandrabhan Verma works at the Department of Chemical Engineering, Khalifa University of Science and Technology, Abu Dhabi, United Arab Emirates. Dr. Verma obtained B.Sc. and M.Sc. degrees from Udai Pratap Autonomous College, Varanasi (UP), India. He received his PhD from the Department of Chemistry, Indian Institute of Technology (Banaras Hindu University) Varanasi, under the supervision of Prof. Mumtaz A. Quraishi in Corrosion Science and Engineering. He has served as a member of the American Chemical Society (ACS) and a lifetime member of the World Research Council (WRC). He is a reviewer and editorial board member of various internationally recognized ACS, RSC, Elsevier, Wiley, and Springer platforms. Dr. Verma published numerous research and review articles in different areas of science and engineering at ACS, Elsevier, RSC, Wiley and Springer, etc. He has a total citation of more than 12000, with an H‐index of 61 and an i‐10 index of 155. His current research focuses on designing and developing industrially applicable corrosion inhibitors. Dr. Verma edited a few books for the ACS, Elsevier, RSC, Springer, and Wiley. Dr. Verma received several awards for his academic achievements, including a Gold medal in M.Sc. (Organic Chemistry, 2010) and Best Publication awards from the Global Alumni Association of IIT‐BHU (Second Prize 2013).
Sidra Subhan2, Muhammad Zeeshan2, Ata Ur. Rahman1, and Muhmmad Yaseen1,*
1 Institute of Chemical Sciences, University of Peshawar, Peshawar, KP, Pakistan
2 Department of Chemistry, Bacha Khan University, Charsadda, Pakistan
Polyphenols are a class of substances that are found in plants and are renowned for having antioxidant qualities [1]. The basic structure of polyphenols consists of one or more aromatic rings with hydroxyl (—OH) groups attached to them as shown in Figure 1.1, which helps to neutralize free radicals (which are highly reactive molecules that can cause damage to cells and contribute to various diseases, including cancer, heart disease, and Alzheimer's disease, etc.) [2]. In order to protect themselves against environmental factors including ultraviolet (UV) radiation, diseases, and pests, plants can produce them. Flavonoids, phenolic acids, lignans, and stilbenes are just a few of the numerous chemically different molecules that comprise the complex group of substances called polyphenols [3]. Fruits, vegetables, tea, coffee, red wine, and chocolate are a few major dietary sources of polyphenols. As per research, polyphenols may provide a wide range of health benefits [4]. For instance, it has been revealed that they possess antioxidant activity anti‐inflammatory, anti‐cancer, neuroprotective activity, antidiabetic activity, and cardiovascular health‐promoting properties. They also reduce the heart disease risk. They may service people manage their blood sugar levels and have neuroprotection [5]. While phenols are generally safe and well‐tolerated, it is important to note that they can also interact with certain medications and affect their absorption and effectiveness. Therefore, before taking high doses of polyphenol supplements, it is essential to speak with a healthcare expert or making significant dietary changes to increase polyphenol consumption [6].
Figure 1.1 Basic structure of polyphenol. Source: Oscar Vidal‐Casanella et al. [2]/Reproduced from MDPI/CC BY 4.0.
The name derives from the Ancient Greek word (polus, meaning “many, much”) and the word “phenol,” which refers to a chemical structure formed by attaching to an aromatic benzenoid (phenyl) ring to —OH group as is found in alcohols (hence the ‐ol suffix). The term “polyphenol” used since 1894 is a Greek‐rooted word polus meaning many and phenol refereeing to the chemical structure formed by attaching phenyl ring to —OH group. The history of polyphenols can be traced back to ancient times when they were used for medicinal purposes and as food preservatives. One of the earliest recorded uses of polyphenols was by the ancient Egyptians, who used tannin‐rich plant extracts to preserve mummies. In ancient Greece, Hippocrates, the father of modern medicine, recognized the medicinal properties of wine, which contains high levels of polyphenols. During the Middle Ages, polyphenols were used as natural remedies for a variety of ailments. For example, extracts of grape seeds were used to treat skin conditions and digestive disorders. In the 16th century, the Spanish physician Andres Laguna wrote about the medicinal properties of tea, which contains high levels of polyphenols. In the 19th and early 20th centuries, the study of polyphenols became more scientific. In 1853, the French chemist Henri Braconnot isolated tannins, which are a type of polyphenol, from oak bark. In the early 20th century, the German chemist Richard Willstätter discovered the chemical structure of flavonoids, which are another type of polyphenol. Today, research continues into the potential health benefits of polyphenols, which include reducing inflammation, improving cardiovascular health, and protecting against certain types of cancer. Polyphenols are found in a wide range of plant‐based foods, including fruits, vegetables, tea, coffee, and wine and are an important part of a healthy diet as shown in Table 1.1.
Table 1.1 List of some polyphenol compounds along with their natural sources.
Polyphenols
Natural sources
Resveratrol
Grapes, red wine, peanuts, and berries
Catechins
Green tea, black tea, cocoa, and apples
Quercetin
Onions, apples, grapes, berries, broccoli, and tea
Flavonols
Onions, kale, broccoli, apples, berries, and tea
Anthocyanins
Berries, cherries, grapes, red cabbage, and eggplant
Proanthocyanidins
Grapes, red wine, cocoa, and apples
Ellagic acid
Strawberries, raspberries, pomegranates, and nuts
Curcumin
Turmeric
Chlorogenic acid
Coffee, apples, pears, and blueberries
Luteolin
Celery, parsley, thyme, and peppers
Apigenin
Parsley, celery, chamomile, and peppermint
Isoflavones
Soybeans, lentils, and chickpeas
Myricetin
Berries, grapes, and red wine
Oleuropein
Olives and olive oil
Rutin
Buckwheat, citrus fruits, and asparagus
Stilbenes
Grapes, blueberries, and red wine
Tannin
Tea, wine, and berry
Caffeic acid
Coffee, fruits, and vegetables such as tomatoes and carrot
Ferulic acid
Brown rice, oats, barley, and wheat bra
Hesperidin
Citrus fruits such as oranges and lemons
Delphinidin
Blueberries, cranberries, and grape
Epicatechin
Green tea, cocoa, and apple
Gallocatechin
Green tea, black tea, and cocoa
Isorhamnetin
Onions, grapes, and tomato sauce
Secoisolariciresinol
Flaxseed, sesame seeds, and whole grain
Prodelphinidin
Cocoa and dark chocolate
Ursolic acid
Apples, basil, and cranberries
Chrysin
Honey, propolis, and passionflower
Epigallocatechin
Green tea, black tea, and cocoa
Gallic acid
Grapes, blueberries, and green tea
Hydroxytyrosol
Olives, olive oil, and red win
Malvidin
Red grapes, blackberries, and blueberries
Piceatannol
Blueberries, and passionfruit
Theaflavins
Black tea
Hesperidin
Oranges and lemons
Lignans
Flaxseed, sesame seeds, and whole grains
Syringic acid
Walnuts, and berries such as raspberries and blackberries
A class of naturally occurring substances called polyphenols are present in plants and are distinguished by having many phenolic rings. They may be found in a variety of fruits, vegetables, cereals, tea, coffee, wine, and other plant‐based meals [7]. They are also extensively spread throughout the plant world. One or more aromatic rings with —OH groups attached compose up the fundamental structure of polyphenols [8]. These —OH groups give polyphenols their antioxidant capabilities, which aid in the body's ability to combat free radicals and oxidative stress. Based on their chemical structure, polyphenols may be divided into a number of distinct classes, including flavonoids, phenolic acids, lignans, and stilbenes. The most prevalent and most researched class of polyphenols are flavonoids, which are further divided into subcategories including flavones, flavanones, and flavonol. Deep research has been done on polyphenols' possible on health advantages, which are mostly related to their anti‐inflammatory and antioxidant characteristics [9, 10]. Many chronic diseases, such as cancer, heart disease, and neurological illnesses have been proven to be protected against by them. Polyphenols have a variety of different biological effects that have been discovered in addition to their antioxidant capabilities [11]. For instance, modify the activity of enzymes involved in cell signaling, control gene expression, and interact with the body's proteins and lipids. The bioavailability of polyphenols might change based on the dietary source and processing techniques. it is important to note. For example, certain polyphenols are better absorbed when taken cooked as opposed to raw, while others are more accessible when consumed along with other nutrients like fat. You may improve your general health and well‐being by including a range of foods high in polyphenols in your diet.
The nomenclature of polyphenols can be complex and varies depending on a specific type of polyphenol. However, there are some general rules that are commonly used to name these compounds. Polyphenols are frequently named based on their chemical structure, which usually contains multiple phenolic rings. The simplest polyphenols, such as catechins and flavanols, are named according to the number and position of the —OH groups on the phenolic rings. For example, catechins have two —OH groups on adjacent carbon atoms, while flavanols have —OH groups on different carbon atoms. The number and position of the —OH groups on the phenolic rings of more complex polyphenols, such as flavonoids and phenolic acids, are used to designate them. For instance, the flavonoid quercetin is so called because of the —OH groups that are located at positions 3, 5, 7, and 4′ on its flavone ring (numbering starts at the top of the ring and proceeds clockwise).
Polyphenols may be given names based on their biological function or place of origin. For example, curcumin, a phenolic molecule included in turmeric, has anti‐inflammatory effects, whereas resveratrol is a stilbene polyphenol found in red wine and grapes. Moreover, shorthand acronyms or chemical symbols can be used to identify polyphenols, such as epigallocatechin gallate (EGCG) (a catechin present in green tea) or gallic acid equivalents (a measure of total polyphenol content in a food or beverage) [12–14]. The nomenclature of polyphenols can be complex, and naming conventions can vary depending on the specific type of polyphenol and the context in which it is being used. However, understanding the basic principles of polyphenol naming can help to clarify the structure and properties of these important plant‐based compounds.
Polyphenols can be classified based on their chemical structure and properties. Figure 1.2 shows some of the common classifications of polyphenols [15]:
Figure 1.2 Classification of polyphenols. Source: Rosaria Meccariello et al. [15]/Reproduced from MDPI/CC BY 4.0.
The most well‐known and well‐researched class of polyphenols is flavonoids. They may be identified by their two aromatic rings joined by a three‐carbon chain, which makes up their fundamental chemical structure. Depending on their chemical structure, flavonoids may be further divided into a number of subgroups, including flavones, flavonols, flavanones, flavan‐3‐ols (catechins), isoflavones, anthocyanidins, and anthocyanins. Moreover, sources from plants have given the identification of over 4000 flavonoids. Flavonols, between C3 and C2, a double bond could be observed, and a OH group is linked at C3. The majority of flavonoids found in various dietary sources are flavonols. These compounds are mostly found in onions however, leeks Kale, lettuce, tomatoes and broccoli also contain flavonols [16]. Flavanones due to their distinct patterns of substitution, flavanones exhibit a wide range of substituted derivatives (such as prenylated and benzylated flavanones). The most typical type of glycosylated flavanones has a disaccharide substitution at the C7 position. Most flavanones are present in aglycone forms and are primarily present in citrus fruits, such as oranges and lemons (e.g., hesperidin) [16, 17].
Flavones have a double bond between the C2 and C3 atoms, a carbonyl group at the C4 position, and ring B linked to the heterocyclic ring at the C2 location. Lutein and apigenin are the two key flavones. Moreover, ring B (in isoflavones) is attached to the heterocyclic ring (C3 position) rather than the C2 as in other classes, and an oxygen atom is placed in the C4 position [16, 18]. Flavanols (flavan‐3‐ols) have a saturated heterocyclic ring, a —OH group at position C3, and no double bond between C2 and C3. catechins' characterization derives from the ability to explain two chiral centers, unlike other types of flavonoids. Only aglycones, a kind of flavanol, are present in food (the glycosylated state is excluded). Moreover, they can be found in polymeric forms known as tannins and in monomeric forms known as catechins and epicatechins. epicatechins are diastereoisomers and have a —OH group linked to the C3 position. Epicatechin has the cis configuration of the stereoisomers (+)‐epicatechin and (−)‐epicatechin, whereas the catechin isomer has the Trans configuration of two stereoisomers, (+)‐catechin and (−)‐catechin. These structures, which are referred to as tannins in connection to polymeric flavanols, have excellent water solubility and a relatively high molecular weight. With the help of the B ring, ring C is joined to its C3 edge in isoflavones. Legumes are a rich source of these substances as well. While soybeans are the major supply for food. isoflavones have a greater impact on health. Together with glycitein, two more important isoflavones present in soy are daidzein and genistein. Such compounds can also be found in red clovers.
The most common types of isoflavone‐aglycones are 7‐O‐glucosides and 6ʺ‐O‐malonyl‐7‐O‐glucosides. Dalbergin is the main neo‐flavonoid found in plant‐based meals [19–21]. The presence of two double bonds in the heterocyclic rings of anthocyanidins and anthocyanins sets them apart from other flavonoids. The hydroxylation and methoxylation patterns on ring B define anthocyanins, which are anthocyanidins in their glycosylated form. A range of anthocyanins are produced by differences in the number of hydroxylated groups, the kind, and the quantity of linked sugar units to their structures. Often, monosaccharides like glucose, galactose, and arabinose make up bonded sugar units. The majority of the colors seen are attributed to molecules called glycosylated anthocyanins, which are water‐soluble pigments found in vibrant flowers and fruits [17, 21].
Nonflavonoids consist mostly of a single aromatic ring. Stilbenes, lignans, and phenolic acids are examples of nonflavonoid chemicals. Phenolic acids, mostly derivatives of benzoic acid and cinnamic acid, make up the bulk of this group's chemical composition.
Phenolic acids: One or more —OH groups are connected to a single aromatic ring, which distinguishes phenolic acids from other polyphenols. These may be found in a variety of plant‐based foods, such as grains, fruits, and vegetables. Gallic acid and hydroxycinnamic acids are the two most prevalent forms of phenolic acids (e.g. caffeic acid) [22].
Stilbenes: A class of polyphenols known as stilbenes is distinguished by two aromatic rings joined by a double bond. The most popular stilbene is resveratrol, which may be found in red wine, peanuts, and grapes. Many possible health advantages, such as anti‐inflammatory and antioxidant capabilities, have been associated with resveratrol [23].
Lignans: Lignans are polyphenols that resemble phenolic acids structurally but are joined by a carbon–carbon bond. Foods including flaxseed, sesame seeds, whole grains, and some vegetables contain them. Bacteria in the stomach break down lignans to create enterolignans, which have been found to improve health [24].
A popular and effective method for extracting polyphenols from plant sources is ultrasonic‐assisted extraction (UAE) shown in Figure 1.3[25]. It is a simple, quick, non‐destructive, and energy‐saving technique that can increase the polyphenols' extraction yield as well as quality. The frequency, power, duration, and solvent type used in UAE all have a significant effect on the quantity and quality of the polyphenols that are extracted. First, a dry, ground‐up sample of plant materials is collected and combined with an appropriate extraction solvent in a process known as UAE. For polyphenol extraction, ethanol, methanol, and water are frequently used as solvents. The most used solvent for polyphenol extraction is ethanol. Put the sample in an ultrasonic bath and sonicate it. The ultrasonic waves help to break down the cell walls and facilitate the release of polyphenols from the plant material. The extract is then filtered via filter paper or a syringe filter to remove any insoluble material. Make the extract more concentrated by using a vacuum concentrator or a rotary evaporator. UAE functions on the basic premise that high‐frequency sound waves cause cavitation bubbles to form in the solvent, which then violently collapses, producing strong shear forces that rupture the cell walls of the plant material and release the desired chemicals. The mass transfer and solubility of the polyphenols in the solvent are also increased by the ultrasonic vibrations, leading to a faster and more efficient extraction. For example, compared to traditional solvent extraction, ultrasonic‐assisted polyphenol extraction from mulberry leaves and grape skins and seeds produced considerably greater yields and total polyphenol contents. Yet, it was shown that a frequency of 40 kHz produced the best extraction yield and antioxidant activity when polyphenols were extracted from bamboo leaves. Methanol was the most efficient solvent for extraction of polyphenols from pomegranate peels when compared to conventional solvent extraction methods. Polyphenols from different plant materials such as EGCG from green tea leaves, quercetin from onion peel, anthocyanins from purple sweet potato, chlorogenic acid from Eucommia ulmoides olive leaves, catechins from grape seeds and Rutin from Sophora japonica L. flowers can be extracted.
Figure 1.3 Ultrasonic assisted extraction of polyphenols. Source: Farida Berkani et al. [25]/Reproduced from MDPI/CC BY 4.0.
In the late 1980s, microwave‐assisted extraction of polyphenols from natural products was introduced. As a result of technical advancements, today it is one of the most common and economical extraction techniques. Microwave‐assisted extraction is a widely used technique for the extraction of polyphenols from plant materials. Microwave energy is used in microwave‐assisted extraction to heat the solvent and the sample, speeding up the extraction process. In order to increase the extraction yield and quality of polyphenols, microwave‐assisted extraction has been recommended as a simpler, quicker, non‐destructive, less time‐consuming, and energy‐efficient method. Microwave‐assisted extraction involves heating the solvent and the sample in a microwave oven, where the microwave energy causes the solvent to heat and release its polyphenols as shown in Figure 1.4[26]