Natural Beverages: Volume 13: The Science of Beverages 9780128166895, 0128166894, 9780128166901, 0128166908

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N AT U R A L B E V E R A G E S

N AT U R A L B E V E R A G E S Volume 13: The Science of Beverages Edited by

ALEXANDRU MIHAI GRUMEZESCU ALINA MARIA HOLBAN

An imprint of Elsevier

Woodhead Publishing is an imprint of Elsevier The Officers’ Mess Business Centre, Royston Road, Duxford, CB22 4QH, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States The Boulevard, Langford Lane, Kidlington, OX5 1GB, United Kingdom © 2019 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www. elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN 978-0-12-816689-5 For information on all Woodhead publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Cockle, Charlotte Acquisition Editor: Osborn, Patricia Editorial Project Manager: Kubilis, Michelle Production Project Manager: Sojan P. Pazhayattil Cover Designer: Matthew Limbert Typeset by SPi Global, India

CONTRIBUTORS S Asha  Department of Biochemistry, St. Thomas College, Pala, Kottayam, India Victoria Konstantinova Atanasova  Department of Hygiene and Ecomedicine, Faculty of Public Health, Medical University, Plovdiv, Bulgaria Irena Barukčić  Department for Food Engineering, Laboratory for Technology of Milk and Milk Products, University of Zagreb, Zagreb, Croatia Biman Bhuyan  Department of Pharmaceutical Sciences, Dibrugarh University, Dibrugarh, Assam Rajka Božanić  Department for Food Engineering, Laboratory for Technology of Milk and Milk Products, University of Zagreb, Zagreb, Croatia Marian Butu  National Institute of Research and Development for Biological Sciences, Bucharest, Romania Pratyasha Dash  Department of Biomedical Sciences, School of Biosciences and Technology, VIT University, Vellore, India V. Devi Rajeswari  Department of Biomedical Sciences, School of Biosciences and Technology, VIT University, Vellore, India S. Escobedo-García  Department of Food Science and Technology, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico Miguel A. Faria  Department of Chemical Sciences, Laboratory of Bromatology and Hydrology, Faculty of Pharmacy, University of Porto, Porto, Portugal Lydia Ferrara  Department of Pharmacy, University of Naples Federico II, Naples, Italy Isabel M.P.L.V.O. Ferreira  Department of Chemical Sciences, Laboratory of Bromatology and Hydrology, Faculty of Pharmacy, University of Porto, Porto, Portugal Adriana C. Flores-Gallegos  Department of Food Science and Technology; Food Research Department, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico Monica Gallo  Department of Molecular Medicine and Medical Biotechnology, University of Naples Federico II, Naples, Italy Penka Dimitrova Gatseva  Department of Hygiene and Ecomedicine, Faculty of Public Health, Medical University, Plovdiv, Bulgaria

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Ángela-Mariela González-Montemayor  Department of Food Science and Technology; Food Research Department, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico Reyhan Irkin  Health Science Faculty, Nutrition and Dietetics Department, Izmir Democracy University, Izmir, Turkey Katarina Lisak Jakopović  Department for Food Engineering, Laboratory for Technology of Milk and Milk Products, University of Zagreb, Zagreb, Croatia Rita Jirillo  Department of Economics and Enterprises, Università della Tuscia di Viterbo, Viterbo, Italy Svenia P. Jose  Department of Biochemistry, St. Thomas College, Pala, Kottayam, India Vahid Mohammadpour Karizaki  Chemical Engineering Department, Quchan University of Technology, Quchan, Iran Shramana Koner  Department of Biomedical Sciences, School of Biosciences and Technology, VIT University, Vellore, India I.M Krishnakumar  R&D Centre, Akay Flavours & Aromatics Pvt Ltd, Cochin, India Mercedes G. López-Pérez  Biotechnology and Biochemistry Department, Center for Research and Advanced Studies-IPN, Irapuato Unit, Guanajuato, Mexico Júlio C. Machado, Jr  Department of Chemical Sciences, Laboratory of Bromatology and Hydrology, Faculty of Pharmacy, University of Porto, Porto, Portugal M. Michel-Michel  Department of Food Science and Technology, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico Julio César Montañez-Sáenz  Food Research Department, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico D.B. Muñiz-Márquez  Instituto Tecnológico de Ciudad Valles, Tecnológico Nacional de México, Ciudad Valles, Mexico Martina Musarra  Department of Management, Sapienza University of Rome, Rome, Italy Daniele Naviglio  Department of Chemical Sciences, University of Naples Federico II, Naples, Italy Gülşah Özcan-Sinir  Department of Food Engineering, Uludag University, Bursa, Turkey Vernita Priya  Department of Biomedical Sciences, School of Biosciences and Technology, VIT University, Vellore, India Krystyna Pyrzynska  Department of Chemistry, University of Warsaw, Warsaw, Poland

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Prakash Rajak  Department of Pharmaceutical Sciences, Dibrugarh University, Dibrugarh, Assam Mattia Rapa  Department of Management, Sapienza University of Rome, Rome, Italy M Ratheesh  Department of Biochemistry, St. Thomas College, Pala, Kottayam, India Steliana Rodino  National Institute of Research and Development for Biological Sciences; Research Institute for Agriculture Economy and Rural Development, Bucharest, Romania Raúl Rodríguez-Herrera  Department of Food Science and Technology; Food Research Department, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico J.A. Salas-Tovar  Department of Food Science and Technology, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico S Sandya  Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India Aleksandra Sentkowska  Heavy Ion Laboratory, University of Warsaw, Warsaw, Poland Lilia E. Serrato-Villegas  Material Science Research Department, School of Chemistry, Autonomous University of Coahuila, Boulevard Venustiano Carranza and Jose Cardenas s/n, Saltillo, Coahuila, Mexico Senem Suna  Department of Food Engineering, Uludag University, Bursa, Turkey Canan Ece Tamer  Department of Food Engineering, Uludag University, Bursa, Turkey S.L. Villarreal-Morales  Department of Food Science and Technology, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico Giuliana Vinci  Department of Management, Sapienza University of Rome, Rome, Italy

SERIES PREFACE Food and beverage industry accounts among the most developed sectors, being constantly changing. Even though a basic beverage industry could be found in every area of the globe, particular aspects in beverage production, processing, and consumption are identified in some geographic zones. An impressive progress has recently been observed in both traditional and modern beverage industries and these advances are leading beverages to a new era. Along with the cutting-edge technologies, developed to bring innovation and improve beverage industry, some other human-related changes also have a great impact on the development of such products. Emerging diseases with a high prevalence in the present, as well as a completely different lifestyle of the population in recent years have led to particular needs and preferences in terms of food and beverages. Advances in the production and processing of beverages have allowed for the development of personalized products to serve for a better health of overall population or for a particular class of individuals. Also, recent advances in the management of beverages offer the possibility to decrease any side effects associated with such an important industry, such as decreased pollution rates and improved recycling of all materials involved in beverage design and processing, while providing better quality products. Beverages engineering has emerged in such way that we are now able to obtain specifically designed content beverages, such as nutritive products for children, decreased sugar content juices, energy drinks, and beverages with additionally added health-promoting factors. However, with the immense development of beverage processing technologies and because of their wide versatility, numerous products with questionable quality and unknown health impact have been also produced. Such products, despite their damaging health effect, gained a great success in particular population groups (i.e., children) because of some attractive properties, such as taste, smell, and color. Nonetheless, engineering offered the possibility to obtain not only the innovative beverages but also packaging materials and contamination sensors useful in food and beverages quality and security sectors. Smart materials able to detect contamination or temperature differences which could impact food quality and even pose a hazardous situation for the consumer were recently developed and some are already utilized in packaging and food preservation.

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This 20-volume series has emerged from the need to reveal the current situation in beverage industry and to highlight the progress of the last years, bringing together most recent technological innovations while discussing present and future trends. The series aims to increase awareness of the great variety of new tools developed for traditional and modern beverage products and also to discuss their potential health effects. All volumes are clearly illustrated and contain chapters contributed by highly reputed authors, working in the field of beverage science, engineering, or biotechnology. Manuscripts are designed to provide necessary basic information in order to understand specific processes and novel technologies presented within the thematic volumes. Volume 1, entitled Production and management of beverages, offers a recent perspective regarding the production of main types of alcoholic and nonalcoholic beverages. Current management approaches in traditional and industrial beverages are also dissected within this volume. In Volume 2, Processing and sustainability of beverages, novel information regarding the processing technologies and perspectives for a sustainable beverage industry are given. Third volume, entitled Engineering tools in beverage industry dissects the newest advances made in beverage engineering, highlighting cutting-edge tools and recently developed processes to obtain modern and improved beverages. Volume 4 presents updated information regarding Bottled and packaged waters. In this volume are discussed some wide interest problems, such as drinking water processing and security, contaminants, pollution and quality control of bottled waters, and advances made to obtain innovative water packaging. Volume 5, Fermented beverages, deals with the description of traditional and recent technologies utilized in the industry of fermented beverages, highlighting the high impact of such products on consumer health. Because of their great beneficial effects, fermented products still represent an important industrial and research domain. Volume 6 discusses recent progress in the industry of Nonalcoholic beverages. Teas and functional nonalcoholic beverages, as well as their impact on current beverage industry and traditional medicine are discussed. In Volume 7, entitled Alcoholic beverages, recent tools and technologies in the manufacturing of alcoholic drinks are presented. Updated information is given about traditional and industrial spirits production and examples of current technologies in wine and beer industry are dissected. Volume 8 deals with recent progress made in the field of Caffeinated and cocoa-based beverages. This volume presents the great variety of

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such popular products and offers new information regarding recent technologies, safety, and quality aspects as well as their impact on health. Also, recent data regarding the molecular technologies and genetic aspects in coffee useful for the development of high-quality raw materials could be found here. In Volume 9, entitled Milk-based beverages, current status, developments, and consumers trends in milk-related products are discussed. Milk-based products represent an important industry and tools are constantly been developed to fit the versatile preferences of consumers and also nutritional and medical needs. Volume 10, Sports and energy drinks, deals with the recent advances and health impact of sports and energy beverages, which became a flourishing industry in the recent years. In Volume 11, main novelties in the field of Functional and medicinal beverages, as well as perspective of their use for future personalized medicine are given. Volume 12 gives an updated overview regarding Nutrients in beverages. Types, production, intake, and health impact of nutrients in various beverage formulations are dissected through this volume. In Volume 13, advances in the field of Natural beverages are provided, along with their great variety, impact on consumer health, and current and future beverage industry developments. Volume 14, Value-added Ingredients and enrichments of beverages, talks about a relatively recently developed field which is currently widely investigated, namely the food and beverage enrichments. Novel technologies of extraction and production of enrichments, their variety, as well as their impact on product quality and consumers effects are dissected here. Volume 15, Preservatives and preservation approaches in beverages, offers a wide perspective regarding conventional and innovative preservation methods in beverages, as well as main preservatives developed in recent years. In Volume 16, Trends in beverage packaging, the most recent advances in the design of beverage packaging and novel materials designed to promote the content quality and freshness are presented. Volume 17 is entitled Quality control in the beverage industry. In this volume are discussed the newest tools and approaches in quality monitoring and product development in order to obtain ­advanced beverages. Volume 18, Safety issues in beverage production, presents general aspects in safety control of beverages. Here, the readers can find not only the updated information regarding contaminants and risk factors in beverage production, but also novel tools for accurate detection and control.

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Volume 19, Biotechnological progress and beverage consumption, reveals novel tools used for advanced biotechnology in beverage industry production. Finally, Volume 20 entitled Nanoengineering in the beverage ­industry take the readers into the nanotechnology world, while highlighting important progress made in the field of nanosized materials science aiming to obtain tools for a future beverage industry. This 20-volume series is intended especially for researchers in the field of food and beverages, and also biotechnologists, industrial representatives interested in innovation, academic staff and students in food science, engineering, biology, and chemistry-related fields, pharmacology and medicine, and is a useful and updated resource for any reader interested to find the basics and recent innovations in the most investigated fields in beverage engineering.

Alexandru Mihai Grumezescu Alina Maria Holban

PREFACE Despite the great progress of engineered foods and beverages, ­ atural beverages are still preferred and consumed worldwide. This n category of drinks contains a wide variety of products, some of them widely known and consumed, such as juices, fermented beverages, teas, but others are manufactured in particular areas only. Natural beverages are preferred because of their nutritious and healthy content, ease to be obtained, and also because they do not usually involve harmful processing technologies. The most important feature still remains their great value for health and well-being. The purpose of this volume is to give an updated overview regarding the variety of the availability of natural beverages, their particularities, and health impact. The volume contains 15 chapters prepared by outstanding authors from Italy, Bulgaria, India, Iran, Poland, México, Croatia, Portugal, Romania, and Turkey. The selected manuscripts are clearly illustrated and contain accessible information for a wide audience, especially food and beverage scientists, engineers, biotechnologists, biochemists, industrial companies, students and also any reader interested in learning about the most interesting and recent advances in beverage science. Chapter 1, entitled An overview of natural beverages, prepared by Monica Gallo et al., aims to explore the classifications, origins, and characteristics of natural beverages, offering an introduction on this field. Chapter 2, Natural beverages and their role as functional foods, by Victoria Konstantinova Atanasova and coworker, discusses the importance of an appropriate starting material for the production of functional beverages with rich content of biologically active ingredients. It seems that the health effects of chokeberry juice, tomato juice, and pastes with a higher content of lycopene and beta-carotene are widely investigated. Chapter 3, Natural beverages of Assam and its ethno medicinal value, by Biman Bhuyan and Prakash Rajak, presents the different plants and production technologies of natural conventional ricebased beverages developed in the area of Assam. Chapter 4, The natural beverages of the Iranian cuisine, by Vahid Mohammadpour Karizaki, aims at documenting and introducing the natural beverages of the Iranian cuisine. The name, variety, major ingredients, and the main property or characteristic of each beverage are presented, as well as the cultural and social aspects of the Iranian beverages are reviewed.

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Chapter 5, Herbal beverages as a source of antioxidant phenolics, by Krystyna Pyrzynska and Aleksandra Sentkowska, summarizes the content of main polyphenolic compounds present in the most popular herbal beverages and their antioxidant activity. Additionally, some remarks are given for possible herb-drug interactions. Chapter  6, Honey and syrups: healthy and natural sweeteners with functional properties, by Ángela-Mariela González-Montemayor et al., discusses differences among commercially available honeys and syrups as well as their functional properties, processing, production, use in the beverage industry, and authentication. Chapter 7, Aguamiel a fresh beverage from Agave spp. sap with functional properties, by S.L. Villarreal-Morales et al., describes the nutritional quality of aguamiel as well as the probiotic and prebiotic activity, which allow this beverage to be considered as a functional beverage. Chapter 8, Whey and buttermilk—neglected sources of valuable beverages, by Irena Barukčić et  al., discusses the great potential of whey and buttermilk which are the main by-products of the dairy industry, to be utilized as valuable sources for natural beverages. Chapter 9, Canapa sativa L. and Moringa oleifera as naturally functional beverages: innovative trends, by Musarra Martina et al., discusses the great demand for natural and functional products which has increased in the last years, demonstrating that consumers are paying more attention to product labels, showing the growing preference for natural and local ingredients that have a positive benefit on body and mental health. Chapter 10, Hops: new perspectives for an old beer ingredient, by Júlio C. Machado Jr. et al., aims to describe the importance of hops in the new trend of beer production, reviewing hops market, varieties, forms and methods of utilization, composition, importance in the beer bioactivity, and new discoveries in hops research. Chapter  11, Fruit and vegetable-based beverages—nutritional properties and health benefits, by Marian Butu and Steliana Rodino, shows the benefits of exploitation of the synergies between raw materials as ingredients, processing methods, and product formulation which could lead to substantial innovations in the natural beverages industry. Chapter 12, Neera: a nonalcoholic nutritious beverage from unopened inflorescence of coconut palm, by Asha S et al., dissects the properties of coconut nectar which is attaining world attention with its valuable products such as coconut honey and coconut sweeteners. Coconut inflorescence sap is identified as a nutritional bio-beverage rich in carbohydrates, minerals, vitamins, antioxidants, and amino acids. The most significant characteristic of this health drink is it’s diabetic friendly due to low Glycemic Index (GI 35), a very less amount of

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sugar is absorbed into the blood. This nonalcoholic beverage is hailed as highly rejuvenative in traditional medicinal systems and it is recommended for the cure/prevention of various diseases continuous. Chapter  13, Trends and possibilities of the usage of medicinal herbal extracts in beverage production, by Senem Suna et al., discusses extraction methods of several herbs, their opportunities to be used in innovative beverage formulations and improvement of functional properties of these beverages. Chapter 14, Natural fermented beverages, by Reyhan Irkin, offers valuable details about the health-promoting benefits and characterization of fermented milk and nondairy fermented natural beverages. Chapter 15, Natural and artificial beverages: exploring the pros and cons, by Shramana Koner et  al., is a critical review discussing properties, customer preferences, and impact of natural and artificial beverages in health and beverage industry. Alexandru Mihai Grumezescu University Politehnica of Bucharest, Bucharest, Romania Alina Maria Holban Faculty of Biology, University of Bucharest, Bucharest, Romania

AN OVERVIEW OF NATURAL BEVERAGES

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Monica Gallo⁎, Lydia Ferrara†, Daniele Naviglio‡ ⁎

Department of Molecular Medicine and Medical Biotechnology, University of Naples Federico II, Naples, Italy, †Department of Pharmacy, University of Naples Federico II, Naples, Italy, ‡Department of Chemical Sciences, University of Naples Federico II, Naples, Italy

1.1 Introduction Thirst is an important physiological stimulus that maintains a constant amount of water in the body, and taking water from the outside environment is necessary when thirst is lacking. Thirst adjustment occurs either in the hypothalamic region of the central nervous system, where osmoreceptors exist that trigger thirst reflections when plasma osmolarity exceeds certain values for imbalance between water and blood-flowing salts, or by reduction of plasma volume caused by excessive sweating, various pathologies, or increased saline concentrations (Thornton, 2010). Thirst reduction occurs at the renal system level by regulating diuresis with arginine vasopressin, also known as an antidiuretic hormone, which promotes renal water reabsorption by reducing the production of urine. In certain conditions, the thirst stimulus is also felt at the local level following drying of the oral mucosa or pharynx, a phenomenon especially felt by elderly and menopausal women (Asplund, 2004; Asplund and Haberg, 2005). Thirst is most often felt in children due to their constant activity and the sensation attenuates in the elderly, who risk dehydration if not opportunely stimulated. Thus, drinking at least 1.5–2 L of water daily independent from the perception of such stimuli is recommended (Begg, 2017; Koch and Fulop, 2017). Water, used as a beverage that favors digestive processes, is a source of mineral salts and plays an important role as a diluent of orally ingested substances, including medicines. In healthy people, water balance is constant because the loss of water through the skin, respiratory tract, urine, and stool is compensated by the intake of water as a drink, water contained in foods, water from food, and tissue metabolism. A negative water balance leads to dehydration and severe damage to the Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00001-8 © 2019 Elsevier Inc. All rights reserved.

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body, resulting in thermoregulation alterations, weakness, asthenia, pulmonary upsurge, dizziness, dryness of the skin and mucosal membranes, lowering of blood pressure, and in severe cases, hallucination, loss of consciousness, and death (Fig. 1.1). Although natural water is the best drink for satisfying the thirst stimulus and for ensuring a bodily electrolyte balance, for socialization reasons, we often consume drinks with the most inviting fruit drinks rich in mineral salts, drinks with functional or energizing compounds, drinks containing alcohol, drinks saturated with advertising or drinks satisfying the search for new tastes (Fig. 1.2).

1.2  Natural Juices In addition to water, nature provides numerous liquid reservoirs distributed differently in various parts of plants that have allowed man to survive in specific conditions. Coconut water is a clear, translucent liquid contained in unripe fruits of the Cocos nucifera plant and is one of the most refreshing

Water 22% of the skeleton 75% of the brain 75% of muscle mass 83% of the blood Helps transform food into energy Helps the body absorb nutrients

75%

Helps breathing Eliminates toxins Lubricates joints Protects the organs Adjusts body temperature Carries oxygen and nutrients to cells

Fig. 1.1  Importance of water for the human body.

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Alcoholic beverages

Nonalcoholic beverages

Soft beverages

Fig. 1.2  Subdivision of the main natural drink categories.

drinks known in nature. Coconut water is widely consumed throughout the tropical zone due to its thirst quenching properties conferred by its remarkable potassium content. Compared to green coconuts that are rich in liquid, ripe coconuts contain much less water and have a thicker endosperm; the latter is the fruiting portion of the fruit, which is rich in lipids. Coconut water is composed of many bioactive and natural enzymes, such as acid phosphatase, catalase, dehydrogenase, diastase, and peroxidase, which could greatly help digestion and nutrients that are essential for human health, such as sugars, vitamin C, folic acid, free amino acids, auxin, pantothenic acid, folic acid, and vitamins B1, B2, and B6. Coconut water also contains the minerals potassium (at a high concentration), sodium, calcium, magnesium, and phosphorus (Yong et al., 2009). The concentration of these electrolytes in coconut water produces osmotic pressure similar to that seen in the blood, so much so that during the Second World War coconut water was used in emergency cases and injected into veins of the injured (Campbell-Falck et al., 2000). High potassium concentrations are useful for lowering blood pressure and have cardioprotective effects in myocardial infarction due to the high mineral ion content (Loki and Rajamohan, 2003). Coconut water has low energy, lactose, and gluten content and can therefore be consumed by those suffering from such intolerances. Coconut water obtained from ripe nuts was mixed with lemon juice to obtain a refreshing drink (Chauhan et al., 2014), and following commercial success, other drinks were prepared by adding coconut water to various juices. Birch water, or birch lymph, is the liquid extracted from a hole drilled through the trunk of the tree in the spring period such that

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the lymph drains easily, preventing it from gelling. Birch lymph must be consumed pure or diluted in water or fruit juices; in antiquity, birch lymph was added to baby’s milk to promote strong and healthy growth. Drinking birch lymph stimulates diuresis, as the increase in the potassium/sodium ratio stimulates urinary elimination, while vitamin C and betulinic acid prevent the formation of kidney stones. Birch lymph is an excellent natural remedy against adiposity and fluid stagnation, as it reduces swelling, which is often accompanied by aching or joint pain. Birch lymph is rich in vitamin C, flavonoglucosides (peroside, quercitrine, and routine), triterpenic saponins, polysaccharides, methylpentosans, and minerals (calcium, magnesium, potassium, and phosphorus; trace amounts of manganese, iron, zinc, and copper). The betulin present in birch lymph has been shown to be effective in reducing hyperlipidaemia and high cholesterol and to prevent the formation of atherosclerotic plaques. Salicylates are recommended as an analgesic, an anti-inflammatory, and an antipyretic, and salicylates in the elderly help fight joint pain, rheumatism, and gout (Klinger et al., 1989). Betulinic acid and some of its derivatives are cytotoxic for neuroblastoma cells, melanoma, and Ewing's sarcoma (Suresh et al., 2012). Birch lymph must not be taken by people allergic to pollution (Lahti and Hannuksela, 1980); in addition to common symptoms of the respiratory system, frequent gastrointestinal disorders are accompanied by local allergic inflammation in the small intestine and gastrointestinal symptoms (Rentzos et al., 2014). Aloe barbadensis or Aloe vera juice is obtained by percolation from leaves previously incised under the thick epidermis and is yellowish, with 5% of the juice being solid and the remaining 95% comprising ­water. The collected liquid is dried to a glassy consistency and packed unpasteurized to prevent the degradation of polysaccharides responsible for aloe's properties without the addition of additives or preservatives. Such juice is rich in anthraquinone substances and is used as a laxative for the treatment of arthritis, gout, acne, dermatitis, burns, and peptic ulcers induced by epithelial alterations; at low concentrations, aloin improves the digestive process, acts as an anti-­ inflammatory agent on gastric mucosa, and protects intestinal bacterial flora (Shokraneh et al., 2016; Keshavarzi et al., 2014). The aloe gel has internal use as a supplement (Sehgal et al., 2013) for vitamins (A, B, C, and E), folic acid, minerals (iron, calcium, phosphorus, sodium, magnesium; trace elements of copper, chromium, selenium, and manganese), essential amino acids, polysaccharides (especially glucomannans), organic acids (aloetic acid, cinnamic acid, and salicylic acid), and phytosterols (Hamman, 2008). Bamboo water, a green liquid drink extracted from bamboo leaves to which cane sugar and citric acid are added, has a delicate taste similar

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to that of green tea with a slightly acidic aftertaste. Like most vegetable extracts, high levels of antioxidants, such as polyphenols and flavonoids exist in bamboo water (Lu et al., 2005; Mao et al., 2013). Bamboo water eliminates alitosis when used in toothpastes and mouthwash and has anti-inflammatory, antimicrobial, and antianxiety activities. For its mineral composition, especially potassium, whose presence in our body is important for controlling blood pressure and heart rate, bamboo water is a low-sugar energizing beverage. Furthermore, bamboo water comprises 17 amino acids, vitamins of the B complex and vitamin A, which are essential for proper metabolism regulation and are therefore indicated in dietary regimens. The juice of this plant is recognized as having an antispasmodic property and is considered useful for naturally counteracting inflammatory respiratory system processes. Recent studies have demonstrated the ability of bamboo juice to improve the symptoms of diabetic nephropathy (Ying et al., 2017) by activating the serine/threonine kinase (AKT) enzyme. Furthermore, regarding Alzheimer's disease characterized by progressive neurological deterioration, bamboo leaf extract demonstrated its effectiveness in an experiment on rats with dementia and improved spatial learning ability (Liu et al., 2015a,b). During the treatment, increased gamma-amyloid acid levels in the hippocampal area of the brain and decreased glutamate levels were noted. The significant therapeutic effects suggest that bamboo water could be a potent drug for treating space memory deficiencies. Maple water is the lymph extracted from some species of maple, specifically Acer saccharum, and its production is typical in the climatic and environmental conditions of Canada and North America that are suitable for harvesting. Lymph harvesting occurs in the spring when the freezing/thawing process creates a pressure increase due to high thermal excursion between above-zero temperatures during the day time that rapidly descend below zero during the night, allowing lymph to translocate from the roots upward to escape and be collected. Lymph has a natural sucrose content of approximately 5%, and the well-known maple syrup is obtained from concentrating and boiling lymph. After filtration, the syrup is usually classified based on its color, which varies according to the refining process following the light transmission method and the various degrees are measured with a spectrometer. Five color categories are distinguishable: very clear, clear, medium, amber, and dark. In addition to this classification, the Government of Canada and Quebec rate syrup according to taste, clarity, and density, and the latter should be between 66 and 68.9 brix. In addition to its main component sucrose, maple lymph also comprises minerals (potassium, calcium, iron, manganese, and magnesium), group B vitamins, polysaccharides (including inulin) (Sun et  al., 2016), phenolic substances, and antioxidant substances that

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make it a valuable tool against cellular ageing (Perkins and van den Berg, 2009; Ball, 2007). In high concentrations, malic acid is responsible for the sensation of light-tasting acidity and also accelerates metabolism by increasing thermogenesis, improves muscle tone, and has a defatting and pain-relief effect. Maple syrup is used instead of sugar in milk, coffee, tea or herbs, and to fresh meat and fish. In fact, despite its high concentration of sucrose, maple syrup has a low glycemic index and can be consumed by diabetics (Honma et al., 2010). According to some researchers, phenolic compounds can contribute to controlling blood glucose through inhibition of enzymes involved in the transformation of carbohydrates into sugars, resulting in the prevention of type 2 diabetes (Apostolidis et al., 2011). The anti-­ inflammatory action of the polyphenolic complex was evaluated in a cellular mouse model by stimulating macrophage production by lipopolysaccharides, and a significant decrease in nitric oxide production and prostaglandin PGE2 was observed (Nahar et  al., 2014). Phenols are also attributed to antimicrobial activity and have a strong synergistic interaction with selected antibiotics against Gram-negative strains of Escherichia coli, Proteus mirabilis, and Pseudomonas aeruginosa (Maisuria et al., 2015). Phenols have also been shown to have antitumor activity in colon cells (González-Sarrías et  al., 2012) and a protective effect on bone destruction by inhibiting the differentiation and function of osteoclasts (Ha et al., 2014).

1.3  Soft Drinks Soft drinks are almost exclusively characterized by their presence of water and do not contain alcohol. Many people completely replace their water intake with these drinks by consuming soft drinks at breakfast and main meals, like aperitifs and as refreshing drinks during the day (Nissensohn et al., 2015; Lopez Diaz-Ufano, 2015). Due to the absence of alcohol, these drinks do not affect psychophysical capabilities; however, they should not be considered completely innocuous because they contain high concentrations of sugars, dyes, artificial flavors, synthetic sweeteners, and carbon dioxide (Mischek and Krapffenbauer-Cemak, 2012; Leth et al., 2010). Concerns related to the excessive consumption of soft drinks during childhood are numerous. Recent studies have shown an increase in metabolic diseases among children and adolescents due to high concentrations of sugary substances, which also cause an increase in dental cavities in children as young as preschoolers (Catteau et al., 2012; Libuda and Kersting, 2009; Haghgou et  al., 2016). Nonalcoholic beverages include carbonated beverages, of which the main component is saturated with carbon dioxide, added sugars or other sweeteners; syrup; citric acid; ­natural

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flavors; dyes; and vegetable extracts. These beverages s­ometimes include vitamins, mineral salts, and energizing substances, and non-carbonated drinks are free of carbon dioxide. While carbonated drinks are generally consumed cold at a temperature of approximately 4°C, non-carbonated drinks can be consumed hot or cold. Carbonated beverages are classified into fancy drinks and juice drinks. The first are the drinks that have names that do not match a fruit, such as Fizzy drink, Sprite, Tonic, Coca Cola; the latter report the names of the fruit, such as orange, lemon, and cedar. In Italy, juice drinks must contain at least 12% juice and the use of certain preservatives, such as benzoic acid and sodium benzoate is allowed. The drinks usually undergo pasteurization at 60–65°C for a period of 20–30 min to inactivate bacteria, molds, enzymes, and yeasts and to facilitate storage. In addition to the name of the product, the label must indicate the ingredients, expiration date, and minimum storage period. These drinks must be protected from both heat and direct light, especially sunlight, to avoid alterations of taste and color; even low temperatures should be avoided to prevent the formation of collars due to the separation of essential oils or lumps to thicken sugary substances. Carbonated drinks are generally consumed cold because low temperatures exacerbate the anaesthetic action of carbon dioxide on the mucous membrane of the mouth. Furthermore, they should always be taken on a full stomach or during meals to prevent excessive stimulation of gastric secretion causing serious disturbances of both the stomach and intestines (Cuomo et al., 2014). The origin of refreshing drinks could date back to Italy in the 17th century when granite and ice-cream craftsmen prepared and sold a refreshing drink called “lemonade,” obtained by mixing water, sugar, and fresh lemon juice. Toward the second half of the 18th century, British chemist Joseph Priestley discovered the carbonated beverage Seltzer, having found a way to saturate natural water with gaseous carbon dioxide to obtain a sparkling, refreshing drink that displays numerous bubbles that act pleasantly on the taste buds. Carbon dioxide gives the drink an acidic taste and maintains a conservative action allowing a long product life. By the end of the century, with the production of soda water obtained by adding water, saturated carbon dioxide, sodium chloride, and sodium carbonate, Jacob Schweppe contributed to the knowledge of sparkling beverages by becoming a provider to the real English home. Seltzer and soda water are widely used as alcoholic and nonalcoholic drink thinners based on consumer taste. In approximately 1870, the company English Schweppes, which had already established itself as a soda water producer, launched tonic water, a refreshing drink containing quinine, which gave the drink a distinctive sweet taste and helped protect against malaria. The drink became very

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popular in India, a British colony where malaria was widespread. In Italy, the gazzosa spread, a colorless drink is prepared with carbonated drinking water and sweetened with sucrose, to which citric and tartaric acids and lemon essence can be added. Increased production of sparkling beverages aromatized from Coca Cola, Pepsi Cola, and Chinotto to fruit-based drinks, such as orange, lemonade, and cedar, to soft, decaffeinated, energetic, and vitaminized drink formulations was observed following the expansion of plant extraction techniques at the end of the 19th century. Nonalcoholic aperitifs are a category of sparkling drinks meant for premeal consumption and can therefore stimulate appetite. It is important for such drinks to comprise a mixture of aromatic components and sweet-bitter components and to have a lively and well-defined color between yellow and red. Although these drinks are sometimes marketed with common names that refer to the “bitter” flavor or to the plant from which “ginger” extracts are used, they are more often given fantasy names. Nonalcoholic aperitifs also include “tonic waters,” which are most often used in cocktails and long drinks in addition to their use as an aperitif for a sweet-bitter taste.

1.4  Nervine and Energizing Drinks Nervine drinks are nonalcoholic drinks characterized by a specific activity on the central nervous system. The adjective “nervine” emphasizes tonic properties capable of acting above the central level to produce a stimulating or calming effect. Coffee, tea, chocolate, bitter orange, cola mate, and guarana are bodily stimulants containing natural alkaloids of the xanthine group, such as caffeine, theophylline, and theobromine. If taken at the right dose, these drinks have positive effects on health, such as the antioxidant properties of tea, cocoa, and dark chocolate polyphenols. However, abuse of these drinks cause tachycardia, hypertension, anxiety, agitation, nervousness, and insomnia. Long-term administration leads to the phenomena of tolerance, a progressive reduction of bodily response; addiction, with migraine onset and inability to concentrate; and depression when the drinks are no longer consumed. Soothing actions on the central nervous system are exercised by infusions of herbs, such as chamomile, rosolaccio, melissa, valerian, passionflower, hawthorn, and linden, whose effects depend on a wide variety of active principles. These plants are officinal herbs, which have therapeutic properties and are therefore also used in the pharmaceutical industry. The most commonly used nervine beverage is coffee, which contains discrete amounts of nitrogenous substances, lipids, glucids, organic acids, mineral salts, and vitamins that pass into solution in

Chapter 1  An Overview of Natural Beverages   9

negligible amounts during preparation. From a nutritional viewpoint, coffee does not produce nutrients indispensable to the body and is not caloric, and the only calories in a cup of coffee originate from the addition of sugar. In addition to trigonellin and theophylline, caffeine is the most abundant alkaloid, which determines the excitatory effect on the central nervous system. Caffeine is rapidly absorbed by the body, and its concentration varies according to quality; Arabica is sweeter and more precious, and its caffeine content is approximately half that of Robusta. The tolerance threshold for caffeine varies from individual to individual, and caffeine promotes increased mental activity, decreases the sense of fatigue, stimulates heart muscle, modifies proper function, dilates blood vessels, promotes gastric secretion, and acts on kidneys by increasing diuresis. Caffeine abuse causes addiction, and individuals who consistently drink coffee can display dangerous symptoms, such as insomnia, anxiety, lack of appetite, and restlessness (Mesas et al., 2011; Kim et al., 2012; Cano-Marquina et al., 2013). The preferable choice for avoiding undesirable phenomena is decaffeinated coffee, which has been evaluated for the antioxidant activities of other important components, such as polyphenols and chlorogenic acids (Ding et  al., 2014; Maalik et  al., 2016); the inhibition of glucose absorption in the intestinal tract; the prevention of oral cavity, endometrial, and colorectal cancers; the thermogenic effect; and the exertion of a positive effect on the prevention of neurodegenerative diseases, such as Alzheimer's and Parkinson's. Some studies have shown that regularly consuming two to three cups of coffee a day results in a marked decrease in the risk of developing serious liver diseases, such as cirrhosis and liver cancer (Liu et al., 2015a,b). Less rich in caffeine is tea, which stimulates gastric secretion and is usually accompanied by the intake of solid foods. During the winter season, heating tea is preferable because it is also an excellent thirst quencher when served hot, and its polyphenol content plays a positive role in regulating blood circulation and increasing capillary permeability. Tea is a great drink for those who carry out physical activity because of its mineral salts, which rebalance water-saline losses. If diluted, tea stimulates kidney function and acts as a light diuretic. Tea can be classified according to several factors, with the most relevant being the method of leaf processing. The degree of leaf oxidation serves as the main tea distinguisher, which is how the following are classified: Green tea is not oxidized and is produced with dried, fresh leaves. Green tea is very rich in flavonoids, including catechin and epicatechin, along with their gallate derivatives; gallate epigallocatechin is the most abundant catechin and appears to play a very important role in the health effects of this drink (Wang and Tian, 2017). Gallate epigallocatechin is attributed to green tea’s ability to reduce v­ ascular

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inflammation, lower blood pressure, reduce the concentrations of LDL cholesterol and triglycerides, and inhibit tumor cell growth (Moradzadeh et al., 2017). Black tea is completely oxidized and is produced with completely dried and fermented leaves. Black tea is rich in caffeine and theophylline, and the high amounts of tannins make it useful for the treatment of diarrhea. Tea low fermentation (oolong), having an intermediate degree of oxidation, is poorly used in Europe. Recent studies have shown that this type of tea exceptionally controls type 2 diabetes and obesity. Furthermore, the prevention of polyphenols, such as (−)-epigallocatechin-3-gallate, has been established in the development of cancer cells, as polyphenols have been shown to reduce the risk of cardiovascular disease, protect teeth and bones, and function as antioxidants and antibacterial agents (Ng et al., 2017). White tea is a very precious and sought-after variety, cultivated almost exclusively in Fujian Province, China. The most delicate and young leaves of white tea plants are harvested at dawn during a limited number of spring days are not fermented and are only dehydrated and air-dried to maintain a whitish color. The reduced infusion times and low temperatures often recommended for its preparation make white tea a natural remedy for connoisseurs. This particular tea is rich in antioxidants, which help prevent ageing-related diseases, including skin diseases, and its effectiveness against cardiovascular disease, stroke, and reducing LDL cholesterol levels is recognized. White tea has ­antibacterial activity against oral cavity germs responsible for the development of plaque and cavities (Pastoriza et al., 2017). According to some studies, white tea can prevent some colon, prostate and stomach-­related pathologies, and mitigate the symptoms of HIV. Because of its thermogenic activity, white tea functions as a natural remedy to reduce excess body fat and as a natural energizer. Other tea varieties are on the market, such as flavored teas, teas mixed with fruit, flower, and spice aromatics; soluble teas obtained by dehydration of the beverage and marketed in easy-to-use filter bags; and detained teas obtained by eliminating tea caffeine. The healthy value of tea, especially green tea, is also linked to the presence of flavonoids, especially quercitin, which have a strong antioxidant capacity. Cocoa is the product obtained from fermented and dried seeds of the Theobroma cacao tree, of the Sterculiaceae family. Chocolate drinks are served hot or cold and are comprised of cocoa, milk or water, and sugar. Several products are suitable for obtaining traditional chocolate and other cocoa drinks, such as cocoa powder, containing soluble cocoa powder and cocoa butter; lean cocoa powder, with a cocoa butter content not exceeding 9%, which may be bitter and sweet; sweetened cocoa, a mixture of cocoa powder

Chapter 1  An Overview of Natural Beverages   11

and sugar containing no less than 32% cocoa powder; instant “cocoa,” which is added to lecithin, an emulsifier, to help disperse particles into liquids and disparage lumps; and “soluble preparations for chocolate-­ flavored drinks,” in which cocoa does not exceed 20% and aromatics, salt, dextrose, glucose syrup, and sometimes dyes, are added. Cocoa contains discrete amounts of protein, lipids, glucides, mineral salts (magnesium, calcium, potassium, iron, etc.), and vitamins (B, E, and A) (Hu et al., 2016). Cocoa also contains theobromine and caffeine alkaloids, which confer tonic and stimulating properties and numerous antioxidant substances, such as flavonoids. Antioxidant substances prevent cardiovascular disease by improving elasticity of the vascular endothelium and reducing arterial stiffness, particularly in obese adults (West et  al., 2014). Cocoa and chocolate help fight depression and make sense of satiety. Results obtained on obese patients following hypocaloric and psychologically depressed diets showed that addition of chocolate to the diet led to increased plasma levels of dopamine and homovanillic acid, resulting in decreased depressive symptoms (Ibero-Baraibar et al., 2016). Bitter orange differs from other substances by its presence in synephrine bark. Originally from India, this tree (Citrus aurantium) grows in subtropical regions, including Spain and Southern Italy. Bitter orange is an ingredient typical of many thermogenic supplements; the unripe and dried fruit is enriched with a mixture of sympathomimetic amines, including synephrine as the main constituent (Stohs et  al., 2012). Bitter orange has anorexia properties that can cause a significant reduction in food intake and plays roles in thermogenesis and lipolysis (Gutierrez-Hellin and Del Corso, 2016). The use of bitter orange supplements may prove harmful to subjects with cardiovascular risk; when taken at high doses, synephrine causes tachycardia, hyperagitation, arrhythmia, and hypertensive crises. Such dose-dependent effects become more severe when bitter orange is taken together with other substances of similar activity, such as “stack” supplements that are widespread in bodybuilding gyms. Supplements are well known to play important roles in improving performance but care regarding which substances to consume must be taken. Furthermore, following supplement directions during pre- and post-workout integration has become a true science. In fact, knowing the function of each substance allows you to create your own “stack” based on your goal (greater resistance, greater strength, slimming, etc.). Energizing drinks are characterized by the addition of ingredients that affect specific physiological functions; initially distributed in Japan, energy drinks have had a great affirmation in America and many European countries. In addition to water that represents the main component, energy drinks contain stimulant substances, such

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as caffeine; ginseng; guarana; amino acids, especially taurine, lysine, and arginine, which exercise anabolic action and promote muscle growth; group B vitamins; plant extracts, such as Pfaffia paniculata, Astragalus membranaceus, Angelica sinensis, and Eleuterococcus senticosus, which act as adaptogenes and immunostimulants by increasing body strength against external and internal physical and chemical agents, producing a false beneficial effect; and dyes, such as quinoline yellow and azorubines, which can be highly damaging for allergic people. Energy drinks help accumulate energy, allowing states of physical and mental fatigue to be addressed. These drinks especially help during stress periods protecting the body from stress damage. The increased consumption of these drinks, especially by young people, has triggered alarm for possible adverse health effects; negative effects can be attributed to both component toxicity and to the simultaneous intake of alcohol. There are known cases of toxic encephalopathy induced by taurine, risk of caffeine overdose, and drunkenness due to excess alcohol, resulting in sexually transmitted episodes, severe injuries, drunkenness, and even death (Bigard, 2010). Therefore, assessment of major disorders related to the daily consumption of energy drinks requires greater attention to the component compositions and the nature of the symptoms that they may cause. Reversible phenomena associated with energy drinks exist, such as difficulty standing for orthostatic intolerance and transient loss of consciousness, which may be accompanied by premonition signs, such as nausea, dizziness, or blurred vision, and these symptoms may regress spontaneously by suspending intake of the drink. Long-term symptomatology, such as impaired cardiac rhythm and renal function impairment, resulting in anxiety and depression are more severe (Chrysant and Chrysant, 2015). Recently, “zero sugar drinks” or “decaffeinated drinks” have appeared on the market to encourage consumers for whom caffeine is not advisable, such as children and the elderly. The most common spreads are low-calorie beverages in which normal sugars have been completely replaced by low-calorie or partially sweetened components, respectively referred to as “sugar-free drinks” and “low-calorie drinks.” The most commonly used sweeteners are sodium cyclamate, acesulfame K, and aspartame. More recently, steviosides, extracted from Stevia rebaudiana plant leaves have been introduced, which are 400 times sweeter than sucrose (Gallo et al., 2017). Herbal teas, also known as infusions, are non-carbonated soft drinks that are consumed hot and obtained by pouring boiling water over various parts of the plant to extract aromatics. The most commonly used herbs for infusions are chamomile, lime, carcade, marjoram, thyme, sage, and lemon. The best parts of the plant or grass is the root, flower, fruit, bark, and leaves. Canary, one of the most popular herbal teas, is prepared by pouring boiling water into a cup containing

Chapter 1  An Overview of Natural Beverages   13

the peel of a spiral-cut lemon, excluding as much white as possible. Hot water poured on the peel extracts lemon colored, aromatic, and refreshing substances, yielding a perfumed and straw-colored drink consumed as a digestive or refreshing drink.

1.5  Fruit Drinks Fruit drinks are nonalcoholic beverages that are obtained by subjecting different types of fruit to certain processes according to a series of rigid standards to avoid food frauds or the marketing of ungenuine foods. There are four types of fruit juice on the market: simple juices, obtained only by squeezing and containing 100% fruit; juices concentrated up to 50% in which a good amount of water is eliminated; dehydrated juices, which are reduced to powder; and nectarine juices, which also contain 30%–50% pulp in addition to juice and are added to sugar diluted in water. For example, in Italy, according to Legislative Decree No. 20 of 19-02-2014, adding sugars or sweeteners to “fruit juices and other similar products intended for human consumption” is forbidden. Exceptions include lemon, raspberry, and currant juices, which can be mixed with up to 200 g/L sugar given the bitter nature of the fruit. All kinds of fruit juices are pasteurized to ensure bacteria are absent and avoid the fermentation phenomenon, which results in the crushing of carbohydrates, especially starches and sugars. This thermal process decreases the contents of vitamins and other thermolabile components, and the nutritional value of these products is thus much lower than that of fresh fruit. Fruit juice production includes several stages: the fruit is harvested, washed, destoned, crushed to reduce pulp, mixed with citric acid, and heated to 100°C for 30 min. The addition of citric acid is necessary to prevent microorganism attack and to avoid color variations. Thermal treatment is intended to inactivate both pectinolytic enzymes and by acting on pectins, decrease the viscosity and phenolase enzyme that causes the browning phenomenon. Thus, the obtained fruit pulp must be separated from the undesirable substances to obtain the finished product. The next step is refinement through a sieve-extracting extractor tube that has small holes through which preheated pulp is passed. The juice is collected, while coarse parts, skins, seeds, and fibers are retained on the sieve and form waste. The next stages of fruit juice preparation are concentration by evaporation, followed by sterilization, cooling at approximately 30°C under aseptic conditions, and packing in containers. Fruit juice containers include tetra packs, glass bottles, and plastic bottles of various shapes and sizes.

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For the production of nectar, after being sterilized and cooled, juice is mixed with sugar in the form of syrup and water preheated to approximately 60–65°C, deaerated under vacuum, homogenized at approximately 180–200 bar, and then either heated to the temperature required for filling in hot glass bottles (approximately 85–90°C) or kept cold at approximately 4°C. Sometimes, the extraction process is modified to improve the juice yield of fruit with particularly compact flesh. For example, apples are subjected to very high grinding with the addition of cellulose to facilitate their disaggregation. By pressing, turbid fresh juice is obtained, which undergoes a heat treatment at approximately 100°C to inactivate pectinolytic enzymes, and ascorbic acid is then added to avoid color variations. If one wishes to obtain clear juice, a clarification treatment with bentonite or casein is required when the juice comes out of the press. Fruit juices can also be consumed by celiac patients after they carefully verify the label to ensure they do not contain gluten. Fruit soft drinks, such as orange juice, lemonade, and cedar fruit, are also found in the market. In these beverages, 12% fruit juice is diluted in smooth or sparkling mineral water or the fruit is added to the juices of various vegetables of which the typical representative is ACE (vitamins A, C, and E), consisting of orange juice, lemon, or carrot. These juices can be fortified with functional bioactive ingredients and integrated with probiotics (Speranza et  al., 2017). However, by altering the organoleptic characteristics, these additions may not be very welcome, as they result in flavor variation with loss of freshness; improper aroma development; possibility of interaction with packaging (Strassburger et  al., 2010); insolubility of certain compounds in water, such as carotenoids, omega-3 fatty acids, polyphenols, flavonoids, phytosterols, tocopherols, water-soluble peptides, proteins, and minerals (Odriozola-Serrano et al., 2014); and influence of thermal treatment for sensitive ingredients, including proteins, vitamins, and probiotics (Gaanappriya et al., 2013). Encapsulation of sensitive and probiotic compounds for application in fruit juices can provide a solution to these problems and ensure the chemical and physical stability of many compounds (Dordevic et al., 2015), as it allows different levels of release to target specific areas of the gastrointestinal tract (Katouzian and Jafari, 2016).

1.6  Smoothies, Extracts, and Centrifuges Smoothies are beverages obtained by shuffling seasonal fruit, water, milk or yogurt, sugar syrup, crushed ice, and possibly adding liquor. Aqueous fruits of high acidity, such as melon, watermelon,

Chapter 1  An Overview of Natural Beverages   15

berry, cherry, pineapple, and kiwi are mixed with only water or yogurt. Furthermore, floury pulp fruits, such as banana, pear, apple, peach, apricot, and figs can be smoothed with water, milk, or yogurt. In the preparation of fruit smoothies, ice cream and sorbet are often used together with other ingredients or as a partial replacement for ice. In some cases, liquors are also added to highlight the flavors. Vegetable smoothies are very close to “dietetic cocktails” and can be prepared not only with whole vegetables but also with centrifuged juices used alone or in blends (Nowicka et al., 2017). The mixer used must be powerful enough to break even raw vegetables or roots and liquid water or milk must be added during the operation to homogenize the final product. Depending on the starting vegetable and the various vegetable combinations, energizing smoothies can be obtained with spinach and green apple or asparagus, celery, and carrots. Vitamin C smoothies can be made with beets and pear or zucchini, tomatoes and basil. Detoxifying smoothies comprise celery, fennel and apple, or red cabbage and apple. To increase the storage period and preserve against bacterial attack, smoothies are subjected to pasteurization, a high-temperature heat treatment lasting only 3 min at 80°C, which has been shown to reduce the bacterial charge, thus preserving principles active during low-temperature storage. The best results are obtained with high-pressure treatment, as this does not induce any variation in the sensory and nutritional characteristics of smoothies during storage at 5°C (Castillejo et al., 2017; Hurtado et al., 2017; Andres et al., 2016). Centrifuges have the disadvantage of excluding fruit and vegetable fibers in the final beverage, but if consumed immediately after preparation, they yield all the vitamins present in the plants used, which are the substances most readily degradable by light and heat. Through a basket that rotates at high speeds and centrifugal force, plant cells are released from juice collected in the container under the filter. While the obtained centrifugal juice is 100% vegetable with no added liquids, some substances may be lost during centrifugation due to the friction and overheating of the moving device. Extracts are produced with a more sophisticated and, therefore, more expensive means. An extractor is used to extract juice from both fruit and vegetables as efficiently as possible and is made of a screw that crushes the plant until juice is produced in a very silent and cold manner (Beveridge and Rao, 1997). The speed of movement is very low prohibiting the loss of micronutrients, such as vitamins and antioxidants, typically lost with high-spin speed blenders and traditional centrifuges. Fruit and vegetable drinks have a detoxifying effect on the body allowing weight loss or increased intake of fruit and vegetables in the diet. However, if such drinks are assumed to contain many beneficial

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micronutrients, such as vitamins, minerals, polyphenols, and various substances with antioxidant properties, daily use may lead to some risks. In fact, although they are prepared without added sugars, fruit contains fructose, which is made more readily available in juice form. This quickly raises blood glucose levels and insulin peaks, causing a sense of hunger and ultimately resulting in increased weight. A limitation of extracts is the absence of fibers, as fibers are essential for proper functioning of the digestive system and intestinal bacterial flora and for maintaining immune system efficiency. In addition, fibers contribute to the sense of satiety and promote the absorption of important minerals, such as calcium. During the period between preparation and consumption, micronutrients and vitamins, which are very sensitive to heat and light, lose their activity following the oxidation process, and preservation also presents the risk of bacterial contamination if the product is not prepared and pasteurized by strict hygienic rules. Another drawback regarding the liquid state is that the organism consuming the beverage does not spend energy on the chewing process; this function fails, as it increases salivation and stimulates the secretion of digestive juices. Slow chewing contributes to determining the sense of satiety and is not available with liquid diets. Furthermore, the sugars naturally contained in these drinks can favor the formation of cavities in the same way as added sugars. Thus, fruits and vegetables can then facilitate bacterial attack by their ability to make the mouth environment acidic (Brand, 2013; Blacker and Chadwick, 2013; Huysmans et al., 2006).

1.7  Alcoholic Beverages Alcoholic beverages are characterized by the method in which sugars present in fruit or various cereals are transformed into alcohol. Known fermented beverages with alcohol contents not exceeding 16° and distilled beverages with alcoholic strengths varying between 15° and 60° exist. Drinks obtained by fermentation have been consumed since ancient times, and archaeological research has used modern analytical techniques to identify specific organic compounds from residues in pots and other sources found during archaeological excavations. For beer, the most indicative compound is calcium oxalate, which characterizes barley beer (Lewis and Young, 2012). Like all alcoholic beverages obtained by the fermentation of amilaceous plant products, beers have “with saliva drinks” as precursors. These, used especially among indigenous South American populations, are obtained by the grain chewing technique and saliva mixing. The resultant mixture is then spat into a vessel and the enzymes present in saliva favor starch saccharification. The process of alcoholic fermentation

Chapter 1  An Overview of Natural Beverages   17

then occurs naturally by the presence of environmental microorganisms. Thus, famous traditional drinks, such as “chicha” from maize, and “cavim” from manioc, have been produced for many centuries. Fermentation is an economically viable conservation technique that improves nutritional quality and sensory food characteristics. The fermentation of milk, cereals, and other substances for the production of health-promoting beverages has been applied since ancient times by indigenous Asian, African, European, and South American populations. Kombucha, a sugary and fermented tea obtained in China in approximately 250 BC, was considered an “elixir of immortal health” for its action on the spleen and stomach, which helped digestion and allowed the body to heal. Today, kombucha is known throughout the world and is obtained by fermentation with a mixture of Acetobacter and Lactobacillus bacteria combined with Brettanomyces or Saccharomyces yeasts. The detoxifying and antibacterial properties of kombucha have been recognized, as its low pH of approximately 2 and the presence of the primary metabolite glucuronic acid helps purify the body by combining with and eliminating toxins through the kidneys (Wang et al., 2014). This tea is rich in functional substances, such as polyphenols, B group vitamins and folic acid (Greenwalt et  al., 2000). To make cereal-fermented drinks that are very popular in tropical regions, especially in Africa, maize, millet, oats, barley, and sorghum are heated, filtered, mixed with sugary substances, and allowed to ferment naturally. Boza is a typical beverage consumed in Bulgaria and Turkey produced by the fermentation of a variety of cereals, including barley, oats, rye, millet, corn, wheat, and rice, obtaining a mixture with a certain viscosity that is made to ferment naturally (Akpinar-Bayizit et al., 2010). Not knowing the type of enzyme employed, this method leads to the production of beverages that have variable characteristics and the nature of the yeast is often unknown. Many studies have shown that fermentation’s ability to improve antioxidant activity is due to increased amounts of phenolic compounds and flavonoids resulting from a microbial hydrolysis reaction. Fermentation causes destruction of cellular plant structures, resulting in the release or synthesis of various antioxidant compounds that can act as free antiradicals, metal ions chelators or hydrogen ion donors. Proteases, α-amylases, and other enzymes that improve the antioxidant capacities of cereal-based foods may result from fermentation contributing to the health and nutritional improvement of the consumer. Fermented cereals have the disadvantage of containing low concentrations of essential amino acids, but they may have low fat content and contain high concentrations of minerals and other functional substances, such as fibers, vitamins, flavonoids, and phenolic compounds that combat oxidative stress, inflammation, hyperglycaemia, and carcinogenesis (Wang et al., 2013).

18  Chapter 1  An Overview of Natural Beverages

1.8 Beer Beer, obtained by the fermentation of barley-based musts flavored with hops, is one of the oldest alcoholic beverages; the first written testimony of beer is dated to approximately 3500–3100 BC. Chemical analyses carried out on ancient organic substances absorbed in pottery jars from Jiahu village in northern China revealed that in the Neolithic period approximately 9000 years ago, a fermented drink mixed with rice, honey, and fruit was made. Evidence of beer production exists at the Sumerians, and the brewery profession appears to have been born in Mesopotamia; testimonies indicate that the workers were paid partially in beer. The oldest law regulating the production and sale of beer is contained in the Code of Hammurabi (1728–1686 BC), which condemned those to deaths who did not comply with the stated manufacturing criteria, such as those who watered beer and those who opened local sales without authorization. In the Mesopotamian culture, beer also had a religious role: it was consumed during funerals to celebrate the dead and as a propitiatory offer to the Gods. In ancient Egypt, beer was considered both food and medicine and was used by the general population as early as childhood; low-grade beer or beer diluted with water and honey was administered to infants when mothers had no milk. For the first time, beer shifted from handicraft to industrial production and the pharaohs themselves owned production factories and paid those who worked on the pyramids with beer. During the Middle Ages, hops was introduced as an ingredient with the added advantage of adding antiseptics to the beverage. This allowed beer to be stored for very long periods of time and made trade possible as the beverage was then considered hygienically “safe.” Subsequently, brewers discovered how to successfully control barley fermentation, improving both the quality and quantity. The development of densimeters and thermometers changed the beer making process, allowing more control over the brewing process and more knowledge of the final result. In addition, specific yeast studies were conducted allowing the production of low-fermented beer, which is by far the most common form globally. Beer production is divided into several stages, as follows: Barley is transformed into malt and left to germinate and after a few days the resulting malt is dried and ground. The ground malt is then mixed with hot water to form a mash and the starches become fermentable sugars. Filtration is performed to separate the must from the solid residue, and the must is brought to boiling after the addition of hops. The must is then filtered and yeast(s) are added for fermentation. Generally, yeasts used in the brewing process are Saccharomyces carlsbergensis and Saccharomyces cerevisiae, which in addition to

Chapter 1  An Overview of Natural Beverages   19

i­ mplementing alcoholic fermentation give the drink its typical organoleptic characteristics. Depending on the temperature and yeast strain, fermentation is either high (over 20°C and takes from 3 to 5 days) or low (below 12°C and takes 7–10 days). Thus, the beer produced is left to rest and mature in high-pressure containers, and the final product is then bottled and pasteurized. The classification system most used refers to the type of yeast and fermentation, as follows: Ale are beers produced with the Saccharomyces cerevisiae yeasts and undergo a high fermentation process; Lager beers are produced with the yeast Saccharomyces carisbergensis and undergo a low fermentation process; Lambic beers are produced exclusively in a region in southern Belgium, wherein must is exposed to local natural yeasts, such as Brettanomyces bruxellensis, and the process occurs with “spontaneous fermentation,” giving the product unique characteristics. Other classifications are based on color, related to the type of malt given by the employed grains, and ranges from golden to black. Emerald Irish beer, produced for the St. Patrick feast, is mixed with the classic blond beer Blue Curaçao, a liqueur whose blue pigments blend with the golden ginger, to impart green coloring. Other classifications are based on the alcoholic strength, generally measured as the percentage of alcohol in the total volume of the drink, or the degree of bitterness, perceived by taste, and measured on the International Bitterness Unit (IBU) scale. Beer production is possible with any cereal treated appropriately to obtain fermentable sugars by cooking or malting. The main additive used to compensate for the sweetness of malt is hops, which may be bitter due to the high presence of α-acids or aromatics, with prevalent essential oils contributing to aroma. Ambivalent hops are characterized by a high percentage of α-acids and good aromatic qualities and they can be used to impart both aroma and bitterness. In addition to hops, fruit, such as cherries and raspberries, fruit juice or syrup is added to some varieties of Lambic beer prior to fermentation. In place of hops beers can be flavored with other types of plants, such as hemp, rosemary, and tobacco. Other spices, such as ginger, coriander, orange or lemon peel, pepper, and nutmeg can also be added. In addition to water, alcohol, and carbon dioxide, beers are also composed of dry extracts containing simple sugars (such as glucose, maltose, maltotriose, and sucrose); dextrin; nitrogen; proteins; peptides; amino acids; nucleic acids; amides; heterocyclic compounds; group B vitamins (especially B6 and folic acid); minerals (including silicon, very high potassium contents with respect to sodium, and an optimal calcium-phosphorus ratio); bitter substances from hops, α-acids (umulones) and β-acids (lupulons); terpenes

20  Chapter 1  An Overview of Natural Beverages

(including mircene, β-cariofyllene, β-farnesene, umulene, linalol, geraniol, and limonene); phytoestrogens; and fibers (Formato et al., 2013). Beer is a drink rich in nutrients and functional substances that perform useful and beneficial actions for the integrity and functionality of human cells if consumed in openness and moderation (Kondo, 2004). Beer helps the heart function properly and slows the production of homocysteine, a major factor underlying heart problems, because it comprises B6 vitamins, antioxidants, iron, calcium, and folic acid. Vitamin B12, important for regular growth and good memory function, together with folic acid prevents anaemia. Beer favors diuresis, as it has high magnesium and potassium content and low sodium content and thus helps the kidneys function normally and decreases the chance of kidney stones. The hop-derived bitter substances can prevent and improve type 2 diabetes and obesity and increase HDL cholesterol by lowering LDL, thus avoiding blood thrombus formation (Tornita et al., 2017). Xanthumol, a flavonoid found in hops, slows down angiogenesis, one of the main causes of tumor formation, and especially prohibits breast, ovarian, and colon cancers. A mineral present in it protects bones from weakening and prevents osteoporosis, as silicon in the diet is the key for bone formation. In addition to stimulating the formation of new bone material, silicon also slows the erosion and decalcification processes, thus preventing density loss that causes disorders that affect many elderly people. Like all alcoholic beverages produced by fermentation, it stimulates the production of gastric acid and facilitates digestion, as the presence of soluble fibers improves intestinal function (Rubbens et  al., 2017; Teyssen et al., 1997). Recent studies (Ano et al., 2017) have shown that iso-α acids, bitter compounds derived from hops in beer, increase microglial phagocytosis and suppress inflammation by improving cognitive function. Therefore, the use of iso-α acids could be useful for preventing dementia and Alzheimer's disease, which are worldwide, thus improving the lifestyles of many patients.

1.9 Wine Wine is the product obtained by the alcoholic fermentation of fresh or slightly dried grape must with or without pomace. Ferments present in grapes and musts are composed mainly of Saccharomyces microorganisms, which transform grape sugars into ethyl alcohol and carbon dioxide. Malolactic conversion, a secondary type of fermentation that leads to the transformation of alic acid into lactic acid, is normally used to make wines softer, though secondary fermentations sometimes make wines less pleasant and more easily alterable. At the completion of fermentation, wine is decanted from dregs (residue

Chapter 1  An Overview of Natural Beverages   21

deposited on the bottom) and poured into barrels, where it is allowed to mature. The organoleptic characteristics of wine are highlighted by the many sensations perceived by our senses, including the color, flavor, odor, and noises produced by bubbles (in the case of sparkling wines). The rite of tasting through sensory stimuli is intended to recognize not only the type of grape from which the wine is produced but also the process of ageing, processing, and defects that may be present (Gawel et al., 2017; Niimi et al., 2017). Wines may be classified according to the quantity of sugars present, and the categories include sec, sweetish, lovable, pasty, and sweet wines. Depending on the alcohol content (% alcohol/100 mL of wine) wines are classified as the following: • meal wines, containing 90–110 g of alcohol per litre; • cutlery wines, containing 110–140 g of alcohol; • luxury or bottle wines, containing 110–190 g of alcohol and having delicate flavoring; • and special wines, containing 130–180 g of alcohol. Wines can also be classified according to their carbon dioxide content: Crisp wines have a low carbon dioxide content and naturally occur as residual fermentation, and sparkling wines have a high carbon dioxide content highlighted by bubbles and foam on uncorking. In sparkling wines, foam can be artificially obtained by the injection of carbon dioxide from a cylinder into sweetened wine for 5 h and cooling to 0°C to facilitate absorption. These are considered low-­ quality sparkling wines with coarse and low perlage grain cost. In natural sparkling wines, foam is naturally produced by yeasts and fermentation can be performed according to the Charmat or Champenoise methods. The Charmat method is used to produce fresh and scented sparkling wines that are not aged, such as Moscato and Prosecco, and takes a fairly short amount of time, which is accompanied by a significant reduction in costs. The Charmat method consists of fermenting wine with added sugar, while carefully selecting yeasts and mineral salts in small quantities, in steel autoclaves. After reaching the desired pressure and being refrigerated, clarified, and poured to separate the lees, the wine is ready for bottling. The Champenoise method consists of a very slow fermentation in a bottle and the process occurs in two phases. First, the wine is obtained by fermenting must in steel autoclaves or barrels to make it into sparkling wine. The product is then supplemented with cane sugar in the form of syrup, yeast, and mineral salts, bottled in very thick, dark-glass bottles, and capped with a crown cap. The bottles are stacked horizontally at a constant temperature of 11–13°C. They are shaken and the stacking position is reversed every 6 months to promote the action of

22  Chapter 1  An Overview of Natural Beverages

the yeast on sucrose gradually forming carbon dioxide. This process yields a sparkling wine with thin grain foam, but it takes 2–8 years to complete by increasing the fineness and substances that comprise the bouquet. Liquors are derived from mixing alcohol, sugars, flavoring substances, and colorants and have a minimum gradient of 15-55°. Flavoring substances are obtained by both cold and hot processes, including infusion, maceration, percolation, distillation, and extraction, and the sugar content must not exceed 100 g/L (Naviglio et al., 2014a, 2014b, 2017; Rodríguez-Solana et al., 2016). In liquors, sugars have the function of imparting a sweet taste, making bitter tastes pleasant with herbs and providing consistency and density to the finished product. After mixing all the ingredients, liquors are left to rest for a period ranging from 1–2 months to 1–2 years or more. Based on the method of production, liquors are classified as: • fantasy liquors, which have an undefinable flavor based on the aromas present; • natural liquors, which have well-defined aromas; and • liquor creams, characterized by a low alcohol content relative to that of other liquors and by sugar added at maximum concentrations of 200–500 g/L in addition to crystallized sugar. Liquors are usually drunk after meals in the afternoon or late evening.

1.10 Spirits Spirits are beverages containing more than 21% alcohol and include distillates, liqueurs, and creams. Distillate spirits are obtained by the distillation of fermented must and have an alcoholic strength between 30° and 60°; they can be flavored or aged in wooden barrels to yield specific aroma and taste characteristics. Distillates are classified according to the type of fermented must and include the following: • wine distillates (brandy, cognac, and armagnac); • grape pomace distillates (grappa); • fruit distillates (kirsch, peach brandy, slivovitz, and calvados); • berry distillates (mores and strawberries); • grape distillates (whiskey, gin, and vodka); and • plant distillates (rum, tequila, and cachaça). Spirits are numerous and as they are obtained from different products, have particular tastes and aromas, with the most famous being armagnac, cognac, and calvados. Armagnac, the oldest spirit in France, is obtained from the distillation of vintage white wines from the Gascogne region and is aged in oak barrels. Cognac is produced by the distillation of mediocre white wines used only for distillation

Chapter 1  An Overview of Natural Beverages   23

and grown in Charente, north of the Armagnac area. Cognacs can have varying characteristics and are aged for long periods in oak barrels. Grappa is a spirit from wine pomace that is produced, vinified, and distilled exclusively in Italy. The name comes from the term “graspa” which indicates the grape branch. Similar distillates from other European countries cannot be called grappa but instead have other names, such as schnapps in Germany, marc in France, and aguardente bagaceira in Portugal. The alcohol content of this distillate varies between 37.5% and 60% by volume, which can be reached directly in “fullscale” grappa or by adding demineralized water. This spirit is obtained by the distillation of three types of grape pomace: fermented red wine pomace, semi-fermented rose wine pomace, and unfermented grape pomace of red wine vinified in white wine. Grappa is classified according to the type of processing followed by distillation, and the classifications include young, not aged, aromatic (derived from aromatic grapes, such as Brachetto, Malvasia, and Moscato), aged a minimum of 12 months in wooden barrels, aged reserve or dung for a minimum of 18 months in wooden barrels, and flavored with natural flavorings (such as herbs, roots, and fruits). Grappa can also be classified according to the origin of the pomace, including monovitigno (grappa comes from a single variety of pomace) and mixed (grappa contains different percentages of several varieties of pomace). Grappa is composed of water naturally derived from the humidity of the pomace, the distillation steam, and distilled during degree reduction; ethyl alcohol, a basic component that is mixed with water in any proportion and solubilizes many flavoring substances formed during ageing; methyl alcohol, a highly toxic substance that can be maximally added at 1 mL/100 mL of anhydrous ethyl alcohol (the greatest danger to grappa producers) that affects the preservation and silage of the pomace; higher alcohols, the predominant substances comprising the bouquet; esters; aldehydes; and organic acids, volatile substances that are formed during fermentation and insulation. Distilled grappa does not possess the few nutritional benefits provided by fermented beverages, such as antioxidants, vitamins, and minerals. The beneficial effects of grappa are highlighted in the ancient ways of peasants, who used grappa as a dental analgesic by placing a few drops directly on the tooth. Grappa can also be used as an adjuvant for osteoarthritis, especially for the knee, foot, and shoulder, when infused with malva leaves and applied as a massage. Grappa is typically consumed in moderation after meals and has excellent digestive properties. To obtain good-quality grappa, the production process must begin with grape pomace with alcoholic degrees between 4° and 5° for red grape pomace and between 2° and 4° for white grape pomace, and the grapes must be free of dirt and dampness to obtain wine or must rich

24  Chapter 1  An Overview of Natural Beverages

in alcohol and fermentable sugars. Notably, grappa has the highest distillation yield safety. Pomace must be treated immediately or properly maintained avoiding contact with the air to prevent fermentation through yeasts. This leads to the development of alterations ranging from the formation of acetic acid to that of methyl alcohol, the formation of molds to microbial proliferation, and the rotation and saponification of essential oils. Distillation is the only method for obtaining grappa, and it has very long historical origins. Grappa distillation can be dated to between the eighth and sixth centuries BC in Mesopotamia, where it was applied to wine to obtain spirits, and the Romans also distilled pomace. Pomaces can have different boiling points and ethyl alcohol bubbles at 78.4°, representing the whole distillation reference. In the first stage of distillation, vapors containing the most volatile substances are formed when the boiling point is lower than that of ethyl alcohol. In turn, these substances form head products, methyl alcohol, acetic aldehyde, and ethyl acetate, which are usually deleted. The “heart” of grappa is then developed, consisting of substances for which the boiling points are between that of ethyl alcohol and 100°, the purest alcoholic vapor. Continuing the process, less volatile substances with boiling points above 100° are obtained, forming “quails” rich in impurities, including phlegm oil (made of amyl alcohol and higher alcohols), which are also discarded. True grappa consists of the “heart” of the distillate, which is sometimes increased by the alcoholic content by deflection. The distillate heart consists of a fractional split of heads and tails to obtain a more concentrated, pure spirit that can reach 80–85°. Rectification is a process needed when a distillate has an unpleasant odor. This process is adopted when grape storage continues for a long period or when distilled solutions are defective and consists of a complete fractional distillation process, repeated several times, to obtain concentrated, pure spirits. Grappas are first aged in barrels, called “pilata,” and go into oak barrels after 2 years. However, acacia, ash, chestnut, cherry, prune, pear, and mulberry wood can also be used. Each of these woods, having optimal levels of tannic and aromatic substances, gives the distillate very different characteristics. Producing so-called “monovitigno” grapes, obtained from a single type of grape, has raised grappa from a low-level product because it comes from waste, a high-quality distillate that has to be served at room temperature to enhance the perfumes and taste. Rum is a spirit obtained from the distillation of fermented sugar cane (Saccharum officinalis), molasses and juices. Agricultural rum, which has higher organoleptic characteristics, is obtained directly from cane juice (Franitza et  al., 2016; Canuto et  al., 2012; de Souza et al., 2006). Rum requires a period of ageing in barrels, and if that passage is not adopted, the rum is considered rummy or artificial rum.

Chapter 1  An Overview of Natural Beverages   25

Young distilled rum is colorless and transparent, while rums aged in casks tend to be pigmented yellow. To simulate maturation caramel is added to young rum, which assumes a yellow-reddish or reddish coloring (Ickes et al., 2017; Regalado et al., 2011; Aquino et al., 2008). Rum varieties are distinct depending on the region of provenance and classifications include Jamaican rum, Cuban rum, Demerara rum, St. Croix rum, Martinique rum, Guadeloupe rum, and Rum Reunion. Rum has an alcohol content of 70%–77%; Cuban and Jamaican rums are approximately 74% alcohol, while those of Martinique and Tafia origin contain only 54%. A residue consisting of sugars, aromatics and traces of impurities, such as acids, aldehydes, ethers, and higher alcohols, results from evaporation. The most famous rum variety in Europe is Jamaican rum, which is colorless or slightly pigmented. The production of artificial or fantasy rums, obtained by the addition of typical rum substances to diluted spirits following by dyeing, is also very well established. Cachaça, distilled from fermented sugar cane juice, is a typical beverage from Brazil. Sugar cane is harvested, washed and pressed with large metal rollers to extract the juice, and Cachaça is produced from the first squeeze (de Souza et al., 2007). Before the fermentation process occurs in wooden or copper saucepans, the juice is filtered to remove any fragment of the cane. After fermentation, the juice is distilled three times, yielding a sticky concentrate that is aged for at least a year in native bushes of the rainforest (Gomes et al., 2010). There are approximately 26 different types of wood known, and Garapeira wood gives the distillate a very special sweet and spicy flavor. Cachaça has an alcohol content that ranges from 38° to 48°. Tequila is a beverage obtained by double distillation in the discontinuous alambic Agave blù, yielding tequila agave that originates in Mexico and Jalisco State and has an alcoholic gradation between 40° and 45°. Tequila processing consists of harvesting ripe agaves, whose pigs are cooked gently in hermetically sealed steel furnaces, and transforming complex carbohydrates from fruit trees into fructose (Stewart, 2015). The cooking takes approximately 24 h, yielding a mass soft with flavors of caramel and honey. The cooked pigs are then triturated under a large stone wheel; the remaining fibrous pulp is often reused as fertilizer, animal food, or fuel to be transformed into paper. The obtained agave juice is poured into a large wooden or steel tin and left to ferment for several days until a low alcohol content is obtained. Fermentation is the process of converting sugars and carbohydrates into alcohol by Saccharomyces cerevisiae under aerobic conditions. The addition of yeast helps accelerate the process that can take anywhere from 3 to 20 days; in the absence of yeast, fermentation may take up to 7 days. The fermentation rate is a key factor underlying the quality and final aroma of the tequila produced. Slow fermentation is

26  Chapter 1  An Overview of Natural Beverages

better, as the organoleptic components produced are higher, and the alcoholic value of the product at the end of fermentation ranges from 4% to 9%. The fermented product then undergoes a double distillation to reach an alcoholic gradient of 40–45° and is then left to rest in large wooden barrels for 2 months to 3 years during which it acquires a golden color and darkens. Classifications according to ageing have three distinct denominations: Blanco-clear is preserved less than 2 months, Reposado-amber is preserved for a period of 2 months to 1 year, and Añejo-golden is preserved for over 1 year. Whiskey is a distillate obtained from the fermentation and subsequent distillation of various cereals, including rye, wheat, corn, and barley, which can either be malted or not, and are matured in oak wood barrels. The term “Scotch whisky” signifies spirits distilled in Scotland and are produced exclusively from malted barley, whereas “whiskey” indicates products distilled in Ireland or the United States. Moreover, bourbons are whiskey products produced in the United States from the fermentation and distillation of maize, rye, and barley malt (Poisson and Schieberle, 2008). Two different kinds of Scotch whiskey are known: “single malt,” comprised of pure barley malt obtained from distillation with discontinuous alambic and produced in a single distillery, and “blended,” obtained by mixing malt whiskey produced from various distilleries with spirits of malted or non-malted cereals and distilled with continuous column alembic. Barley contains many enzymes in its seed and this characteristic differentiates barley from other cereals. Other peculiarities of barley include the use of water with peat for the production of must, the yeasts chosen specifically for fermentation, the peat to feed the fire to dry sprouted barley, the size of the alambic for distillation, the wood of the barrels, and the place for ageing. Peat, the main and characterizing component of the distillate, is used to smoke and dry malt in perforated laminae furnaces. Peat is a young charcoal that burns with lots of smoke, which according to its marine or mountain origin, imparts iodine, salty, balsamic, and floral smells to the whiskey. With fermentation the must reaches 7–8° and is filtered and subjected to two distillations, each of different durations. With the first duration of approximately 7 h, an alcoholic content of 20–24° is obtained, called “low wine,” with the aim of eliminating heavy alcohols and other typical cereal fermentation products. The second 12-h distillation, from which the head and tail parts have been removed, yields an alcoholic content of 60–70° and constitutes the “new spirit” that is ready for ageing. This last stage is the most delicate, as the distillate gets more delicate losing its strong ethereal and medicinal notes. The ageing period lasts at least 3 years, and the age of single malts can reach 5 years. However, the best distilleries extend this period to 8–12 years

Chapter 1  An Overview of Natural Beverages   27

and use barrels previously utilized for fine wines, such as sherry, port, madeira, and bourbon, that will donate fruity aromas to the distillate. This wood finish practice is typical of Scottish whiskeys, which are distinguished from the others by their typical organoleptic profile. Gin is a super alcoholic drink obtained from the distillation of wheat and barley fermented and flavored with juniper, and by law, its alcoholic strength must not be less than 37°. Gin production methods are different, as described below: • an added alcoholic beverage of juniper berries and other natural aromas subjected to moderate fermentation and subsequent distillation to extract the aromas; • distillation of fermented grape must, which is then redistilled in the presence of aromas and juniper; and • pure ethyl alcohol to which aromatic substances, with a prevalence of juniper aroma, are added. Various substances are used to flavor gin, including citrus fruits (such as lemon and orange), bitter spices, anise, angelica, liquorice, cinnamon, saffron, and nutmeg, which contribute to formation of the bouquet. Given the high alcohol content, consumption of pure gin is of lesser importance, and gin is thus a very present ingredient in cocktails such as Gin and Tonic, Gin Fizz, and Gin Old Fashioned. Vodka, a traditional Russian drink, is obtained from the fermentation and subsequent distillation of various cereals and potato pulp. Dating back to the eighth century, vodka is thought to be of Polish origin and was primarily used as a medicine. Vodka was originally produced by only fermentation had a gradation of 14°; distillation and other purification methods were introduced in 1700. To obtain the final product with a gradient of 40°, vodka is subjected to at least three distillations. Currently, vodka is produced from various cereals, such as sorghum, corn, rye, and wheat; certain vodkas are produced from only potatoes, molasses, soy, grapes, rice, and sugar beets. Vodka-based drinks, typically having a much lower alcohol content, produced with the aromas of fruit, lemon, peach or melon, are considered sweet liqueurs. Cereals used in the production of vodka must be melted to disintegrate starch in fermentable monosaccharides, and the sugars of other plants present are also trimmed by amylases. After separating the solid part the fermentation and distillations processes occur. “Brantovka,” or burnt vodka, is yielded from the first distillation and has a gradation of 15°. The second distillation yields “prostka,” known as rustic vodka and has a gradation of 30°. Finally, the third distillation yields “okovita,” known as the spirit and has a gradation of 70°. The distillates are filtered using different materials, such as activated charcoal, diamond powders, and fossil flours, to eliminate unwanted odors and to obtain a neutral product. With subsequent stretches of rain water, distilled

28  Chapter 1  An Overview of Natural Beverages

water or spring water, a gradient of 40° is obtained, and the product can then be placed on the market. Vodka is traditionally consumed smooth and is often chilled and it is used as the basis of many popular cocktails, such as Bloody Marys, Bullshots, and Vodka Martinis.

1.11  Fruit Distillates The production of fruit distillates occurs in several stages. After selecting the most ripe and scented fruit, the fruit is smeared, deprived of impurities, and fermented for approximately one month. Yeasts that transform sugar contained in the pulp into alcohol are then added. When fermented, the must is distilled in continuous or discontinuous alembics depending on the type of distillate desired. In some cases, only the juice of the fruit is fermented to obtain a more delicate liquor (Caldeira et  al., 2017). The distilled liqueur can be aged in wooden barrels or in steel or glass containers to sharpen the taste and scents and can reach gradients ranging from 38° to 43°. Calvados is a cider distillate, a sparkling low-alcohol beverage produced by apple fermentation in a department having the same name in Normandy. “Calvados del Pays d'Auge” enjoys a privileged denomination clearly indicated on the label due to the homogeneity of its production grounds, its apple characteristic, and the double distillation that gives the spirit an extreme finesse. Apples of the Pays d'Auge variety have the characteristic of being sweet-loving, and the secret aroma lies in the size of the fruit; smaller apples have stronger aromatic intensities. Apples are picked by hand and stored in airy boxes, where they finish maturing in ideal conditions within 3 to 4 weeks. At their maximum aromatic potency, apples can be pressed to extract the juice; the aromatics are concentrated in the skin and not in the pulp, and the apples are grated and left to macerate for 2 h to soften the skin and improve the aromatic juice character. A membrane press has been adapted for apple pressing. Juice extraction takes approximately 2 h, stirring the grated apples every 10 min. At the completion of the twisting, the must takes on a beautiful amber and golden cider color. Fermentation of the distillate cider is carried out over a period of 2 months, leaving it as long as possible with its lees to avoid all possible aromatic deviations and to develop the Calvados “fondu.” The cider is first distilled to collect the “petite eau,” a light water with a gradient between 28% and 30% in volume, which contains all the elements essential for a quality Calvados. Subsequently, the “petite eau” is distilled to obtain the Calvados by eliminating the heads and tails to preserve only the “coeur,” which contains between 80% and 60% alcohol by volume. Ageing is a process that provides a bouquet of aromas and occurs in oak barrels grown on sandy soil, as they release a vanilla flavor; the slatted wood is lightly burnt to preserve its full potential. Ageing in

Chapter 1  An Overview of Natural Beverages   29

Fig. 1.3  Correct consumption of beverages.

barriques occurs over 3 months to allow Calvados to assume the vanilla taste of the wood while simultaneously regulating the concentration of the aromatics, reaching up to 42% alcohol by volume. In addition to Calvados, other fruit distillates are known: kirsh is the fruit distillate resulting from cherry distillation, Williamine is produced with Williams pears, and slivovitz is obtained from plum processing. Special distillates prepared with quinces, wild cherries, chestnuts or berries also exist (Fig. 1.3).

1.12 Conclusions The classifications, origins, and characteristics of the main natural drinks described in this chapter have shown that they are numerous, varied, and satisfy all tastes at any time of day. Nevertheless, in the face of constant and painstaking market stress, consumers must make careful choices to determine whether a drink suits their needs. The product label should always be read to understand the composition of the drink, which can help avoid excess sugars, dyes, and alcohol that can harm the health of the consumer. In fact, even fruit juice drinks, consumed by children of all ages, may be harmful if the consumer is allergic to any type of fruit or additive present in the drink itself. Finally, one must remember that water remains the most excellent beverage, as water is a well-known fundamental component of

30  Chapter 1  An Overview of Natural Beverages

all living organisms, varying in percentage depending on age, sex, and weight. Water is found in high percentages in the protoplasms of all cells, including both prokaryotes and eukaryotes, and acts as a solvent for all biomolecules (carbohydrates, proteins, water-soluble vitamins, etc.), allowing them to react among themselves in various biochemical reactions. Apart from being a solvent, water actively participates as a reagent in various metabolic reactions and is therefore of fundamental importance for the transport of nutrients in all bodily regions and for the elimination and excretion of waste produced in biochemical reactions through urine. Water also plays a decisive role in regulating body temperature via sweating and concentrating mineral salts and participates in digestion promoting intestinal transit and nutrient absorption. Because water must be present in very high amounts, it is consequentially classified as a “macronutrient” in human nutrition. No other substances are better for human consumption than water, as it is suitable both for children and adults for its richness of mineral salts and allows toxic substances to be diverted from our body and can always be taken without restriction.

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Brand, H.S., 2013. Summary of: an in  vitro investigation of the erosive potential of smoothies. Br. Dent. J. 214 (4), 172–173. Caldeira, I., Lopes, D., Delgado, T., Canas, S., Anjos, O., 2017. Development of blueberry liquor: influence of distillate, sweetener and fruit quantity. J. Sci. Food Agric. https://doi.org/10.1002/jsfa.8559. Campbell-Falck, D., Thomas, T., Falck, T.M., Tutuo, N., Clem, K., 2000. The intravenous use of coconut water. Am. J. Emerg. Med. 18 (1), 108–111. Cano-Marquina, A., Tarin, J.J., Cano, A., 2013. The impact of coffee on health. Maturitas 75 (1), 7–21. Canuto, M.H., Rosa, C.A., Moura, F., Augusti, R., Siebald, H.G., 2012. Distillation of fermented sugarcane juice: fractions characterized by electrospray ionization mass spectrometry and multivariate data treatment. J. Mass Spectrom. 47 (7), 901–904. Castillejo, N., Martinez Hernandez, G.B., Monaco, K., Gomez, P.A., Aguayo, E., et  al., 2017. Preservation of bioactive compounds of a green vegetable smoothie using short time-high temperature mild thermal treatment. J. Food Sci. Technol. Int. 23 (1), 46–60. Catteau, C., Trentesaux, T., Delfosse, C., Rousset, M.M., 2012. Consumption of fruit juices and fruit drinks: impact on the health of children and teenagers, the dentist's point of view. Arch. Pediatr. 19 (2), 118–124. Chauhan, O.P., Archana, B.S., Singh, A., Raju, P.S., Bawa, A.S., 2014. A refreshing beferage from mature coconut water blended with lemon juice. J. Food Sci. Techonol. 51 (11), 3355–3361. Chrysant, S.G., Chrysant, G.S., 2015. Cardiovascular complications from consumption of high energy. J. Hum. Hypertens. 29 (2), 71–76. Cuomo, R., Andreozzi, P., Zito, F.P., 2014. Alcoholic beverages and carbonated soft drinks: consumption and gastrointestinal cancer risks. Cancer Res. Treat. 159, 97–120. de Souza, M.D., Vásquez, P., del Mastro, N.L., Acree, T.E., Lavin, E.H., 2006. Characterization of cachaça and rum aroma. J. Agric. Food Chem. 54 (2), 485–488. de Souza, P.P., Augusti, D.V., Catharino, R.R., Siebald, H.G., Eberlin, M.N., Augusti, R., 2007. Differentiation of rum and Brazilian artisan cachaça via electrospray ionization mass spectrometry fingerprinting. J. Mass Spectrom. 42 (10), 1294–1299. Ding, M., Bhupathiraju, S.N., Chen, M., van Dam, R.M., Hu, F.B., 2014. Caffeinated and decaffeinated coffee consumption and risk of type 2 diabetes: a systematic review and a dose-response meta-analysis. Diabetes Care 37, 569–586. Dordevic, V., Balanc, B., Belscak-Cvitanovic, A., Levic, S., Trifkovic, K., Kalusevic, A., et  al., 2015. Trends in encapsulation technologies for delivery of food bioactive compounds. Food Eng. Rev. 7, 452–490. Formato, A., Gallo, M., Ianniello, D., Montesano, D., Naviglio, D., 2013. Supercritical fluid extraction of α- and β-acids from hops compared to cyclically pressurized solid-­liquid extraction. J. Supercrit. Fluids 84C, 113–120. Franitza, L., Granvogl, M., Schieberle, P., 2016. Influence of the production process on the key aroma compounds of rum: from molasses to the spirit. J. Agric. Food Chem. 64 (47), 9041–9053. Gaanappriya, M., Guhankumar, P., Kiruththica, V., Santhiya, N., Anita, S., 2013. Probiotication of fruit juices by Lactobacillus acidophilus. Int. J. Adv. Biotechnol. Res. 4, 72–77. Gallo, M., Vitulano, M., Andolfi, A., DellaGreca, M., Naviglio, D., 2017. Rapid solid-­liquid dynamic extraction (RSLDE), a new rapid and greener method to extract two steviol glycosides (stevioside and rebaudioside a) from stevia leaves. Plant Foods Hum. Nutr. 72, 141–148. Gawel, R., Smith, P.A., Cicerale, S., Keast, R., 2017. The mouthfeel of white wine. Crit. Rev. Food Sci. Nutr. Available from: https://doi.org/10.1080/10408398.20 17.1346584.

32  Chapter 1  An Overview of Natural Beverages

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Libuda, L., Kersting, M., 2009. Soft drinks and body weight development in childhood: is there a relationship? Curr. Opin. Clin. Nutr. Metab. Care 12 (6), 596–600. Liu, F.X., Wu, G., Chen, L., Hu, P., Ren, H., Hu, H., 2015a. Coffee consumption decreases risks for hepatic fibrosis and cirrosi: a meta-analysis. PLoS One 10. e014257. Liu, J.X., Zhu, M.Y., Feng, C.Y., Ding, H.B., Zhan, Y., Zhao, Z., Ding, Y.M., 2015b. Bamboo leaf extract improves spatial learning abilitymin a rat model with senile dementia. J Zhejiang Univ Sci B 16 (7), 593–601. Loki, A.L., Rajamohan, T., 2003. Hepatoprotective and antioxidant effect of tender coconut water on CCl4 induced liver injury in rats. Indian J. Biochem. Biophys. 40, 354–357. Lopez Diaz-Ufano, M.L., 2015. Consumption estimation of non alcoholic beverages, sodium, food supplements and oil. Hosp. Nutr. 31 (3), 70–75. Lu, B., Wu, X., Tie, X., Zhang, Y., Zhang, Y., 2005. Toxicology and safety of anti-oxidant of bamboo leaves, Part  1: Acute and suchronic toxicity studies onon anti-oxidant bamboo leaves. Food Chem. Toxicol. 43 (5), 783–792. Maalik, A., Bukhari, S.M., Zaidi, A., Shah, K.H., Khan, F.A., 2016. Chlorogenic acid: a pharmacoloogically potent molecule. Acta Pol. Pharm. 73, 851–854. Maisuria, V.B., Hosseinidoust, Z., Tufenkji, N., 2015. Polyphenolic extract from Maple syrup potentiates antibiotic susceptibility and reduces biofilm formation of pathogenic bacteria. Appl. Environ. Microbiol. 81, 3782–3792. Mao, J.W., Yin, J., Ge, Q., Jiang, Z.L., Gong, J.Y., 2013. In  vitro antioxidant activities of polysaccharides extracted from Moso Bamboo Leaf. Int. J. Macromol. 55, 1–5. Mesas, A.E., Leon Munoz, L.M., Rodriguez-Artalejo, F., Lopez Garcia, E., 2011. The effect of coffee on blood pressure and cardiovascular disease in hypertensive individuals: a systematic review and meta-analysis. Am. J. Clin. Nutr. 94, 1113–1126. Mischek, D., Krapffenbauer-Cemak, C., 2012. Exposure assessment of food preservatives (sulphites, benzoic acid and sorbic acid) in Austria. Food Addit. Contam. Part A Chem. Anal. Control Expo. Risk Assess 29 (3), 371–382. Moradzadeh, M., Hosseini, A., Erfanian, S., Rezaei, H., 2017. Epigallocatechin-3-gallate apoptosis in human breast cancer T47D cells through down-regulation of P13K/ AKT telomerase. Pharmacol. Rep. 69 (5), 924–928. Nahar, P.P., Driscoll, M.V., Li, L., Slitt, A.L., Seeram, N.P., 2014. Phenolic mediated anti-­ inflammatory propertirs of a maple syrup extract in RAW264.7 murine macrophages. J. Funct. Foods 6, 126–136. Naviglio, D., Ferrara, L., Formato, A., Gallo, M., 2014a. Efficiency of conventional extraction technique compared to rapid-solid liquid dynamic extraction (RSLDE) in the preparation of bitter liquors and elixirs. IOSR J. Pharm. 4 (5), 14–22. Naviglio, D., Formato, A., Gallo, M., 2014b. Comparison between 2 methods of solid–­ liquid extraction for the production of Cinchona calisaya elixir: an experimental kinetics and numerical modeling approach. J. Food Sci. 79 (9), 1704–1712. Naviglio, D., Formato, A., Vitulano, M., Cozzolino, I., Ferrara, L., Zanoelo, E.F., Gallo, M., 2017. Comparison between the kinetics of conventional maceration and a cyclic pressurization extraction process for the production of lemon liqueur using a numerical model. J. Food Process Eng. 40 (2). e12350. Ng, K.W., Cao, Z.J., Chen, H.B., Zhao, Z.Z., Zhu, L., Yi, T., 2017. Oolong tea: a critical review of processing methods, chemical composition, health effects and risk. Crit. Rev. Food Sci. Nutr. https://doi.org/10.1080/10408398.2017.1347556. Niimi, J., Danner, L., Li, L., Bossan, H., Bastian, S.E., 2017. Wine consumers' subjective responses to wine mouthfeel and understanding of wine body. Food Res. Int. 99 (Part 1), 115–122. Nissensohn, M., Lopez-Ufano, M., Castro-Quezada, I., Serra-Majem, L., 2015. Assessment of beverage intake and hydration status. Hosp. Nutr. 31 (3), 62–69. Nowicka, P., Wojdyto, A., Teleszko, M., 2017. Effect of mixing different kinds of fruit juice with sour cherry puree on nutritional properties. J. Food Sci. Technol. 54 (1), 114–129.

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Thornton, S.N., 2010. Thirst and hydration: physiology and consequences of dysfunction. Physiol. Behav. 100 (1), 15–21. Tornita, J., Mochizuchi, S., Fujiirnoto, S., Kashihara, N., Akasaka, T., et al., 2017. Acute improvement of endothelial function after oral ingestion of isoglucose, bitter beer components. Biochem. Biophys. Res. Commun. 484 (4), 740–745. Wang, L., Tian, X., 2017. Epigallocatechin-3-gallate protects against homocysteine-­ induced brain damage in rats. Planta Med. https://doi.org/10.1055/s-0043-114865. Wang, C.Y., Wu, S.J., Shyu, Y.T., 2013. Antioxidant properties of certain cereals as affected by food-grade bacteria fermentation. J. Biosci. Bioeng. 117 (4), 449–456. Wang, Y., Ji, B., Wu, W., Wang, R., Yang, Z., et al., 2014. Hepatoprotective effects of kombucha tea: identification of functional strains and quantification of functional components. J. Sci. Food Agric. 94, 265–272. West, S.G., Mc Intyre, M.D., Piotrowski, M.J., Poupin, N., Miller, D.L., Preston, A.G., et al., 2014. Effects of dark chocolate and cocoa consumption on endothelial function and arterial stiffness in overweight adults. Br. J. Nutr. 111 (4), 653–661. Ying, C., Mao, Y., Chen, L., Wang, S., Ling, H., Li, W., Zhou, X., 2017. Bamboo leaf extract ameliorates diabetic nephropathy through activating the AKT signaling pathway in rats. Int. J. Biol. Macromol. https://doi.org/10.1016/j.ijbiomac.2017.03.124. Yong, W.J.W.H., Ge, L., Ng, Y.F., Tan, S.N., 2009. The chemical composition and biological properties of coconut (Cocos nucifera L.). Molecules 14, 5144–5164.

Further Reading Williams Jr., R.D., Housman, J.M., Odum, M., Rivera, A.E., 2017. Energy Drink use linked to high sugar beverage intake and BMI among teens. Am. J. Salute Behav. 41 (3), 259–265.

NATURAL BEVERAGES AND THEIR ROLE AS FUNCTIONAL FOODS

2

Victoria Konstantinova Atanasova, Penka Dimitrova Gatseva Department of Hygiene and Ecomedicine, Faculty of Public Health, Medical University, Plovdiv, Bulgaria

2.1 Introduction Currently, functional foods are an important branch in the area of nutrition science. Over the recent years, studies have led to the discovery of a large number of substances and components in foods, including beverages, which can have a beneficial effect on health. Functional foods which contain significant amounts of bioactive components may bring desirable health benefits beyond basic nutrition and play a major role in preventing chronic diseases (Taheri Rouhi et al., 2017). An important issue is whether a purified phytochemical has the same health benefits as whole foods or food combinations, where the phytochemical is contained. A number of studies suggest that the additive and synergistic effects of phytochemicals in fruit and vegetables account for their potent antioxidant and anticancer activities, and that the benefit of a diet rich in fruit and vegetables is due to the combination of natural phytochemicals available in whole foods. Nowadays, there are numerous and undisputed pieces of evidence that diets abundant in fruit and vegetables but moderate in meat and fats are associated with a lower risk of developing various forms of cancer and cardiovascular diseases (CVDs), as well as other diseases such as arthritis, diabetes, cataracts, and age-related macular degeneration. Even the process of aging can be beneficially influenced by the high intake of fruit and vegetables (Coyne et al., 2005; Wootton-Beard and Ryan, 2012; Shu et al., 2014; Farvid et al., 2016; Martí et al., 2016; Aune et al., 2017; Taheri Rouhi et al., 2017). The increased intake of fruit and vegetables is enshrined in the recommendations of the World Health Organization (WHO, 2003), the population nutrition recommendations in the each individual country, the World Foundation and the Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00002-X © 2019 Elsevier Inc. All rights reserved.

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American Institute for Cancer Research (WCRF/AICR, 1997; WCRF/ AICR, 2007). The suggested mechanisms and favorable health effects of phytochemicals found in vegetables and fruits are attributable to their antioxidant properties. A lot of studies are focused on the relationship between the dietary intake of antioxidant vitamins (vitamin C, α-tocopherol, and beta-carotene) as well as some phytochemicals (lycopene, flavonoids, and anthocyanins) and the risk of developing chronic diseases (Agarwal and Rao, 2000; Wootton-Beard and Ryan, 2012; Taheri Rouhi et  al., 2017). They discuss the effect of intaking these micronutrients with food and adding supplements to the diet (Agarwal and Rao, 2000; Jian et al., 2005; Massini et al., 2016). The evidence of the protective effect of single antioxidant nutrients intake is less convincing because it has been found that other dietary ingredients also play a major role in the prevention of chronic noninfectious diseases (Langseth, 2000; Chandra et al., 2012; Burrows et al., 2015). For this reason, the intake of a combination of antioxidant nutrients, especially ones from natural plant sources, is more beneficial than the intake of single antioxidants (Langseth, 2000; Chandra et al., 2012; Massini et al., 2016). Natural substances are commonly preferred over the chemical ones and are generally considered to be healthy. The increasing demand for natural ingredients that improve health and appearance also applies to beverages as the fastest growing section of the market for functional foods. Functional beverages are launched, such as fortified water, tea, or juices, claiming to bring overall nutrition, essential energy, antiaging, or relaxing effects. The so-called “superfruits,” for example, berries, grapes, or pomegranates, provide an effective range of healthy compounds, including vitamins, fatty acids, minerals, and antioxidants. In this sense, the new exotic and African fruits might be useful sources in the near future. Tea and green botanical plants, such as algae or aloe vera, are also rich in effective bioactive compounds and are traditionally used (Gruenwald, 2009). Nutritionists and healthcare specialists are constantly revealing the beneficial health effects of various functional foods, functional beverages, and food supplements. About 2500 years ago, the father of modern medicine Hippocrates proclaimed the connection between food and health benefits: “Let food be thy medicine and medicine be thy food” (Hippocrates, 460–377 BC). Nutraceuticals and functional foods are increasingly gaining popularity all over the world, especially the demand for functional nutritional beverages. Some examples include orange juice which is rich in vitamin C, calcium and phytosterols, soft drinks with their anthocyanins, and green tea with its epigallocatechin gallate. It is essential for functional beverages to carry appropriate labeling information in favor of the consumer. A matter of great importance is also that these functional beverages shall be strictly compliant

Chapter 2  Natural Beverages and Their Role as Functional Foods   39

with the regulatory guidelines in order to win consumer trust in the market (Swaroop et al., 2016; Ogundele et al., 2016). Functional beverages, a subsector of functional food production and the fastest growing sector of the functional food market, are getting more and more popular among consumers because of their perceived health benefits. Comfort and health benefits are two of the most important factors when consumers make decisions to purchase food and drinks. Functional beverages claim to improve the athletic (sport) endurance, energy status, and hydration of the body and they are associated with various health benefits, such as antioxidant activity, a healthy cardiovascular system, cancer prevention, a well-functioning digestive system, and good immune protection (Li et al., 2016). Apart from water, the most popular and traditional functional drinks on a global scale are tea, coffee, and fruit juices (Adams, 2014). Newly developed functional beverages contain vitamins and minerals, amino acids, and proteins but in most cases, they contain functional ingredients from fruit, vegetables, or other parts of medicinal plants, such as acai, pomegranates, blueberries, etc. Therefore, phytochemical constituents, which are the structural elements of functional beverages that provide a purposeful health functionality, should be well studied. Bioactive phytochemicals in functional beverages can be classified according to their chemical structures as polyphenols, including flavonoids, terpenoids, carotenoids, saponins, phytosterols, polysaccharides, and alkaloids, although there are some overlaps of the abovementioned classifications (Swaroop et  al., 2016; Li et  al., 2016; Ogundele et al., 2016). Our review aims to examine the role of some natural beverages as functional foods in the prevention of chronic diseases. We have paid special attention to certain popular and commonly consumed foods, such as tomato products and Aronia melanocarpa ones and their beverages.

2.2  Bioactive Food Compounds in the Prevention of Chronic Diseases It is generally assumed that a diet based mainly on foods of plant origin, with a high intake of fruit and vegetables, reduces the risk of oxidative stress-related diseases, such as cancer, atherosclerosis, Alzheimer’s disease, diabetes, and age-related macular degeneration. The relation between nutrition and these chronic diseases is complicated because a large number of nutrients are consumed every day. The typical eating pattern includes more than 25,000 bioactive food components. It is hard to make an intake assessment of some of them because of the large variations in their content in food (Carlsen et al., 2010;

40  Chapter 2  Natural Beverages and Their Role as Functional Foods

Wootton-Beard and Ryan, 2012; McDougall, 2017). It is now known that besides the traditional nutrients in foods of plant origin, there are also many bioactive ingredients that can lower the risk of chronic diseases. These ingredients are generally called “phytochemicals.” Most of these phytochemicals are redox-active molecules, and therefore, they are defined as antioxidants. Antioxidants eliminate free radicals and other reactive oxygen and nitrogen species thus causing a large majority of chronic diseases (Carlsen et al., 2010). Antioxidant nutrients, including carotenoids, may have beneficial health effects through other mechanisms, apart from their antioxidant properties, such as gap junction communication, cell growth regulation, modulation of gene expression and immune response, and modulation of phase I and II drug-metabolizing enzymes. Besides combating oxidative stress, dietary constituents like lycopene, tocopherol, and ascorbic acid, also have other effects (e.g., the neuroprotective effect of γ-tocopherol in neurodegenerative disorders such as Parkinson’s disease) (Li et al., 2002; Carlsen et al., 2010; Johary et al., 2012). The natural micronutrients most commonly found in food and the most frequent antioxidants in serum are retinol, alpha-­tocopherol, lycopene, and alpha and β-carotene. Bioactive compounds have been studied with great intensity in order to assess their impact on health. The results of many epidemiological studies have indicated the protective effect of diets based on plants rich in phytochemicals on CVDs and cancer. A large number of bioactive plant ingredients have been identified which differ in chemical structure and function. The most studied phytochemicals are phenolics and carotenoids (Kris-Etherton et  al., 2002; Liu, 2013a, 2013b; Fiedor and Burda, 2014; Di Pietro et  al., 2016; Gormaz et  al., 2016; Zhou et  al., 2016; Tressera-Rimbau et  al., 2017). There is a sufficient evidence, resting on the data from population-­based research, regarding recommendations for consumption of natural plant products that are rich in bioactive compounds (Kris-Etherton et  al., 2002; Liu, 2013a; Liu, 2013b; Tressera-Rimbau et al., 2017). In spite of the complexity of the interrelations between nutrients and bioactive substances in food and cancer processes, in recent years, a large number of studies have provided convincing evidence that dietary factors can have an effect on each of the various cancer development stages—initiation, promotion, and progression, or on the prevention of genetic alterations, whatever the reason is. On the other hand, several stages in the carcinogenic process can be modified by one (the same) nutrient (Abdulla and Gruber, 2000; Li et al., 2002; Sheytanov, 2003; Krinsky and Johnson, 2005). The main mechanisms, by which the ingredients in food as a whole have their effect, are through direct influence on cell genetic apparatus or by rendering the detoxifying enzymes more active. This influence can be exercised directly by food ingredients, by their

Chapter 2  Natural Beverages and Their Role as Functional Foods   41

­ etabolites, or by the metabolic responses caused by them (Langseth, m 2000; Sheytanov, 2003). A large number of mechanisms have been demonstrated to account for the anticarcinogenic activities of dietary constituents, but attention has recently been focused on intracellular signaling cascades as common molecular targets for various chemopreventive phytochemicals (Surh, 2003). By studying the cellular antioxidant activity (CAA) (a more biologically representative method to quantify antioxidant activity by screening fruit, vegetables, natural products, and dietary supplements for potential health benefits) of common vegetables and fruit, Song et al. (2010), Wolfe et al. (2008), and Wan et al. (2015) found that CAA values are significantly correlated to the total phenolic content and not correlated to the total flavonoid content or oxygen radical absorbance capacity (ORAC) values. Pomegranates and berries (wild blueberries, blackberries, raspberries, and cultivated blueberries) have the highest CAA values, whereas banana and melons—the lowest ones. Greater fruit and vegetable consumption is an effective strategy to increase antioxidant intake and decrease oxidative stress and it may lead to a lower risk of developing chronic diseases, such as cancer and CVD. Study data on the CAA of the commonly consumed fruit and vegetable species could be useful for consumers to plan antioxidant-rich diets and for nutritionists to estimate health benefits of fruit and vegetables based on their daily intake (Wan et al., 2015).

2.3  Epidemiologic Evidence of a Relation Between Food and Chronic Diseases A large number of epidemiologic studies have indicated that an increase in the consumption of fruit and vegetables is associated with a decrease in the incidence of CVD, coronary heart diseases (CHD), and stroke (Bazzano et al., 2002; Bhupathiraju et al., 2013; Aune et al., 2017). More than 200 studies have examined the relation between the consumption of fruit and vegetables and the risk of various cancers (Gandini et al., 2000; Kolonel et al., 2000; Smith-Warner et al., 2001; Farvid et al., 2016; Aune et al., 2017). A meta-analysis of 26 studies by Gandini et al. (2000) found a relation between the risk of breast cancer and the intake of fruit and vegetables. When comparing high and low intake, a statistically significant difference was found in 17 studies of the consumption of vegetables and in 12 studies involving fruit consumption. However, the consumption of fruit and vegetables was not significantly related to a lower risk of breast cancer in a study by Smith-Warner et al. (2001), which used summarized data from eight cohort studies. A multiethnic case-control study, which involved 1619 African Americans, white Americans, Japanese, and Chinese people

42  Chapter 2  Natural Beverages and Their Role as Functional Foods

with confirmed diagnosis of prostate cancer and 1618 control subjects, examined the protective effects of fruit and vegetable intake on prostate cancer. The data showed that the risk of prostate cancer is unrelated to the consumption of fruit; it is rather associated with the intake of cruciferous and yellow-orange vegetables. This relation iss strongest for advanced cases of prostate cancer for the highest quintile of yellow-orange vegetable intake (odds ratio/OR/ = 0.67; P = 0.01) and for the highest quintile of cruciferous vegetable intake (OR = 0.61; P = 0.006). These results were consistent among various ethnic groups (Kolonel et al., 2000; Kris-Etherton et al., 2002). Although most research data do not prove the important role of the total intake of fruit and vegetables in the prevention of prostate cancer, it is possible for food sources rich in specific bioactive ingredients to have a beneficial effect. Some micronutrients, like selenium and vitamin E, actually have a potential cancer-protective effect (Chan et al., 2009; Choi et al., 2015; Perez-Cornago et al., 2017). The strongest evidence, complying with the judgment “convincing” and “probable,” shows that probably foods containing lycopene and selenium, and foods containing selenium protect against prostate cancer. There is a small probability that β-carotene (from foods or supplements) might have a crucial effect on the risk of this malignant disease (World Cancer Research Fund/American Institute for Cancer Research (WCRF/ AICR), 2007). The results from the Nurses’ Health Study, involving 77,283 women, and the Health Professionals’ Follow-up Study, involving 47,778 men, that defined the relation between the risk of lung cancer and fruit and vegetable consumption, were equivocal. A 21% reduction in risk was observed in women when the highest quintile of fruit and vegetable intake was compared with the lowest one (RR/ relative risk/ = 0.79; 95% CI, 0.59–1.06). Among men, however, a lower risk of lung cancer was not observed with increased fruit and/or vegetable intake (RR = 1.12; 95% CI, 0.74–1.69). When smoking status was considered, both men and women demonstrated a relation between total fruit and vegetable intake and a decreased risk of lung cancer that was not statistically significant (RR = 0.63; 95% CI, 0.35–1.12 in the highest tertile) (Feskanich et al., 2000; Kris-Etherton et al., 2002). Two other studies of the health of nurses (the Nurses’ Health Study) and healthcare specialists (the Health Professionals’ Follow-up Study) also define the relation between total fruit and vegetable intake and the incidence of colon and rectal cancer. No relation between the consumption of fruit and vegetables and colon and rectal cancer incidence was observed in either of these two cohorts. In the combined results of men and women, a difference of one extra portion of fruit and vegetables per day was related to the risk of rectal cancer (RR = 1.02; 95% CI, 0.95–1.09) and the risk of colon cancer (RR = 1.02; 95% CI, 0.98–1.09). These two large studies (the Nurses’ Health Study, n = 88,764 women

Chapter 2  Natural Beverages and Their Role as Functional Foods   43

and the Health Professionals’ Follow-up Study, n = 47,325) did not show a protective effect of fruit and vegetables against colon and rectal cancer, but a diet rich in these foods is recommended because of the protection they provide against other chronic diseases (Michels et al., 2000; Kris-Etherton et al., 2002).

2.4  Natural Beverages of Fruit Origin 2.4.1 Cancer Chemopreventive Effects of Selected Fruit Juices It is now well accepted that cancer is a preventable disease because many of the lifestyle factors causing cancer are simply modifiable and the biochemical changes taking place during tumor promotion can be reversed. About 30%–40% of cancers can be prevented by appropriate dietary habits and lifestyle modifications (Kundu et al., 2016). Since oxidative stress and inflammation play key roles at all stages of carcinogenesis by causing oxidative or covalent changing of cellular macromolecules and activation of oncogenic signal transduction pathways, substances with antioxidative and anti-inflammatory properties are considered to be effective in preventing cancer. Thus, the introduction of the concept of cancer prevention termed “chemoprevention” (Sporn et al., 1976). Numerous studies have demonstrated that antioxidant and anti-­ inflammatory plant constituents are effective in preventing carcinogenesis (Surh et al., 2001; Kundu and Surh, 2005; Zhou et al., 2016). The biochemical basis of cancer chemoprevention by means of a wide variety of structurally diverse plant metabolites, also known as phytochemicals, includes inhibition of carcinogen activation and oxidative damage of cellular macromolecules, suppression of inflammatory responses, induction of growth arrest and apoptosis in cancer cells, inhibition of tumor growth by blocking angiogenesis and cancer invasion, migration, and metastasis (Surh et al., 2001; Kundu and Surh, 2005). Current epidemiological and preclinical studies suggest that an inverse correlation exists between the regular consumption of fruit or fruit juices and the risk of various organ-specific cancers (Donaldson, 2004; Wu et  al., 2009; Aune et  al., 2017). The European Prospective Investigation into Cancer and Nutrition (EPIC) has demonstrated that regular consumption of fruit can reduce the risk of certain cancers (Miller et al., 2004; van Duijnhoven et al., 2009). There have been thorough studies of the anticancer effects of various fruit, fruit extracts, fruit juices, and the isolated fruit-derived phytochemicals. Much of the chemoprevention research of fruit extracts includes the effects of organic extract of fruits, fruit peels, as well as the partially purified fractions of whole fruit extracts. Moreover, ­molecular

44  Chapter 2  Natural Beverages and Their Role as Functional Foods

mechanisms of cancer chemoprevention with phytochemicals which are commonly found in various fruit and fruit juices have been studied in detail (Kundu et al., 2016). As the purpose of this chapter is to focus on the chemopreventive potential of fruit juices, studies with organic extracts or fractions of fruits have been ignored. It has been well documented that fruit juices can trigger cancer chemoprevention activities by means of their antioxidant, antigenotoxic, anti-inflammatory, antiproliferative, apoptosis inducing, and antiangiogenic features (Fig. 2.1).

2.4.1.1  Berry Juices Different varieties of berry fruit juices are widely consumed. These include juices from blueberries, blackberries, raspberries, strawberries, gooseberries, cranberries, and chokeberries among others. A great deal of research has been done into the cancer-preventive potential of berry juices. Fresh juices from strawberries, blueberries, and raspberries showed a significant inhibition of mutagenesis caused by methyl methanesulfonate and the metabolically activated carcinogen benzo[a]pyrene (B[α]P) (Smith et  al., 2004). Berries contain several phytochemicals, such as proanthocyanidins, anthocyanins, and other flavonoids. Boivin et al. (2007) examined the anticancer effects of 13 different berry juices in a wide variety of human cancer cells. Juices from raspberries, black currant, white currant, gooseberries, velvetleaf blueberries, low-bush blueberries, sea buckthorn, and cranberries notably inhibited the growth of various cancer cells, including those of stomach, prostate, large intestine, and breast. The inhibitory impact of berry juices was due to cell cycle block, but not through caspase-dependent apoptosis pathways, as evidenced by the downregulation of the expression of cell cycle regulatory proteins, such as cyclin-­dependent kinase (Cdk)-4, and Cdk-6 and cyclin-D1 and ­cyclin-D3. Out of the 13 berries tested, the juice of raspberries, black currant, gooseberries, sea buckthorn, cranberries, and blackberries

Fig. 2.1  Cancer chemopreventive effects of fruit juices.

Chapter 2  Natural Beverages and Their Role as Functional Foods   45

greatly inhibited tumor necrosis factor (TNF)-α-induced expression of cyclooxygenase-2 (COX-2) and the activation of nuclear factor kappalight-chain-enhancer of activated B cells (NF-κB) (Boivin et al., 2007).

2.4.1.2 Chokeberries The fruit of A. melanocarpa [Michx] Elliot and Aronia arbutifolia [L] Elliot are commonly known as black chokeberries and red chokeberries, respectively (Kulling and Rawel, 2008). Because of the high content of anthocyanins, chokeberries have been used as a food colorant for a long time. The astringent taste of chokeberries limits their consumption, but recent advances in fruit juice blending technology improve the taste of the juice by mixing it with other fruit juices, such as that of apples, pears, or black currant. Phytochemicals contained in chokeberries include anthocyanins (cyanidin-glycosides), phenolic acids (chlorogenic acid, cryptochlorogenic acid, and neochlorogenic acid), and carotenoids (β-carotene, β-cryptoxanthin, and violaxanthin) (Kulling and Rawel, 2008; Lee et  al., 2014; Wangensteen et  al., 2014). Anthocyanins, which make about 25% of total polyphenols in chokeberry juice (Oszmianski and Wojdylo, 2005), demonstrated inhibitory effects on the mutagenicity of B[α]P and 2-aminoflourene (Gasiorowski et  al., 1997). Thus, the intake of chokeberry juice inhibited the endogenous formation of N-nitrosamine in rats opposing aminopyrene and sodium nitrite (SN) and it also protected against liver damage (Atanasova-Goranova et  al., 1997). As N-nitrosamine is a potent hepatocellular carcinogen, the study herein suggests that chokeberry juice can prevent liver cancer. The pathomorphological and histochemical studies which Atanasova (2013) conducted of the organs of white rats from the test group, treated with diethylnitrosamine (DENA)+chokeberry juice, showed the potential protective effect of the 6-month intake of black chokeberry juice used on the applied model of experimental DENA tumorigenesis. The changes in hepatocytes were significantly less pronounced in the rats of DENA+chokeberry juice group than in those of the DENA control group. This was evidenced by the lower degree of cell swelling and steatosis of the hepatocytes in the test group animals, the reduced relative number of livers affected by cirrhotic processes, the increase in glycogen in the hepatocytes with these rats, as well as the decrease in the degree of cell swelling of the renal epithelial cells with animals from the same (test) group (Fig. 2.2A and B). The positive changes in the structure and some histochemical parameters in the organs of the animals from the test group treated with DENA+aronia juice were associated with the biologically active ingredients contained in the black chokeberry juice used (anthocyanins, phenolic compounds, tanning agents, and ascorbic acid), as well as suitable pH (Tables 2.1 and 2.2).

Fig. 2.2  (A, B) Histopathological photomicrographs of rat liver from the DENA control and test groups. (A) Fibrotic septas in the liver parenchyma of a rat, treated with DENA. Van Gieson Stain 8 × 12.5; (B) Expansion of fibrous connective tissue in the liver of a rat, treated with DENA+chokeberry juice. Hematoxylin and eosin stain 8 × 20.

Table 2.1  Basic Technological Indices of Aronia Juice Used Coefficient of Refraction, 20°C

Dry Matter (by Refractometer) %

Total Sugar (Inverted) (mg/mL)

Titrated Acidity (as Malic Acid) (mg/mL)

1.3719

24.70

98.0

114.7

pH

Ascorbic Acid (mg/mL)

Tanning Matter (mg/mL)

3.63

0.033

5.6

Table 2.2  Quantitative Determination of Individual and Total Polyphenols, Cyanidin, and Total Anthocyanins (mg/mL) in Aronia Juice Used Individual Polyphenols Replicates Chlorogenic Neochloro­ 4-0-Caffeoylquinic Total Total (n) Acid genic Acid Acid Rutin Polyphenolsa Cyanidin Anthocyaninsb 5 SD % RSD

0.39 0.02 5.5

0.34 0.01 4.2

0.115 0.006 5.6

SD, standard deviation; RSD, relative standard deviation. Total polyphenols are the sum of chlorogenic acid, its isomers and rutin. Total anthocyanins are the sum of all peaks.

a b

0.049 0.002 4.8

0.894 0.040 4.5

0.0124 0.001 8.2

0.106 0.006 5.8

Chapter 2  Natural Beverages and Their Role as Functional Foods   47

Similar results were reported by Bhattacharya and Chatterjee (1998) on the effect of an extract from the Indian medicinal plant Trianthema portulacastrum L. in the conditions of DENA-induced hepatocancerogenesis in rats and by Ismail et al. (2009) when investigating the effect of spirulina on experimental DBN carcinogenesis. The results of the electron microscopic studies of rat liver conducted by Atanasova et  al. (2012) showed that the ultrastructural changes in hepatocytes were more prominent in the rats from the DENA control group, compared with the DENA+chokeberry juicetreated group, although these changes were quite similar and manifested in a light or moderate degree. The hyperplasia of the smooth endoplasmic reticulum (SER) observed was a sign of regenerative processes in liver cells. Finally, the manifested changes under the influence of aronia juice were associated with adaptation and regenerative changes in hepatocytes. Ultrastructural analysis revealed that black chokeberry juice could cause apoptosis in tumor cells in the applied model of experimental DENA-induced carcinogenesis. The studies of Atanasova (2013) on the effect of black chokeberry juice on induced DENA experimental tumorigenesis in white rats showed that the relative share of non-tumorigenesis animals treated with DENA+chokeberry juice was 18% vs 2% in the DENA control group. Hepatomas predominated among benign tumors. Among malignant tumors, differentiated hepatocellular carcinomas ranked first, followed by differentiated cholangiocellular carcinomas (Fig. 2.3). On average, 94% of all tumors in the DENA control and test groups were localized in the liver. In 35% of malignant tumors in the DENA-treated group, compared to 26% in the group receiving DENA+chokeberry juice, there were metastases found in the regional

Fig. 2.3  Localization, pathomorphological picture, and number of the tumors found.

48  Chapter 2  Natural Beverages and Their Role as Functional Foods

lymph nodes, peritoneum, spleen, and lungs. In the parametric analysis conducted, there was a strong negative relationship between the number of DENA-induced tumors and their 6-month-long diet containing chokeberry juice. Based on the results obtained by Atanasova (2013) during a study of the 6-month impact of chokeberry juice on experimental DENAinduced tumorigenesis, it can be concluded that black chokeberry juice has an inhibitory effect on DENA-induced experimental hepatocarcinogenesis. This is confirmed by the inhibition of more than 50% of the total DENA tumorigenesis, the decrease in number of malignant neoplasms, the reduced relative share of clinical symptoms of a disease in animals, as well as metastases in malignant neoplasms. Undoubtedly, the chemical composition of chokeberry juice, applied in this experiment, is essential for the resultant reliable antitumor effect. A leading role in this process plays the content of bioactive substances—anthocyanins, tannins, phenolic compounds, and ascorbic acid [included as anticancerogenic factors in plant products of the classification of Wattenberg (1985) and Johnson et al. (1994), quoted from Hill (1995), and a suitable pH (3.28) (Rubenchick, 1990). Chokeberry juice is particularly effective in reducing liver tumor incidence, allowing its potential therapeutic effect in the experimental model applied by Atanasova (2013). It is believed that the ability of chokeberry juice to inhibit carcinogenesis is due to its antioxidant features that protect tissues from cellular damage (Valcheva-Kuzmanova and Belcheva, 2006; Kujawska et al., 2011). The study of Atanasova (2013) reported for the first time about the in  vivo chemopreventive effect of chokeberry juice against DENAinduced experimental hepatic carcinogenesis, which suggested its potential use in the prevention of malignant neoplasms, especially those of the liver. Chokeberry juice treatment inhibited cell proliferation of colon cancer (Caco2) in tissue culture by the induction of G2/M phase cell cycle arrest and restoration of the normal expression of the tumor suppressor—the protein carcinoembryonic antigen-related cell adhesion molecule 1 (CEACAM1), which is less in early adenomas and carcinomas (Bermudez-Soto et al., 2007). Furthermore, the extract of chokeberry, which is rich in anthocyanin, induced apoptosis in human colon cancer (HT29 cells) but did not affect the growth of normal colon epithelial (NCM460) cells (Malik et  al., 2003). The preventive effect of chokeberry juice extract on colon cancer could be attributed to its antioxidant activity (Zheng and Wang, 2003). Moreover, the constituents of chokeberry juice, such as β-cryptoxanthin (Narisawa et  al., 1999), chlorogenic acid (Park et  al., 2010), and cyanidin-3-­ glucosides (Lea et al., 2008), manifested chemopreventive effects on colon cancer.

Chapter 2  Natural Beverages and Their Role as Functional Foods   49

2.4.2 Health Effects of Chokeberry Juice The beneficial health effects of chokeberry juice, demonstrated in experimental models and clinical trials, indicate that the mechanisms of action of its bioactive constituents and/or metabolites are not limited to their antioxidant effect. The interactions of the bioactive constituents of chokeberry juice with molecules, cells, and tissues of animals and humans are both kinetic and dynamic (Denev et al., 2012; Sainova et al., 2012; Glibetić and Konić-Ristić, 2016). Most of the studies conducted up to now are directed to the effects of chokeberry juice on biomarkers and the risk factors for CVD and cancer, and the interactions of chokeberry juice constituents with the relevant cells and molecules, although scientific evidence of its effects on the prevention of other types of diseases is emerging (Glibetić and Konić-Ristić, 2016; Borowska and Brzóska, 2016).

2.4.2.1  In Vitro Studies Among the numerous studies investigating the effects of chokeberry juice and extracts in different cellular models in vitro, most relevant to their presumptive effects in humans are the studies conducted in cultures of endothelial cells derived from the gastrointestinal tract (GIT) that are exposed to the bioactive components of the juice after its consumption (Glibetić and Konić-Ristić, 2016). Atanasova et  al. (2015) examined the effect of black chokeberry juice (AJ) (from A. melanocarpa Michx. cv. Elliot) on the generation of DENA by the precursors during in vitro experiments. She assessed the amount of changes in the polyphenol complex and the anthocyanins of AJ during the nitrosation process. The main constituents having the flavonoid skeleton of AJ which participated in the nitrosation process and interacted with SN were chlorogenic acid (3-caffeoylquinic acid) and its isomers [neochlorogenic acid (5-0-caffeoylquinic acid) and 4-0-caffeoylquinic acid], and anthocyanins. The high-performance liquid chromatography (HPLC) analysis of polyphenols and anthocyanins indicated a diminished content of chlorogenic acid, its isomers, as well as anthocyanins, in the reaction mixture SN+AJ. It could be concluded that upon the availability of AJ, the generation of DENA does not decrease; furthermore, AJ components participated in the nitrosation reactions during in vitro experiments. In this way, AJ turned out to be a strong chemical agent to counteract a nitrosamine precursor SN (Atanasova et al., 2015). Further studies are required to find out whether chokeberry juice, the bioactives contained in it or their metabolites, exert some of the abovementioned activities for other types of polyphenols (Hollands et al., 2013; Konić-Ristić et al., 2013; Woodcock et al., 2013). The bioactive components of chokeberry juice have also been shown to have

50  Chapter 2  Natural Beverages and Their Role as Functional Foods

i­ nhibitory effects on the activity of cytochrome P450 3A4, an important enzyme of human xenobiotic metabolism. The most effective constituent was procyanidin B5, while the inhibitory effect of anthocyanins was determined by sugar moiety, with cyanidin 3-arabinoside the having stronger inhibitory effects compared with cyanidin 3-galactoside and cyanidin 3-glucoside (Braunlich et al., 2013). This manifested putative synergistic therapeutic effects and encouraged further research in the area of drug-food interactions, determining interindividual variations.

2.4.2.2  Animal Studies The antioxidant and anti-inflammatory properties of chokeberry juice were also confirmed in animal models. The components of chokeberry juice again exerted anti-inflammatory effects, as shown in an animal model of paw edema induced by histamine and serotonin. The observed effects were more pronounced than those of rutin used as a positive control (Borissova et al., 1994). In other experiments carried out on rats, chokeberry juice consumption prevented indomethacin-­ induced damage in the gastric mucosa (Valcheva-Kuzmanova et  al., 2005), and had beneficial effects on disturbed levels of glucose and lipids in streptozotocin-induced diabetes, without effect on these parameters in normal rats (Valcheva-Kuzmanova et  al., 2007a), and prevented the harmful impact of carbon tetrachloride on the activities of liver enzymes, lipid peroxidation, and glutathione depletion in the liver of rats (Valcheva-Kuzmanova et al., 2004). In rats treated with high-cholesterol diet, supplementation with chokeberry juice prevented elevated levels of plasma cholesterol, low-density lipoprotein (LDL) cholesterol, and triacylglycerols (TAG), without significant effects observed in animals fed on a standard diet (Valcheva-Kuzmanova et al., 2007b). With regard to that, the studies of Atanasova (2013) on the effect of black chokeberry juice on lipid parameters in the serum of rats that were exposed to a model of DENA carcinogenesis showed that the levels of high-density lipoprotein (HDL) cholesterol and triglycerides in the animals treated with DENA+chokeberry juice were close to those of the “pure” control group. Under conditions of acute experiment, targeted at studying the effect of black chokeberry nectar on the endogenous formation of N-nitrosamines in rats, Atanasova (2013) found that chokeberry nectar exerted a marked effect on the levels of urea in white rats, which was reduced by 34% compared with the “pure” control group. The latter was evidence of improved renal function. This might be due to the specific chemical composition of the black chokeberry nectar used (Table 2.3). The content of ascorbic acid and tannins, as well as a

Chapter 2  Natural Beverages and Their Role as Functional Foods   51

Table 2.3  Chemical Composition of Aronia Nectar Used Food Product

Dry Matter by Refract. (%)

Total Sugars (%)

Acids (as Citric Acid) (%)

pH

Ascorbic Acid (mg%)

AIa

Aronia nectar

10.80

3.82

0.39

3.3

110.00

1.64

a

AI (ascorbic index) = ratio ascorbate: nitrate.

suitable pH (3.3–4.8 of the food product or the reaction mixture), have a key role for inhibiting the generation of nitrosamines (Rubenchick, 1990). The high ascorbic index (AI), which is indicative of the relevant concentrations of ascorbic acid and nitrates in plant products, may be the cause of the protective effect observed. In the dissertation paper of Valcheva-Kuzmanova (2014) on the organo-protective and psychopharmacological effects of A. melanocarpa fruit juice in experimental pharmacological studies, it was manifested that this juice had extremely high levels of polyphenol compounds (proanthocyanidins, flavonoids, and phenolic acid). Chokeberry juice showed very high antioxidant capacity in vitro with regard to ABTS+, galvinoxyl, peroxyl, and hydroxyl radicals. It had a marked psychopharmacological activity in rats, suppressing locomotor activity and exploratory behavior, without disturbing the animal's habituation to a new environment, producing an anxiolytic-like effect, improving learning and memory, exerting antidepressant action, and not influencing pain sensitivity. In an experimental model of streptozotocin-­induced diabetes in rats, A. melanocarpa fruit juice proved preventive against hyperglycemia, hypertriglyceridemia, and lipid peroxidation. In a rat model of amiodarone-induced pulmonary toxicity, this juice prevented oxidative stress, inflammation, and fibrosis in lung tissue. In a paracetamol-induced pulmonary toxicity model in rats, it inhibited lung damage and lipid peroxidation. In a rat model of cisplatin-induced cytotoxicity of renal embryonic cell line, this fruit juice decreased the toxicity of cisplatin. In a model of alcohol-­induced oxidative stress in rats, it counteracted lipid peroxidation. The obtained data on the composition of chokeberry juice, its antioxidant activity, psychopharmacological and organo-­protective effects have made an original contribution (Nematbakhsh et al., 2013; Valcheva-Kuzmanova, 2014, 2015; Valcheva-Kuzmanova et al., 2014a, 2014b).

52  Chapter 2  Natural Beverages and Their Role as Functional Foods

2.4.2.3  Human Intervention Studies Similar to the studies performed in vitro, most of the studies dealing with the effects of chokeberry consumption on human health in vivo were conducted by using chokeberry fruit extracts. However, several studies investigated in greater details the results of chokeberry juice consumption, showing its numerous effects on antioxidant/prooxidant status, biomarkers and risk factors for CVD, its prevention of urinary tract infections, or beneficial actions on skin. Regarding the effect of aronia juice as in vivo antioxidant, it is commonly thought that the effects of polyphenol-rich foods or native polyphenols shown in chemically based assays and cellular models do not guarantee their potential in vivo. The main factor excluding extrapolation between in vitro and in vivo systems is the extensive metabolism of polyphenols, especially anthocyanins, and consequently, their “poor” bioavailability in the native form (Glibetić and Konić-Ristić, 2016). The beneficial effects of berries on cardiovascular health were subject of numerous human intervention studies using “traditional” risk factors (e.g., dyslipidemia, hyperglycemia, obesity, and blood pressure) and other biomarkers (e.g., platelet function, chronic inflammation, endothelial function, and oxidative stress) being “nontraditional” risk factors. Several studies focused on the effects of chokeberry juice consumption on lipid status. Skoczynska et  al. (2007) demonstrated that the consumption of 250 mL of this juice in the course of 6 weeks beneficially affected lipid status of men with mild hypercholesterolemia by a significant reduction in total cholesterol, LDL cholesterol, TAG, and increased the HDL cholesterol. Significant reductions in the serum glucose, homocysteine (Hcys), and fibrinogen concentrations were also detected (Skoczynska et al., 2007). A study of Boncheva et al. (2013) on tracking the effect of the application of Dr. Barry Sears’ lifestyle program, combined with the intake of A. melanocarpa juice (in a daily dose of 150–200 mL) in patients with nonalcoholic fatty liver disease—steatosis, found that after 60 days of treatment, the achieved laboratory values for liver function, carbohydrate, and fat metabolism were within the reference area. The control echocardiac and clinical tests after 60 days indicated a lack of the finding that is specific for steatosis. The beneficial effects on different kinds of discomfort present in patients' lives for a long time and the improved sense of health noted by the recipients of A. melanocarpa juice are significant advantages (Boncheva et al., 2013). By investigating the effect of chokeberry juice consumption on antioxidant capacity, lipids profile, and endothelial function (as important indicators for cardiovascular risk assessment) in healthy people, Nowak et al., 2016a) found that a 3-week consumption of chokeberry juice significantly increased serum antioxidant capacity, and the best results were observed just after 1 week of the experiment. However,

Chapter 2  Natural Beverages and Their Role as Functional Foods   53

there was no significant change in the blood lipid profile, except for the persons with a higher triglyceride level, where the consumption of chokeberry juice reduced triglycerides to normal values. The endothelial function was normal in all patients and did not significantly change during the study (Nowak et al., 2016a). The results of a comparative analysis of the antioxidant capacity of selected polyphenol-rich fruit juices and nectars, conducted in Poland, showed that organic chokeberry juice possessed the highest antioxidant capacity, which was 4–10 times higher than in the other popular juices. Therefore, chokeberry juice turns out to be a rich source of chlorogenic and neochlorogenic acids. The high total content of polyphenols and remarkable antioxidant capacity encourage further clinical research on chokeberry juice in the context of CVDs prevention (Nowak et al., 2016b). A study of the effect of chokeberry juice intake on the antioxidant capacity of blood plasma in healthy volunteers over 15 days found a statistically significant increase in plasma antioxidant capacity on the 10th day, as compared to the initial value, with a reduction in this capacity on the 15th day, as compared to the 10th day (Denev et al., 2011). It was concluded that the intake of chokeberry juice would have a positive effect in preventing the development of diseases caused by oxidative stress. In order to clarify the exact mechanism whereby the antioxidant capacity of blood plasma increased, it is necessary to do further research. Simeonov et  al. (2002) showed that long-term consumption of 200 mL of pure chokeberry juice resulted in a significant decrease in total cholesterol in patients with noninsulin-dependent diabetes mellitus. The potential of chokeberry juice and the bioactives contained in it on blood pressure was evaluated in a number of human studies on dietary intervention. Five studies (three with chokeberry fruit extract and two with juice) reported a marked decrease in systolic and diastolic blood pressure, including a study in patients with myocardial infarction, upon regular consumption of chokeberry extract (255 mg/ day) over 6 weeks (Naruszewicz et al., 2007); in patients with mild hypercholesterolemia who consumed chokeberry juice (250 mL/day) over 6 weeks (Skoczynska et al., 2007) and in patients with noninsulin-­ dependent diabetes mellitus over a 12-week-long consumption of chokeberry juice (200 mL/day) (Simeonov et  al., 2002). In a clinical study, it was found that the use of dietary chokeberry nectar in diabetics led to a reduction in blood glucose by 10%–30% (Kratchanova et al., 2010). Consumption of chokeberry juice was also shown to significantly reduce fasting blood glucose levels in patients with risk factors, compared with the control group (Skoczynska et al., 2007), and fasting blood glucose levels and levels of oxidized hemoglobin (HbA1C) in patients with noninsulin-dependent diabetes mellitus, compared with the initial values (Simeonov et al., 2002).

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One of the new targets of bioactive compounds in the realm of their beneficial effects on cardiovascular health are platelets, based on their role in the processes of thrombosis and atherosclerosis, assisted in their interactions by other platelets, monocytes, and neutrophils. Disturbed platelet function correlates with other CVD risk factors and the effect of polyphenol on platelets is generally considered to be beneficial for cardiovascular health, as defined by the European Food Safety Authority (EFSA Panel on Dietetic Products, Nutrition and Allergies (NDA), 2011). A preliminary study in healthy people showed that the acute consumption of chokeberry juice (150 mL) caused significant decrease in the expression of P-selectin, as a marker of platelet activation, as well as a decrease in platelet-monocyte and platelet-neutrophil ­aggregation, both in vivo and ex vivo, after the action of platelet agonists (adenosine-­ diphosphate and arachidonic acid) (Konić-Ristić, 2013). Vladimirova-Kitova et  al. (2010) found that the daily intake of 200 mL of chokeberry juice over 2 months in asymptomatic patients with mild hypercholesterolemia led to a statistically significant increase in HDL cholesterol and apolipoprotein-A1 and statistically significant decrease of LDL cholesterol. The anti-lipid effects of chokeberry juice found, primarily on the reverse phase of cholesterol, as well as the good tolerance, make it a valuable part of the dietary regimen in patients with mild hypercholesterolemia for daily clinical practice. Some new research on diets rich in bioactives caused favorable changes in fatty acid profiles in healthy, as well as in a lot of diseased patients (Ristić-Medić et al., 2009). The effects of a diet rich in plant and fruit bioactives on dietary fat and glucose metabolism, justify future work to formulate meals supplemented with bioactives from chokeberry juice as a functional ingredient. The number of human studies targeted at evaluating the effects of chokeberry juice is far less than the number of studies involving chokeberry fruit extracts, and most of them are not designed as randomized controlled studies, not considered as the “gold” standard of clinical research. However, their results, mostly showing the effects of chokeberry juice consumption on different risk factors and biomarkers of cardiovascular risk in humans, are promising and justify further research in this area for final confirmation of its functional features (Glibetić and Konić-Ristić, 2016).

2.5  Natural Beverages of Vegetable Origin 2.5.1 Tomato Juice The tomato is the second most produced and consumed plant food in the world. According to the data of the World Processing Tomato

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Council in 2013, 35 million metric tons of tomatoes were processed into different industrial products such as tomato puree, tomato paste, canned tomatoes, tomato sauce, diced tomatoes, and tomato juice. Tomato juice is mainly consumed as a beverage and an appetizer, and other ingredients are often added, such as spices, olive, and vegetable oil. In addition, tomato juice is the main ingredient of different cold beverages, cocktails, and soups, which are made by mixing tomato juice with other vegetables (onion, pepper, cucumber, garlic, celery, etc.), beef broth, clam broth, and alcoholic drinks. From a nutritional point of view, tomato juice has the same nutritional features as fresh tomato fruit, and hence it is characterized by a low fat and protein content, soluble sugar, and a low glycemic index. It also provides a wide variety of minerals and vitamins, being low in sodium, high in potassium, and containing small amounts of vitamins C, E, and folate (Martinez-Alvarez and Villarino Marin, 2006). The other bioactive compounds of tomato fruit, which have antioxidant properties, such as phenolic compounds (hydroxycinnamic acids and flavonoids) and carotenoids (mainly lycopene and β-carotene), remain intact in the tomato juice after the industrial processes (Gupta et  al., 2010, 2011; Jacob et al., 2010). Moreover, their content increases during that treatment due to the extraction, concentration, and heating, leading to a reduction of water content and hence concentrating the bioactive compounds. Furthermore, industrial processing enhances the availability of these compounds as a result of the breakdown of cell walls and other cellular organelles, thus increasing their extractability and facilitating their absorption during digestion in the human large intestine (Frolich et al., 2006). In view of the aforesaid, tomato juice preserves the nutritional properties of fruit and the bioactive compounds with antioxidant properties, except for vitamin C, and hence it can be considered a good dietary source of antioxidants, especially lycopene.

2.5.2 Health Effects of Tomato Juice The beneficial health effects associated with the consumption of tomato juice are mainly related to the high levels of lycopene and its antioxidant properties, but other bioactive compounds of tomato juice, for example, vitamin C, phenolic compounds, and folate, can have a synergistic effect in suppressing free radicals.

2.5.2.1  Prevention of Cardiovascular and Other Chronic Diseases Tsitsimpikou et al. (2014) studied the relationship between dietary consumption of tomato juice and risks factors, like inflammation, insulin resistance, and hyperlipidemia, included in the metabolic syndrome. Several parameters revealing the metabolic syndrome were monitored both in the group that consumed tomato juice and the

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control group (ADMA—asymmetric dimethylarginine) for entdothelial function, TNF-α and interleukin 6 (IL-6) for inflammation, and fasting insulin resistance index (FIRI) for insulin resistance. The results of the study indicate a significant improvement in the inflammation status and the endothelial dysfunction of the patients supplemented with tomato juice, better glycemic control by reducing insulin resistance, and a decrease in LDL cholesterol levels, along with a slight increase in HDL levels cholesterol. Investigation data suggest a mitigating effect of tomato juice regarding the risk factors associated with the metabolic syndrome (Tsitsimpikou et al., 2014). The systematic review and meta-analysis of observational studies, conducted by Song et al. (2017) and Cheng et al. (2017a), on the connection between lycopene and CVDs, found a statistically significant reciprocal link between lycopene exposure and CVD risk. The intake of lycopene with food (dietary lycopene) is statistically significant with CHD and stroke. The systematic review and meta-analysis of the effect of tomato and lycopene supplementation on CV risk factors, conducted by Cheng et  al. (2017b), found that the available evidence on these effects supports the view that increasing the intake of tomato and lycopene proved positive on blood lipids, blood pressure, and the endothelial function. These results supported the development of promising personalized nutritional strategies which included tomatoes to manage CVD. Some authors found that the consumption of single, standard daily portions of processed tomato products (sauce, soup, and juice) over 2 weeks significantly increased the concentrations of lycopene in plasma and oral mucosa (Allen et al., 2003; Bermudez et al., 2005). Dewanto et al. (2002) found that heat processing improved tomato nutritional value by increasing the bioavailability of lycopene and the overall antioxidant activity, and he argued against the view that processed fruit and vegetables have a lower nutritional value than the fresh ones. This information can have a significant impact on the dietary choices of consumers by increasing the intake of processed fruit and vegetables, so as to reduce the risk of chronic diseases. In a study of the frequency of intake of foods rich in lycopene and beta-carotene in 17–20-year-old pupils, Atanasova and Gatseva (2012a) found that the consumption of tomato juice, which is rich in antioxidants, is between 1 and 4 times a week, and in the case of consumption 2–3 times a month, the difference between men and women is statistically significant in favor of men (P 50% NaCl and KCI, calcium salts) while metals such as zinc and copper are present in negligible amounts (Venetsaneas et al., 2009). Total solids of whey contribute about 6%–6.5% of the dry matter. The type of whey depends upon the processing technique used to remove casein from the milk, with the two main types being sweet whey and acid whey. Whey, as a by-product from the manufacture of cheese and rennet casein, is known as sweet whey with a pH of 5.9–6.6. Manufacture of mineral acid precipitated casein or cheese produced by bacterial culture yields acid whey with a pH of 4.3–4.6. Whey’s composition and sensory characteristics vary depending on the kind of the whey (acid or sweet), the source of the milk (cow, sheep, bovine milk, etc.) and the feed of the animal which produced the milk, the cheese processing used, the time of the year, and the stage of lactation. But the chemical composition of whey varies mostly in relation to method used for its production (acid whey or sweet whey). The main differences are in the calcium, phosphate, lactic acid, and lactate contents, which are higher in acid whey (Table 8.1). Constituents like citric and Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00008-0 © 2019 Elsevier Inc. All rights reserved.

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210  Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages

Table 8.1  Approximate Composition of Whey (Bylund, 2015) Constituent %

Sweet Whey

Acid Whey

Total solids Water Fat True protein NPN (non-protein nitrogen) Lactose Ash (minerals) Calcium Phosphorus Sodium Potassium Chloride Lactic acid

6.0 94 0.05 0.60 0.20 4.5 0.5 0.035 0.040 0.045 0.14 0.09 0.05

6.4 93.6 0.05 0.60 0.20 4.6 0.8 0.12 0.065 0.050 0.16 0.11 0.4

lactic acid, urea and uric acid as well as vitamin B are also present in whey, but in much lower amounts. Colloidal calcium becomes more soluble in acidic environment and, consequently, by the acid coagulation of casein, part of the calcium dissolves and passes into the whey. In contrast, sweet whey, except whey proteins, contains glycomacropeptides (GMPs) formed by the enzymatic hydrolysis of κ-casein. Thus, the GMP constitutes approximately 20% of the whey protein fraction of sweet, rennet whey but is not found in the acid whey unless renneting was included in the fresh cheese manufacturing process (Jelen, 2011). In addition, the proportion of whey protein is slightly lower in whey obtained from ultrafiltered (UF) milk, and in whey obtained from milk heated at high temperature. Such processing steps allow partial retaining of certain whey protein fractions in curd which results in an increased cheese yield. In the conventional processes of cheese making, proteins which are insensitive to the action of enzymes and/or acids, pass into the whey. Consequently, this group of proteins was termed as whey proteins (Božanić et al., 2014). Whey proteins are nutritionally the most valuable components in whey. They are composed of thermosensitive fractions, such as β-lactoglobulin (β-Lg), α-lactalbumin (α-La), blood serum albumin, and immunoglobulin as well as thermostable proteose-­ peptone. Another soluble protein found in small amounts is lactoferrin, lactoperoxidase and in case of cheese whey caseino-macropeptide.

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Table 8.2  Biological Functions of Whey Proteins (Hernández-Ledesma et al., 2011) Protein

Biological Function

References

β-Lactoglobulin

Carrier of retinol, fatty acids. and triglycerides Transfer of passive immunity Immunomodulatory activity Anticarcinogenic activity Lactose synthesis Treatment of chronic stress-induced diseases Anti-carcinogenic activity Synthesis of lipids Antioxidant activity Anti-carcinogenic activity Antimicrobial activity Antifungal activity Anti-proliferative activity Antiviral activity Immunomodulatory activity Anti-thrombotic activity Anticariogenic activity Immunomodulatory activity Prebiotic activity Anti-thrombotic activity

Pérez et al. (1992) Sutton and Alston-Mills (2006) Wong et al. (1998) Mcintosh et al. (1995) Markus et al. (2002) Ganjam et al. (1997) Hallgren et al. (2008) Choi et al. (2002) Smith et al. (1992)

α-Lactalbumin

Serum albumin

Lactoferrin

Caseinomacropeptide

Immunoglobulins Lactoperoxidase

Immunomodulatory activity Growth and development Antimicrobial activity Antiviral activity Immunomodulatory activity

Orsi (2004) Olakanimi et al. (2002) Xu et al. (2010) Van der Strate et al. (2001) Togawa et al. (2002) Qian et al. (1995) Oh et al. (2000), Kawasaki et al. (1992, 1993) Otani and Monnai (1995), Otani et al. (1995, 1996) Azuma et al. (1984), Idota et al. (1994) Manso et al. (2002) Balan et al. (2010) Balan et al. (2009) de Wit and van Hooydonk (1996) Shin et al. (2005) Wakabayashi et al. (2007), Mercier et al. (2004)

Biological functions of whey proteins are summarized in Table  8.2. Whey proteins have a compact globular structure that accounts for their solubility (unlike caseins that exist as a micellar suspension, with a relatively uniform distribution of nonpolar, polar, and charged groups). These proteins have amino acid profiles quite different from caseins; they have a smaller fraction of Glu and Pro, but a greater fraction of sulfur-containing amino acid residues (i.e., Cys and Met). They are dephosphorylated, easily denatured by heat, insensitive to

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Ca2+, and susceptible to intramolecular bond formation via disulfide bridges between Cys-sulfhydryl groups. The protein content in acid and sweet whey is very similar; however, the amount of free amino acids can vary and depends on a degree of casein hydrolysis during the manufacture of cheese (acid or sweet). Thus, the amount of free amino acids in sweet whey is about 4 times higher, and in acid whey even 10 times higher than in milk (Božanić et al., 2014). In addition, whey proteins have excellent functional properties, such as good solubility, viscosity, gelling, and emulsifying properties, and their concentrates are often applied in the food industry. Since whey proteins are easier to digest than casein, they are used for purposes such as the manufacture of infant formulas or to increase the nutritional value of dairy and other food products. Also, immunoglobulin and other glycoproteins (lactoferrin, transferrin) and enzymes (lysozyme, lactoperoxidase) are very important factors that contribute to a human immunoactive system. They exert antimicrobial properties, and may reduce or inhibit allergic reactions (Brandelli et al., 2015). However, the largest constituent of whey is lactose (approximately 70% based on dry matter basis). Incidentally, most milk carbohydrates pass into the whey after cheese making of which 90% is lactose including some glucose, galactose, oligosaccharides, and amino sugars (Božanić et  al., 2014). Lactose is a very important source of energy, and has multiple roles. Some of the following beneficial effects of lactose are: • stimulation of intestinal peristalsis, facilitate calcium and phosphorus absorption (Kwak et al., 2012), • establishment of a mildly acid reaction in the intestines and thereby preventing the growth and multiplication of harmful bacteria, • ensures optimal magnesium levels and improves digestion of fat and other nutrients in the human body, • participate in the development of dental plaque, and • heat treatment of whey converts lactose into lactulose, which is one of the growth promoters of the bifidobacteria. Also, during the manufacture of cheese or casein some water-­ soluble vitamins permeate from milk into the whey, but their amounts are very variable and greatly dependent on whey handling. The most important of these vitamins are riboflavin, folic acid, and cobalamin. However, the latter two vitamins are bonded to whey proteins, what is the reason why they pass into the whey during cheese making. It is of interest to note that whey contains higher amounts of vitamin B2 than milk due to the activity of some starter cultures (i.e., lactic acid bacteria– LAB) during the manufacture of cheese. Due to relatively high levels of riboflavin, whey has a characteristic yellowish-green color (PopovićVranješ and Vujičić, 1997; Božanić et al., 2014).

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8.1.2  Possibilities of Whey Utilization? The main problem associated with whey comes from its potential to damage the environment. It has a very high biochemical oxygen demand (BOD) that can vary from 40,000 to 60,000 mg/L and a very high chemical oxygen demand (COD) of between 50,000 and 80,000 mg/L (Chatzipaschali and Stamatis, 2012). The waste load of whey is equivalent to 100–175 times that of a similar volume of domestic waste water (Mockaitis et al., 2006; Smithers, 2008). This high-polluting potential makes disposal of surplus whey expensive. Lactose, the largest constituent of whey (70%–72% of the total solids), is the main component causing these high values for BOD and COD (Jelen, 2011; Patel and Murthy, 2011). Whey is created in near equal volumes to the processed milk used during cheese manufacture. Worldwide production of whey is estimated at around 190 × 106 ton/year (Baldasso et al., 2011). It has been shown that for every 1 kg of cheese made approximately 9 L of whey is produced (Kosikowski, 1979). On average across the world, volumes of whey are growing at about the same rate as milk volumes (>2% per year; Smithers, 2008). Whey contains proteins and peptides with great functional properties, lipids, vitamins, minerals, and lactose that could be exploited by the agri-food, biotechnology, medical, and related industries and in the last several decades major research efforts have resulted in transforming whey and whey proteins from “gutter-to-gold” (Smithers, 2008). Traditionally whey (in an unmodified form) was used as an animal feed (pigs, sheep, cattle) or was land spread as a fertilizer. As a direct animal feed whey (usually diluted with drinking water) provides high-quality proteins and lactose as energy sources and also provides calcium, phosphorus, sulfur, and water-soluble vitamins. Excessive lactose and minerals however can cause issues for farm animals that necessitate a limit in untreated whey use as an animal feed. There are also issues with land spreading the application of large quantities of whey leaves high saline deposits in the soil, damaging fertility (Kosikowski, 1979). Both uses have difficulties concerning volumes and high transportation costs that make these solutions impractical for the amounts of whey being created today. Whey (sweet and acidic) can also be dried into powder; however, considering other processing options to improve the economic value such by-product, whey could be utilized, for example, in the production of whey protein concentrate (WPC) and whey protein isolate (WPI), fractionation of certain protein components, such as isolation and purification α-lactalbumin (α-la) including specific peptides. However, it requires rather expensive equipment and large financial investments. Huge volumes of whey can be processed into bioethanol. But for small and medium volume of whey it is most economical and simpler to produce whey-based beverages, whether fermented or unfermented.

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8.1.3  Whey Beverages As previously highlighted, the production of beverages appears to be the most economical solution for whey utilization in human nutrition. The need for development of whey-based beverages relies on the nutritional and functional properties of whey proteins, as well as on expectations of modern consumers who demand innovative products with enhanced functionality (Chavan et al., 2015b). The production of the beverage called Rivella in the 1970s in Switzerland belongs to one of the first attempts of placing whey-based beverages on the market. Up to now, numerous research studies focused on investigating whey beverage production from native sweet or acid whey, or from processed whey-like powdered, deproteinated, or diluted (Jeličić et  al., 2008). More recently alternative food processing methods such as membrane processes, high-intensity ultrasound, or supercritical carbon dioxide technology are being investigated for implementation in whey processing. By applying novel, nonthermal processing method problems such as microbiological instability, sediment formation, or whey protein denaturation are trying to be overwhelmed but also to improve the properties of existing products (Jeličić et  al., 2012; Barukčić et al., 2015a, b; Smithers, 2015; Amaral et al., 2018). Over the past two decades numerous whey-based beverages and similar products containing isolated whey components (mainly whey proteins) were placed on the market as refreshing, value added, and/or functional foods (Chavan et  al., 2015b). Despite the applied processing technology, whey beverages can generally be divided into two main groups—nonalcoholic and alcoholic beverages.

8.1.3.1  Nonalcoholic Whey Beverages This group comprises a large number of various whey beverages usually classified as: (a) mixtures of whey with fruit or vegetable extracts, grains, spices, seeds, and similar ingredients (b) fermented, yogurt-like beverages (c) refreshing beverages with the addition of carbon dioxide (Jeličić et al., 2008; Darade and Ghodake, 2012). Over the past 25–30 years a large number of studies focused on researching the production possibilities of beverages obtained by mixing whey with nondairy components such as fruit or vegetable extracts, grains, seeds, aromatic compounds like vanilla extract, cocoa powder, etc. The most economical solution for designing such beverages was proved to be using native, unprocessed sweet or acid whey as a basis, although recently it has also been suggested to use deproteinized whey or permeate remaining after ultrafiltration of whey (Jeličić et al., 2008; Chavan et al., 2015b). Creating such beverage

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would fulfill the idea of producing beverage similar to fruit juice which could be consumed as a breakfast-type or snack-type beverage or a nutritionally enriched drink which is in the first line a valuable source of vitamins and minerals. Considering the general findings up to now, the addition of citrus and tropical fruits to whey appeared to be most appreciated due to the effective covering of undesirable sour salty taste and the odor of cooked milk (Đurić et  al., 2004). The addition of orange juice to whey belongs to one of the most commonly investigated combinations in creating whey-fruit juice beverages whereby adding CO2 was also frequently applied. In that manner Sady et  al. (2013) examined the production of whey-based beverage with orange juice addition and compared their properties, including shelf life, with the same beverage produced without whey. According to the obtained results, the beverage containing whey was characterized by higher contents of proteins, ash, glucose, lactose, and vitamin B, but contained less sucrose, fructose, and vitamin C. Also, no considerable difference was detected in the polyphenolic content and the sensory evaluation of color desirability. Pareek et  al. (2014) investigated the production of refreshing carbonated beverage constituted of orange juice and whey in different ratios (70:30, 60:40 and 50:50). The mixture consisting of 70% orange juice and 30% whey was most acceptable and was characterized by a general increase in nutrients in comparison to the standard orange juice. Similarly, Chatterjee et al. (2015) tested the production of refreshing and nutritionally enriched beverage made from concentrated whey and orange juice. According to the obtained results, the mixture of orange juice and concentrated whey in ratio 3:2 appeared to be the optimal formulation attributed by the best sensory properties. The shelf life at room temperature was determined to be 11 days, while it accounted up to 3 months at refrigerator temperatures. Kumar and Bangaraiah (2014) tested several formulations of orange juice and whey for sensory properties, chemical composition, and shelf life. Among all of the tested combinations, two formulations (70% whey and 30% orange juice; 65% whey and 35% orange juice) were characterized by the best sensory properties, while all of the test beverages showed a negligible microbial growth and potential to be stored up to 2 months at room temperatures without spoilage. Besides orange juice, many other fruits were also tested for use in whey beverage production. Chavan et  al. (2015a) investigated the production of whey-mango refreshing beverage by mixing whey powder, WPC, or fresh whey with mango pulp or mango powder. The obtained beverages were tested for chemical composition, sensory properties, and microbiological parameters. The obtained results demonstrated that acid whey, whey powder, and WPC could be successfully utilized for beverage production. During the storage of the tested whey-mango juices there was a significant increase in the acidity in all samples.

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The beverage made from WPC and mango powder showed good overall acceptability after 30 days of storage at refrigeration temperature. Interesting findings were published by Baccouche et  al. (2013) who investigated the addition of prickly pear juice to acid whey. According to the obtained results the beverages were physically stabilized by adding sugar and pectin to the heat-treated whey. Very often red fruits were suggested for the addition of whey beverage preparation. Valadao et  al. (2016) examined the possibilities of utilizing Ricotta cheese whey in sports drink production and found that tangerine, passion fruit, and strawberry-passion fruit recipes achieved the best sensory scores. Jaworska et  al. (2011) studied the addition of blackcurrant to acid whey and compared the characteristics between pure blackcurrant juice and whey-blackcurrant beverage. They found that blackcurrant-whey beverage was characterized by higher amounts of ash, proteins, and vitamin B2 while pure blackcurrant juice showed somewhat higher antioxidant activity and received higher score at sensory evaluation. Janiaski et al. (2016) analyzed strawberry flavored fermented and nonfermented whey beverages. According to the obtained results, nonfermented whey-strawberry beverages were less liked since they were recognized as not enough acidic and viscous, with a more intense artificial strawberry aroma. Many authors have studied the addition of herbs or similar species in order to design a novel type of whey-based beverages. Yadav et al. (2010) studied the production of whey beverage enriched by banana juice and addition of Mentha arvensis extract. The optimal addition of Mentha extract appeared to be up to maximum of 2%, while the shelf life was determined to be 15 days. Some authors suggested the addition of exotic fruits such as guava. Singh et al. (2014) investigated the production of whey-guava beverage consisting of approximately 68% whey and 20% guava pulp, which was pasteurized at different temperature/time regimes and was cool stored for 90 days. According to the obtained results the best beverage in terms of overall quality appeared to be the one pasteurized at 65°C/25 min and cool stored for 45 days. Yonis et  al. (2014) studied the production of nutritious beverages consisting of whey and guava juice in different ratios where at chemical, microbiological, and sensory properties of each beverage type were analyzed. The most appropriate beverage appeared to be the one prepared by mixing 75% whey and 25% guava juice. Jain et al. (2013) examined the production of a refreshing whey-based beverage fortified with barley extract and green tea. According to the obtained results, a recipe implying beverage preparation by mixing whey and green tea/barely water in ratio 30:70 was the most appropriate one. Besides fruits, there are numerous possibilities how to enrich whey by adding cereals, bran, chocolate, cocoa powder, vanilla extract, etc. Dietetic beverages, beverages with hydrolyzed lactose, milk-like

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beverages, and powdered whey drinks also belong to the category of nonalcoholic whey beverages. The production of milk-like beverages relies on mixing liquid or powdered whey with milk, buttermilk, selected vegetable oils, and additives intended for improving consistency and stability of the prepared drink. Way-Mil is one of the most popular drinks belonging to this category. It has a very similar appearance to milk, specific taste and can contain components such as chocolate or fruits. Way-Mil consists of approximately 2%–4% milk fat, 1%–1.5% proteins, 4%–5% lactose, and 0.7% minerals and water soluble vitamins (Popović-Vranješ and Vujičić, 1997; Chavan et  al., 2015b). Powdered whey beverages must be characterized by good instant properties and a long shelf life. Compared to liquid beverages, powdered products are much easier to handle, especially considering transport and storage. Such features are very important in the nourishment of population suffering under hard surviving conditions and lack of protein sources. Whey powder drinks are usually prepared by mixing whey with soy, powdered fruits, concentrated fruit juices, or WPCs. They can also be fortified with vitamins, minerals, and aroma compounds like vanilla, strawberry, or chocolate. It is very important to adjust the whey composition before dehydration, while the process of mixing powdered whey with other components depends on the type of add-ins. For instance, if liquid concentrated fruit juice is being added, powdered whey must be previously reconstituted in water. When adding crystallized fruit juices or powdered fruit bases, there is no need for prior whey reconstitution (Jeličić et al., 2008). However, the formation of undesirable sediment, salty sour taste, and odor of cooked milk still remain the main difficulties which need to be overcome when considering whey beverage processing. On the one hand, adding sufficient amounts of fruit base are of crucial importance for reaching desired taste and odor, but on the other hand certain components of the fruit dry matter tend to precipitate and adversely influence beverage appearance. The use of hydrocolloids, CO2, metal gluconate, citric acid, etc. is only some of the proposed solutions on the way of overwhelming the above-mentioned difficulties during whey processing into beverages.

8.1.3.2  Fermented Whey Beverages Fermentation is one of the oldest ways of food preservation. Fermented beverages have been recognized by consumers all over the world for their therapeutic value. Thus, there is an ongoing trend in developing new types of such products whereby whey was also identified as a potentially good raw material. Due to the fact that almost 70% of lactose contained in starting milk ends up in whey remaining after cheese production (Jeličić et al., 2008), fermentation to yogurt-like drinks appears to be logical and meaningful way of whey

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utilization. Since fermentation process implies the decrease in pH due to the transformation of lactose to lactic acid, sweet whey is a better choice for fermented beverage production. Whey fermentations are usually performed by a starter culture which is able to metabolize lactose and often probiotic cultures of lactic acid bacteria are used. Many studies have focused on whey fermentation by strains such as Lactobacillus acidophilus, Lactobacillus delbrueckii ssp. bulgaricus, Streptococcus thermophilus, Lactobacillus reuteri, Bifidobacterium bifidum, Lactobacillus rhamnosus, Propionibacterium freudenreichii ssp. shermanii, Lactobacillus casei, Lactobacillus plantarum, Lactobacillus helveticus, Enterococcus faecium, Bifidobacterium animalis ssp. lactis, and Lactobacillus paracasei (Jeličić et al., 2008; Chavan et al., 2015b). That way fermented whey beverage with desirable nutritive properties is produced, without the implementation of complex and expensive technologies like ultrafiltration or evaporation which are usually employed in processing WPIs or concentrates or powdered whey to beverages. Gallardo-Escamilla et  al. (2007) indicated that whey fermentation by yogurt culture (Lb. delbrueckii ssp. bulgaricus and S. thermophilus) results in a more intense yogurt flavor in comparison to the one obtained by skim milk yogurt fermentation. Sohrabi et  al. (2016) studied the production of whey beverage fermented by commercially available yogurt culture DELVO®-YOG TY-17A. For the purposes of beverage production, WPC was reconstituted and enriched by adding vitamin E prior to pasteurization and fermentation. At the same time, identical beverage was produced but without fermentation. Both of the produced drinks were subjected to chemical, microbiological, and sensory analyses. While there was no considerable difference in the nutritional properties, fermented beverage achieved significantly higher overall acceptability and sensory scores. Thus it might be possible to produce beverages from whey with similar sensory profiles to those of fermented milk drinks or with some flavor attributes of drinking yogurt, following manufacturing procedures conventionally used for milk (Jeličić et al., 2008). Over the past three decades probiotic bacteria have been proved to exert numerous health promoting effects like lowering cholesterol level in blood, improving lactose metabolism, lowering blood pressure, resistance to enteric pathogens, anticarcinogenic properties, and immune system stimulation (Shah, 2007). Therefore, it is not surprising that probiotic whey beverages are considered as one of the target segments of development on the way of whey utilization to minimally processed functional products with added value (Marsh et  al., 2014). One of the most important factors is the chosen probiotic strain since it determines the unique flavor and texture of the fermented beverage. Among the examined strains, Lb. rhamnosus was frequently used, but since it lacks on enzyme β-­galactosidase, it does not have the ability

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to metabolize lactose. Therefore, it is necessary to hydrolyze lactose prior to the fermentation process or to use a proper coculture. Finnish dairy producer Valio developed Gefilus—a whey beverage fermented by Lb. rhamnosus GG. As a starting raw material demineralized whey or WPCs subjected to prior lactose hydrolysis are used. Gefilus is mostly being flavored by addition of fruit juices or fruit aromas and fructose as sweetening agent (Tratnik and Božanić, 2012). Pescuma et al. (2010) studied the fermentation of WPC by the selected strains Lb. acidophilus CRL 636, Lb. delbrueckii subsp. bulgaricus CRL 656, and S. thermophilus CRL 804, as single or mixed (SLaB) cultures. Fermented whey was then mixed with peach juice and calcium lactate and stored for 28 days at 10°C. According to the obtained results, mixed cultures and S. thermophilus CRL 804 used as a single culture showed a good surviving potential during the examined storage period. Also, all of the tested strains degraded β-lactoglobulin in a range of 41%–85% after 12 h incubation, which is of a great importance since β-LgB is one of the major milk allergens. In conclusion, by choosing a proper starter culture, whey can be utilized for the production of functional fermented beverages with improved characteristics such as the reduced β-LgB content. Faisal et al. (2017) investigated the production of probiotic fermented whey beverage enriched with orange powder. Beverages were produced from the fresh Cheddar cheese whey supplemented by orange juice powder and orange flavor and fermented at 42°C by a combined thermophilic probiotic culture consisting of following strains: L. acidophilus La-5, Lb. delbrueckii subsp. ­bulgaricus, S. thermophilus, and Bifidobacterium sp. BB-12. The best-ranked beverage followed consisted of 1 L cheese whey, 0.70 g stabilizer, 8% sugar, 1% orange powder and 0.40 mL flavor. The authors concluded that the incorporation of orange flavor and sugar into whey fermented with probiotic culture might be a successful pattern for utilizing cheddar cheese whey into organoleptically acceptable beverages. Koc et  al. (2013) fermented whey by probiotic strains. Lb. plantarum, L. brevis, and a combined culture Lb. plantarum + Lb. brevis, respectively. Fermented whey was then enriched by the addition of different fruit concentrates (lemon, mango, pineapple, apple, grape) and sucrose in order to mask a bitter flavor and achieve acceptable sensory attributes. According to the obtained results, beverage inoculated with Lb. plantarum and enriched by pineapple concentrate was most preferred. Seyhan et al. (2016) studied the production of fermented whey beverages from whey powder fortified with soy isoflavones or phytosterols and inoculated by probiotic strains L. acidophilus La-5 or Lb. casei LBC-81, respectively. The addition of nutraceuticals did not change the basic composition of the produced beverages, but the results of sensory evaluation indicated that ­phytosterols-fortified beverages were significantly more acceptable

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and thus would be recommending for an industrial scale production. Skryplonek and Jasińska, 2015 examined the potential of acid whey to be utilized in fermented drink production. Acid whey was inoculated with probiotic strains Lb. acidophilus La-5 and B. animalis spp. l­actis BB-12 were supplemented with buttermilk powder or sweet whey powder. The obtained results showed that acid whey could also be used as a raw material to manufacture probiotic-fermented beverages and could also provide sufficient levels of bacteria required to ensure health benefits to consumers. To improve the growth of applied probiotic strains, prebiotics such as oligofructose or inulin have also been successfully incorporated into fermented whey beverages (Marsh et  al., 2014). Matijević et  al. (2009) investigated the effect of lactulose on growth and survival of probiotic strains Lb. acidophilus La-5 and B. animalis subsp. lactis BB-12 in reconstituted whey. The obtained results showed that lactulose—well-defined prebiotic did not considerably affect the fermentation and survival of tested strains in whey, regardless of the added amount. Schlabitz et al. (2015) studied the shelf life of probiotic fermented beverages produced from different mixtures of whey and powder milk. The beverages were produced by inoculation with probiotic strains Lb. acidophilus LA-5, B. animalis spp. lactis BB-12, and S. thermophilus, and were fortified with the addition of prebiotics, strawberry pulp, and strawberry flavor. That way 11 formulations were developed and were submitted to chemical, microbiological, and sensory analysis. The obtained results demonstrated the possibility of preparing a prebiotic and probiotic fermented dairy beverage consisting of 70% ricotta cheese whey. Yasmin et al. (2015) highlighted the importance of fermented whey beverages supplementation with probiotics by proving their hypocholesterolemic effect in rats. Recently, some studies focused on the production of kefir-like whey beverages. Pereira et  al. (2015) studied the fermentation of WPCs ultrafiltration by kefir grains and/or selected probiotic strains. The fermented drinks showed acceptable physicochemical and sensorial properties, and contained satisfying levels of microorganisms after 14 days of refrigerated storage, which was in agreement with the standards required by international organizations like European Food Safety Authority (EFSA) and Food and Drug Administration (FDA) for products containing probiotics. Magalhães et al. (2011) compared kefir produced from milk to the one produced from whey by using kefir grains. Lactose hydrolysis, ethanol production, and the formation of organic acids and volatile compounds were determined during whey and deproteinized whey fermentation by kefir grains and were compared to values obtained during the production of traditional milk kefir. The obtained results indicated that kefir grains utilized lactose from whey and deproteinized whey and produced similar amounts

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of ethanol, lactic acid, and acetic acid to those obtained during milk fermentation. Thus, it could be concluded that whey was a valuable substrate for the production of kefir-like beverages. Nonetheless, liquid whey has a low total solid content (6%–7%) which results in poor and watery mouthfeel of fermented whey beverages in comparison to fermented milk. Consequently, it is necessary either to use exopolysaccharide-producing probiotic strains or to add hydrocolloids in relatively low amounts in order to enhance viscosity of the product and prevent sedimentation of dispersed particles. In fact, it is very important that added hydrocolloids do not mask natural flavor of the product and that they are effective at the typical product pH range, that is, 4.0–4.6. Thus, the choice of adequate hydrocolloid is one of the most important factors in the manufacture of fermented dairy products. Carboxymethyl cellulose (CMC), pectin, alginate, and xanthan gum (XG) are suitable for use in fermented whey beverages since their addition significantly enhances mouth feel of the end product (Gallardo-Escamilla et al., 2007; Jeličić et al., 2008).

8.1.3.3  Alcoholic Whey Beverages With lactose being the main constituent (70%) of the dry matter, whey is also a very good substrate for ethanol production. Consequently, the production of an alcoholic whey beverage is an alternative of great interest for the utilization of this industrial by-product. Various research efforts have been done on this theme, and yeasts like Kluyveromyces fragilis, Kluyveromyces marxianus, and Saccharomyces lactis were proposed as suitable biocatalysts for this bioprocess (Dragone et  al., 2009). Alcoholic whey beverages relate to the production of beverages with a low alcohol content (≤1.5%), whey beer and whey wine. The production of whey beverages with a low alcohol content includes process stages like removal of proteins and concentration, lactose fermentation, or addition of sucrose until reaching the desired alcohol content (0.5%–1%), flavoring, sweetening, and bottling. Certain amount of lactose is transformed to lactic acid which gives a refreshing and sour taste to the end product, while the rest ferments to alcohol (Jeličić et al., 2008). There are some records of utilizing whey for the production of alcoholic beverages in Poland. For example, Milone was a beverage obtained by whey fermentation with kefir culture and Serwovit was a whey sparkling wine also produced in Poland (Popović-Vranješ and Vujičić, 1997). Dragone et al. (2009) studied volatile compounds in alcoholic beverage produced from whey and concluded that cheese whey continuous fermentation with K. marxianus could be used for the production of a new spirit that is organoleptically acceptable. Whey beer can be produced with or without the addition of malt and can be fortified with minerals or can contain starch hydrolysates

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or vitamins. Some of problems that can occur during whey beer production are the presence of residual milk fat which can cause loss of beer foam. Due to poor solubility of whey proteins, undesirable odor and taste may occur while many strains of yeasts commonly used in beer production do not ferment lactose. Despite that whey beer production appears more attractive. In 2016, Belvoir Brewery located in Old Daly, UK, released an innovative flavored whey beer called Blue Brew, which is being produced by from whey remaining after Stilton cheese production (Arla Foods, 2016). Whey wine contains relatively a low alcohol amount (10%–11%) and is mostly flavored with fruit aromas. The production of whey wine includes clearing, protein removal, lactose hydrolysis by β-galactosidase, decanting and cooling, addition of yeasts and fermentation, decanting, aging, filtering, and bottling (Popović-Vranješ and Vujičić, 1997). Regarding everything mentioned above, there are numerous possibilities to prepare whey-based beverage, but the ideal recipe has not been found yet. Despite scientific evidence, processing whey to alcoholic beverages did not sustain at larger scale. Nevertheless, whey is a too valuable source of nutrients to be given up from trying to utilize it in the food industry.

8.1.4 Application of Nonthermal Processing Methods in Whey Beverages Production When designing whey-based beverages several problems were identified which refer to adverse phenomena like the lactose crystallization during cool storage, whey protein denaturation and sedimentation due to thermal processing, the shorter shelf life at room temperatures, poor mouthfeel, or appearance of the undesired salty sour taste (Jeličić et al., 2008; Chavan et al., 2015b). Nowadays lots of efforts have been put into optimizing application of novel nonthermal processing methods into whey processing. In order to partially or entirely prevent the occurrence of those, different attempts were made including for example the application of membrane processes or whey treatment by high-intensity ultrasound. Barukčić et al. (2014, 2015a) examined the possibility of processing sweet native whey by microfiltration and ultrafiltration in order to achieve adequate microbiological stability without whey protein denaturation and sediment formation. Promising results were obtained by applying a combined process consisting of microfiltration by a 0.5 μm membrane and a subsequent ultrafiltration by a 0.2 kDa membrane. Both of the used membranes were ceramic and the process was performed at 20°C. That way optimal microbiological quality was obtained and the nutritional quality was almost completely preserved meaning the whey proteins were maintained in native state. Such findings were better in comparison

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to those achieved by the usually applied pasteurization at 73°C/20 s which opened new possibilities of producing minimally processed whey-based beverage of excellent nutritional quality. Ultrafiltration or reverse osmosis allows whey concentration and could solve the problem of the poor mouthfeel inherent to whey beverages (Barukčić, 2013). Accordingly, Dilipkumar and Yashi (2014) investigated a production of refreshing fruit beverage using the native, pre-filtered, and ultrafiltered (UF) acid whey as basis. Thereby, the addition of mango, pineapple, and orange juice in different amounts (18%, 20%, 22%, 24%) was tested. According to the obtained results best properties and overall acceptability among consumers was recorded for the beverage consisting of UF whey basis enriched by the addition of 22% of pineapple juice and carbonated. Since the implementation of membrane processes eludes great nominal financial expenses, they are mainly used for the production of highly appreciated and more cost-effective products such as WPCs or isolates. In order to establish a production process with no waste products, many authors have proposed the utilization of the remaining UF permeate. Beucler (2004) investigated the utilization of whey permeate for the production of carbonated beverage enriched by the addition of different flavors and vitamins. According to the obtained results, whey permeate could be successfully incorporated in carbonated thirst-quenching beverages. Amaral et al. (2018) investigated the application of supercritical carbon dioxide for application as alternative technology to thermal processing during whey-grape juice. They found no differences in juice characteristics (acidity, total solids, antioxidative activity) processed by conventional heat treatment and by the supercritical carbon dioxide technology which, thus, proved to be a promising new processing technology. High-intensity ultrasound was also investigated for the purposes of preventing sediment formation or reducing its amount, for improving the fermentation process or for partial substitution of pasteurization (Jeličić et al., 2012; Barukčić et al., 2015b). Barukčić et al. (2015b) investigated the influence of high-power ultrasound application on the quality and on the fermentation process of reconstituted sweet whey. In the first stage of the study, whey was treated with different power inputs (480 and 600 W) during 6.5, 8, and 10 min at moderate temperatures (45°C and 55°C) which were maintained constant for the whole period of treatment. Subsequently, the treated whey samples were analyzed for microbiological quality, physical properties (particle size distribution, electrical conductivity, viscosity), chemical parameters (protein content, acidity), and sensory properties. All of the determined parameters were compared to the control sample (pasteurized) and to fresh whey. Treatments by nominal power of 480 W for 10 min at 55°C resulted in better microbiological quality and sensory properties in comparison to whey pasteurization. Hereafter, the influence of

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high-intensity ­ultrasound on whey fermentation with yogurt culture YC-380 and with monoculture Lb. acidophilus La-5 (both Christian Hansen, Hersholm, Denmark) was investigated. Different ultrasound treatments were applied for activating starter culture before or after the inoculation, and treatment with nominal input power of 84 W over 150 s was selected as the best one in terms of increasing the viable count of starter culture cells. Jeličić et al. (2012) studied the application of a combination of high-intensity ultrasound with nominal inlet power of 400 W with moderate heat (55°C) in whey processing. The applied treatment resulted in a better reduction of total bacteria, coliform bacteria, and yeasts and molds number in comparison to conventional pasteurization process. Also, sensory properties were improved regarding mouth feel, the absence of sediment, and unchanged color in all of the ultrasound-treated whey samples. Thus, along with the development of new processing technologies whey utilization could be improved too. There are numerous scientific studies that have proven not only the feasibility but also the importance of producing whey-based beverages and similar products, not only for resolving the question of this environmental pollution, but also for their outstanding nutritional value.

8.1.5 Nutritional and Therapeutic Value of Whey and Whey-Based Beverages Whey-based beverages target a large scale of consumers—from old people to little children. Because of its health benefits, since the time of Ancient Greece whey was used to treat illnesses such as tuberculosis, skin, and digestive tract diseases. In the 18th century in countries like Switzerland, Germany, and Austria specialized institutions were built for curing illnesses with whey treatments. That designated the start of studies focused on the nutritional and therapeutic properties of whey. Whey was successfully applied for treatments of diarrhea, bile illness, scales in the urinary tract, gonorrhea, arthritis, anemia, liver complaints, and certain intoxications. (Darade and Ghodake, 2012). From the nutritional point of view, whey protein fractions are most valuable proteins since they contain a high concentration of essential amino acids (especially lysine, cysteine, and methionine) and a high concentration of cysteine. The utilization of proteins in the body is closely related to the ratio of cysteine/methionine, which is about 10 times higher in whey proteins than in casein. Thermally denatured α-lactalbumin is almost completely absorbed in the human digestive system, which is considerably higher than the digestion rate of casein (75%). Regarding all of the above mentioned, whey proteins have a higher biological value in comparison to casein and other proteins of animal origin, including egg (Jeličić et al., 2008).

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Whey proteins are also a rich source of branched chain aminoacids (BCAAs) such as isoleucine, leucine, and valine. BCAAs unlike other essential aminoacids are metabolized directly into the muscle tissue and are first amino acids used during periods of exercise and resistance trainings (Sherwood and Jenkins, 2007). Thus, whey proteins could be regarded as especially effective in stimulating muscle protein synthesis rates due to high contents of essential amino acids and the almost identical amino acid profile to that of skeletal muscle (Chavan et al., 2015b). Daily requirements for the most essential amino acids may be obtained by consuming approximately 1.5 L of whey or 0.5 L of milk (Tratnik and Božanić, 2012). In conclusion, whey-based beverages are excellent not only for rehydration but also for improving lean body mass in athletes. Whey protein fractions also include lactoferrin—an iron-binding protein so that whey beverages can be used as functional food intended to improve iron absorption from food and/or help to keep pathogens from attaching to the intestinal walls. Whey also contains GMP which derives after cheese making using rennet and is naturally free of phenylalanine A drink with addition of GMP isolate would be a very good source of energy and micronutrients for those suffering from phenylketonuria (Miller, 2005). Alpha-lactalbumin is one of major whey proteins and is a calcium-binding protein, which is very important for nutrition of little children and infants (Lisak Jakopović et al., 2016). Thus, whey-based beverages may improve the absorption of calcium which is determinal for bone health in elderly women often suffering from osteoporosis. Whey and whey-based beverages can also serve as a pool of bioactive peptides. Bioactive peptides have been defined as specific protein fragments that have a positive impact on body functions or conditions and may ultimately influence health. On oral administration, bioactive peptides may affect the major body systems—namely, the cardiovascular, digestive, immune, and nervous systems. The beneficial health effects may be classified as antimicrobial, antioxidative, antithrombotic, antihypertensive, antimicrobial, or immunomodulatory. The following peptides were identified in the β-lactoglobulin sequences: β-lactorfin which influences the smooth muscles, β-lactotensin which exhibits hypocholesterolemic and anti-stress activities, and in the α-lactalbumin sequences: α-lactorfin which displays effects similar to that of morphine, namely blood pressure reduction (Krolczyk et al., 2016). Very important roles, such as antiulcerative, anti-appetizing or mineral binding, have been identified for bioactive peptides originating from whey protein hydrolysis and influencing gastrointestinal system (Brandelli et  al., 2015). For instance, Zafar et  al. (2013) conducted a clinical trial in which young normal-weight and overweight

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females were given sweetened beverages supplemented with whey proteins. Out of all obtained results it could be concluded that whey protein-sweetened beverages attenuated blood glucose and appetite in both normal-weight and overweight females and reduced energy intake in normal-weight females. Beverages based on whey permeate remaining after ultrafiltration and fortified with rice, oat bran, or with isolates of soy and potato proteins are optimal for people allergic to milk proteins or suffering from celiac disease. Many clinical studies have proved the antihypertensive effect of whey beverages. They are also being used as meal replacement for people suffering from overweight problems, older population, and athletes or as a healthy alternative to fast food. Food market studies have shown that fermented and/or fruit whey beverages are mainly consumed by health conscious women, children, and working people who consume those beverages for breakfast or as a snack (Miller, 2005; Huth et al., 2006). These are only some of possible uses of whey-based beverages, but depending on the production technology, there is a much wider range of applications. Therapeutic and health-promoting properties of whey were accented already 460 B.C. by Hippocrates—father of modern medicine. It seems that time has come when a modern man has also realized the importance of using whey in everyday nutrition.

8.2 Buttermilk The definition of buttermilk is different from the country to country. Buttermilk is sometimes associated or even confused with sour milk, natural (conventional) buttermilk, cultured milk, cultured buttermilk, and cultured skim milk or even sometimes with fermented milk. Buttermilk is a liquid that releases during the churning of cream in a butter production. Buttermilk contains water-soluble components like milk protein, lactose, and minerals. In addition, what is specific for buttermilk, it encloses material that derives from milk fat globule membrane (MFGM) and is disrupted during the churning process and mainly passes in to the buttermilk fraction. Because of the presence of MFGM material, buttermilk contains more phospholipids than milk. Phospholipids in buttermilk constitute about one-third of the MFGM dry matter. Literature quotes that buttermilk has seven times more phospholipids than whole milk and their concentrations are 0.89 mg/g in buttermilk and 0.12 mg/g in whole milk (Libudzisz and Stepaniak, 2002). This high content of phospholipids in buttermilk makes it interesting dairy ingredient as a functional component in food industry because they have very good emulsifying properties (Wong and Kitts, 2003). Phospholipids have shown some bioactivity. Some studies have demonstrated the anticarcinogenic potential of phospholipids,

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e­ specially against colon cancer, and their protective effect against bacterial toxins and infection (Libudzisz and Stepaniak, 2002). Besides the buttermilk, a by-product of the milk industry is butter serum. Butter serum is the aqueous phase obtained after melting and centrifugation of butter in the production process of anhydrous milk fat (AMF). AMF consists of a 99.9% pure milk fat product with specific techno-functional properties like high resistance to heat and mechanical treatments (Vanderghem et  al., 2010). The large production of butter and AMF worldwide (10 million tons of butter and AMF in 2013) consequently results in a large production of buttermilks and butter serums which are mainly mixed together (with a higher proportion of buttermilk due to a higher production of butter) and spray dried into powder for animal feed (Lambert et al., 2016). In terms of composition, buttermilk and butter serum are similar to skimmed milk when focusing on proteins, ashes, and lactose content (Vanderghem et  al., 2010). However, they largely differ in terms of lipid fractions. Buttermilk contains about 4.6%–14.5% fat in a dray matter, and butter serum contains about and 24% fat in a dry matter (Lambert et al., 2016). Buttermilk is most commonly used in the baking industry (39%), followed by powder industry for preparing dry mixes (33%), and for the dairy industry (23%). Baking industry uses buttermilk for improving flavor and texture of bakery products. Other food industries use buttermilk as a functional ingredient for various foods, such as sauces, chips, and chocolate products. In the dairy industry, buttermilk is used in cheese making in the formulation of ice cream or yogurt, or in the manufacture of recombined milks and nowadays, it is widely used for buttermilk-based beverages. Libudzisz and Stepaniak (2002) reported about the functionality of buttermilk and ability of buttermilk to increase the heat stability of recombined milks. The main reason that buttermilk acts as a heat stabilizer is because of the phospholipid-protein interactions which prevents protein coagulation during thermal processes. In addition, they reported about the addition of buttermilk in the manufacture of low-fat Cheddar, and their results implied that addition of buttermilk can improve the texture of the cheese because phospholipids possess a high water-holding capacity. Thanks to the phospholipids buttermilk possess great emulsifying properties for wide use in food industry. Foaming capacity in buttermilk is lower than in skim milk (Wong and Kitts, 2003) due to the antifoaming properties of the phospholipids when they are combined with proteins. Heat treatment of cream in butter production damages functionality of buttermilk, because during the heat treatment, whey protein denaturation occurs and they interact with MFGM (Libudzisz and Stepaniak, 2002). Flow diagram in Fig.  8.1

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Milk

Cheese production

Separation and cream standardization

Whey

Raw cream∼ 40% milk fat

Whey butter

Pasteurization, 85–95°C/10–30 s

Maturation, 6–8°C

Whey buttermilk

Maturation of cream with addition of Mesophilic culture, 18–22°C/12– 20 h

Churning Churning Sweet cream buttermilk

Mesophilic culture

Sour buttermilk

Addition of citrate, milk, buttermilk or whey powder, pasteurization, cooling

Fermentation

Breaking, cooling

Fermented buttermilk

Fig. 8.1  Flow diagram of the production of sweet, fermented, sour, and whey buttermilk.

shows types of buttermilk that have been revived in this chapter, from milk through butter production. Most of the work on buttermilk-based beverages has been done with sweet buttermilk. Sweet buttermilk is the major source of commercial buttermilk. Buttermilk types can be produced from milk fat. Usually sour buttermilk forms during churning of cultured cream, in

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the production process of European-style butter or fermented sweet buttermilk. This kind of buttermilk is often called conventional buttermilk. In addition, whey buttermilk, from churning of whey cream, in manufacture of whey butter can be produced (Fig.  8.1). Production of whey buttermilk is present in a smaller quantities than that of sweet buttermilk (Sodini et al., 2006). Since large volume of whey generates after cheese production there is a potential market for whey buttermilk production. Average fat content in whey is 0.13% and 57,000 tons of liquid whey buttermilk can be produced in the United States every year, thus mentioned amount of whey buttermilk presents 10% of the current production of sweet buttermilk (Libudzisz and Stepaniak, 2002). In some countries (Russia, Poland, Czech Republic, Finland, Germany), naturally fermented buttermilk is merchandised as a beverage for consumption or sometimes used for animal feed. Problems with increasing the consumption of traditional buttermilk is its short shelf-life (about 1 week at 4–7°C), the difficulty in obtaining a uniform quality and the lack of promotion as a beverage. Therefore, without a special effort to commercialize natural buttermilk, consumption will decrease and it will be treated only as a regional drink (Sodini et al., 2006). Table 8.3 presents gross composition (%) of different types of buttermilk on a dry matter basis. Sodini et  al. (2006) in their research determined gross composition of sweet and sour cream buttermilk as well as whey buttermilk. According to their results, sweet cream buttermilk has the highest content of total nitrogen (31.5%) and the lowest content of fat (13.1%). Whey buttermilk has the highest content of phospholipids and lactose. The lowest amount of nitrogen in whey buttermilk can be explained because of the lack of casein in whey cream since the casein lagged in cheese production. In addition, the lactose content in whey buttermilk was the highest probably because in cheese production most of the lactose from milk passes to whey (Tratnik and Božanić, 2012).

8.2.1  Sweet Buttermilk Traditionally, buttermilk is the fresh serum that was separated during butter production on farms after churning cream ripened with naturally occurring lactic acid bacteria. Sometimes, it contained small flakes of butter. Under industrial conditions, buttermilk is a by-product in butter production. Depending on the processing conditions, either sour cream or sweet cream buttermilk is obtained. Sweet buttermilk is obtained from the sweet (raw) cream. Sweet buttermilk can be further processed to fermented buttermilk by mesophilic lactic acid bacteria. The chemical composition of sweet buttermilk depends on the

230  Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages

Table 8.3  Gross Composition (%) of Different Types of Buttermilk on a Dry Matter Basis (Sodini et al., 2006) Sample

Total Nitrogen

Fat

Phospholipids

Ash

Lactose

pH

Sweet cream buttermilk Sour cream buttermilk Whey buttermilk

31.5 27.8 14.1

13.1 22.3 15.5

1.27 1.15 1.87

6.7 6.2 7.0

48.7 43.7 63.4

6.61 5.39 5.98

­ utter-making technology and season of the year but it is very similar b to skim milk to around 1% of milk fat. Besides proteins and lactose like in skim milk, buttermilk also contains proteins and phospholipids derived from MFGM (Sodini et al., 2006; Jiménez-Flores et al., 2009). Most of the times, sweet buttermilk is concentrated by evaporation, then spray dried and used in the food industry, mainly as an ingredient for breads, biscuits, pancakes, waffles, or cakes. In the United States, for example, it is generally used as an ingredient in ice cream and processed cheese foods. Buttermilk contributes unique flavor characteristics to chocolate (Sodini et al., 2006). Conventional sweet buttermilk may also provide additional emulsifier functionality in products like chocolate, reconstituted butter, cheese analogues, and cheese sauces. To overcome a problem of short shelf life of sweet buttermilk, attempts have been made to produce buttermilk-based beverages. At market worldwide, buttermilk-based beverages can be found with the addition of fruit or some functional ingredient or they can be even carbonated.

8.2.2 Fermented Buttermilk Sour buttermilk is a by-product in butter production from sour cream, or by fermentation of sweet buttermilk. The sweet buttermilk used for buttermilk production should be of the highest quality from the compositional and microbiological points of view. Because the amount of citric acid in milk is not constant and varies during the year, supplementation of milk with 0.1%–0.2% of citric acid or sodium citrate is recommended to obtain a sufficiently a high level of diacetyl by aroma-producing bacteria. Supplements that can be added, apart from citric acid or sodium citrate, are stabilizers (0.01%–0.02%), nutritive carbohydrate sweeteners, flavoring ingredients, skim milk, buttermilk, or whey powders (1.5%–2.0%), NaCl (0.1%), freeze-dried butter flakes or granules at a level of 0.002%. After incubation for 15–20 h, the coagulum at pH 4.6–4.7 (0.75%–0.85% titratable acidity) is broken by gentle agitation. Cooling and braking of buttermilk must be c­ oordinated.

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Commonly, cooling starts 15 min before breaking the buttermilk coagulum and after that the buttermilk is packed, cooled, and stored. Disruption of the gel can occur due to the production of CO2 by citric acid-fermenting bacteria, giving rise to the phenomenon of “curd floating.” The important sensory characteristics of buttermilk resulting from mesophilic fermentations are the typical consistency, which is due to the coagulation of milk proteins by lactic acid, and the aroma and flavor produced by the fermentation of citric acid and lactose. Fermented buttermilk is characterized by thick, smooth, and fairly viscous properties. The texture also depends on whether or not p ­ olysaccharide-producing strains are included in the starter culture and on the concentration of total solids (Libudzisz and Stepaniak, 2002).

8.2.2.1  Starter Cultures for Fermented Buttermilk Production Starter cultures for the production of fermented buttermilk are mesophilic lactic acid bacteria. Used cultures are those that contain strains of Lc. lactis subsp. lactis, Lc. lactis subsp. cremoris and L. ­mesenteroides subsp. cremoris (Wróblewska et al., 2016). The first two species produce mainly lactic acid and are often referred to as acid producers, in contrast to Leuconostoc spp., which ferment citric acid and produce important metabolites, such as CO2, acetaldehyde, and diacetyl which are referred to as aroma and flavor compounds (Tratnik and Božanić, 2012). The most important is the balance between obtained aroma and acid that strain produces. Wróblewska et al. (2016) reported in their research that not more than 20% of aroma-producing bacteria are recommended. Diacetyl, at a concentration of 2–5 mg/kg, is responsible for the characteristic “buttery” flavor and aroma. The citrate content in milk is highly dependent on its microbiological quality; for example, in summer, it is closely correlated with the level of contaminating bacteria, particularly with Enterobacter spp. and pseudomonads. Therefore, supplementation of milk with citrate or citric acid is often recommended. Another very important carbonyl-­flavoring compound produced by lactic acid bacteria in buttermilk is acetaldehyde. It is undesirable and if present in excess is responsible for the flavor defect described as “green” or “yogurt”-like. In starters for the production of buttermilk, in which acetaldehyde is undesirable, it is better to use L. mesenteroides subsp. cremoris rather than citric Lb. lactis subsp. lactis for flavor production. To obtain buttermilk with desirable organoleptic properties, the optimum ratio of diacetyl and acetaldehyde needs to be around 4:1 (Libudzisz and Stepaniak, 2002).

8.2.3  Whey Buttermilk Composition as well as functional properties of whey buttermilk is quite different from sweet or cultured buttermilk. Sweet or sour

232  Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages

­ uttermilk, according to their composition, can be compared with the b skim milk and whey buttermilk can be compared with whey, although whey buttermilk contains more milk fat. Buttermilk is often defined as plasma where fat globules are dispersed, hence follows linkage skim milk to sweet or cultured cream and whey to whey cream. In addition, functional properties of whey buttermilk are different from sweet and sour buttermilk. Whey buttermilk has higher emulsification properties and lower foaming ability than sweet or cultured buttermilk. Possible reason is that whey buttermilk has a higher ratio of phospholipids to protein. In addition, specifically for whey buttermilk is that in acid pH ranged from 4 to 6 had stable levels of protein solubility, emulsifying capacity, and viscosity. Sweet or cultured buttermilk compared with whey buttermilk showed lower solubility and emulsifying capacity, and a higher viscosity, also at acidic pH (pH < 5). Possible explanation is that sweet or cultured buttermilk contain more casein than whey buttermilk. Findings of Sodini et al. (2006) suggest that whey buttermilk could be an interesting and novel dairy ingredient, especially in the formulation of low-pH food.

8.2.4 Usage of Buttermilk Buttermilk is a dairy ingredient, used mostly in a powder form in the food industry because of its emulsifying capacity and its positive impact on flavor. Recent usage of buttermilk is in a form of beverages. Buttermilk-based beverages can be with a fruit addition, functional ingredient addition or carbonated beverages.

8.2.4.1  Fruit-Based Buttermilk Beverages Worlds market for beverages has increased for 31% in terms of sales and 26% in terms of volume since 1996 and modern standard of living and consumersʹ knowledge increased consumption of foods with biological and functional value. In addition, food with reduced fat content became very popular. Nowadays, innovative technologies, their implementation and also development, are focused in production of food products based on protein and carbohydrate dairy raw material for example from whey, skimmed milk, or buttermilk. Meshram, 2015assumes that this is a base and areas of priority for food industry enterprises and restaurants in the modern context. Concept of products based on proteins and carbohydrate dairy raw material is production of different milk beverages. Knowing these facts, Meshram (2015) developed a method for production of sweet buttermilk by optimizing conditions for the production of fruit-based buttermilk. Meshram also developed buttermilk beverages based on mango, orange, and banana juices. Composition of buttermilk beverage recipe varied concerning fruit type and thus juice content ranged from 10%

Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages   233

for mango to 35% for orange. The buttermilk content of the beverages ranged from 62% to 83%. Total solids, fat, and protein content in different fruit beverages varied from 11.3% to 18.3%, 0.12%–0.38%, and 0.25%–0.68%, respectively. Among the beverages that were developed mango buttermilk beverage, according to sensory panel, was the best graded. Composition of mango buttermilk beverage was 12% mango juice, 81% buttermilk, 7% sugar, 0.05% pectin, 0.12% CMC, and pH 4.25 (Meshram, 2015). Besides fruit beverages, buttermilk can be a functional ingredient in a milkshake production, since it offers a protein and carbohydrate components. Buttermilk is a great source of proteins with a high nutritional value. When buttermilk is produced, around 80%–90% of milk proteins pass to buttermilk, and also 0.4%–0.7% of milk fat, and a significant part of minerals and water-soluble vitamins. The main feature of buttermilk is the presence of phospholipids. Phospholipids decreases surface tension on “liquid-air” boundary and thus help to form foam at mechanical beating of buttermilk (Deynichenko et  al., 2014). Furthermore, Buddhadasa et  al. (2015) investigated the addition of fruit juices or pulps for the utilization of buttermilk beverages. Soursop (Annona muricata) is one of the fruit which can be incorporated to manufacture beverages with a good consumer demand. The fruit is rich in vitamin B, potassium, fructose, and vitamin C. Soursop fruit is a proven cancer remedy for all types of cancers and a broad spectrum antimicrobial agent for both bacterial and fungal infections, antiparasitic activity, lowers high blood pressure, and is used for depression and stress. According to their sensory results, addition of 13% soursop and 12% sugar had the best results for the production of fruit buttermilk beverages (Buddhadasa et  al., 2015). Bassi et al. (2012) evaluated three fermented milk beverages to which sugar and strawberry puree had been added post-fermentation. The base was composed of 70% of milk, with whey and buttermilk in the concentrations of 30% and 0%, 15% and 15%, and 0% and 30%, respectively. The starter culture developed well with all formulations reaching pH 4.7–4.9 in 180 min of fermentation. Lactic acid bacteria in the products were above 8 log cfu/mL throughout the study. They reported that obtained beverages had similar pH, acidity, and viscosity. Authors concluded that buttermilk and whey could be interesting ingredients for fermented milk beverages, because the consumers liked all the products equally (Bassi et al., 2012).

8.2.4.2  Carbonated Buttermilk Beverages By carbonating buttermilk beverages, the shelf life can be prolonged up to 30 days. Burhanuddin Shaikh and Dagdulal Rathi (2009) in their study stated that the process developed for the preparation of fruit-flavored carbonated buttermilk beverages was highly acceptable. According to sensory analysis, physicochemical and nutritional

234  Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages

parameters were all improved during this process. For beverage production, they use mango, pineapple, and orange fruit fresh juices. The fruit juices helped in improving sensory qualities such as appearance, color, taste, aroma, mouth feel, and overall acceptability, as well as nutritional aspects such as vitamin A, C, and calcium content. These results reveal that the process developed for the preparation of fruit-flavored carbonated buttermilk beverage was highly acceptable in terms of sensory and physicochemical qualities. The prepared products had higher acceptability than the market samples. The best combination, evaluated from the sensory panel, of fruit-flavored carbonated buttermilk beverages was prepared by the addition of 12% sugar and 24% pineapple juice, respectively (Burhanuddin Shaikh and Dagdulal Rathi, 2009).

8.2.4.3  Functional Buttermilk Beverages Functional foods are the products that resemble traditional foods but possessed physiological benefits due to the presence of some bioactive components. Milk and dairy products have been an important part of human diet from ancient times in many parts of world. For example, from ancient times in India, buttermilk was consumed at the end of the meal and the meal was considered incomplete without it. Therapeutic properties of buttermilk are well known. Buttermilk is similar in composition with skim milk but has more nutritious than skim milk. Buttermilk is a good source of calcium, phosphorus, vitamin B2, vitamin B12, pantothenic acid-vitamin B5, zinc, potassium, protein, iodine, and molybdenum (Mudgil and Barak, 2016). The presence of all these nutrients in buttermilk makes it a nutritious and health-­ supportive food. Buttermilk has been attributed nutraceutical, therapeutic, and probiotic effects, such as digestion enhancement, immune system boosting, anticarcinogenic activity, and reduction in serum cholesterol. Buttermilk, without addition of fruit, is deficient in iron, vitamin C and dietary fiber like milk and milk products. Buttermilk is considered a healthy food due to inherent nutritive value but is deficient in dietary fiber. Knowing this fact, Mudgil and Barak (2016) performed research where they enriched buttermilk with soluble fiber. They enriched buttermilk with partially hydrolyzed guar gum. Guar gum is a good source of soluble fiber. Enzymatic hydrolysis of native guar gum leads to the production of partially hydrolyzed guar gum, and in that form, human organisms can use it better. In addition, partially hydrolyzed guar gum is low-molecular-weight galactomannan having low viscosity, colorless, tasteless, odorless in nature and hence do not affect the product characteristics. Generally, guar gum is used as stabilizer and thickener in different foods such as tomato ketchup, ice cream, and beverages. Mudgil and Barak (2016) optimized buttermilk production with enrichment of 4% soluble fiber and improved

Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages   235

physicochemical and desirable sensory characteristics. Fiber fortification in buttermilk markedly reduced the phase separation which is a serious problem in reference to consumer acceptance. It is concluded that partially hydrolyzed guar gum can be used for the fiber fortification of buttermilk (Mudgil and Barak, 2016). Furthermore, Sheth and Hidryani, 2016reported about the development and sensory analysis of a buttermilk-based fermented drink using barley and fructooligosaccharide as functional ingredients. They performed experiments by cooking barley and fermenting it with buttermilk, followed by addition of FOS, flavors (rose, khus, chocolate and salt jeera), and colors. A panel of 24 semi-trained members evaluated the products for color and appearance, mouthfeel, texture, taste, after taste, and overall acceptability. Obtained results showed a significant difference among drinks with different flavors. Salt-jeera flavor was liked most by all the panel members followed by rose. No after taste or bad mouthfeel was reported in any of the products (Sheth and Hidryani, 2016).

8.2.5 Nutritional and Functional Value of Buttermilk The concentration of lactose in buttermilk varies from 3.5% to 4.9% in sour or fermented product and from 4.8% to 5.2% in sweet. The biological activities of mesophilic lactic acid bacteria can also be resulted in changes of the levels of vitamins in fermented buttermilks. The level of vitamins in buttermilk depends on the culture used and may be lower or higher than in sweet buttermilk (Table 8.4). The level of vitamins is also influenced by seasonal variations. During storage at 5°C, there are considerable losses of riboflavin, pyridoxine, folic acid, and vitamin B12, while biotin, thiamin, and pantothenic acid are stable (Libudzisz and Stepaniak, 2002). From the Table 8.4 it can be seen that there is no significant differences between vitamin content in various buttermilks compared to the milk. The noticeable difference is in pantothenic acid between sweet buttermilk and sour/fermented buttermilk and milk, where sweet buttermilk has 4 times less amount of pantothenic acid. During butter manufacture, milk fat globules are destabilized, and an aqueous by-product, buttermilk, containing milk-derived components as well as the MFGM is produced. When milk fat globules are disrupted during the churning of cream, the membrane covering the lipid core is excluded from the lipid matrix and is recovered in buttermilk along with most of the proteins, lactose, and minerals contained in the aqueous phase. The MFGM is particularly rich in various proteins and phospholipids which have outstanding potential for functional and nutraceutical applications related to the prevention or amelioration of widespread chronic diseases such as cancer, obesity, diabetes, and cardiovascular disorders (Conway et  al., 2013., Conway et  al., 2014).

236  Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages

Table 8.4  Comparison of Vitamin Content (μg/100 g) in Sweet, Sour and Fermented Buttermilk and Milk (Libudzisz and Stepaniak, 2002) Vitamin

Sweet Buttermilk

Sour and Fermented Buttermilk

Milk

Thiamin Riboflavin (vitamin B2) Pantothenic acid Vitamin B6 (pyridoxine) Niacin Biotin Vitamin B12 (cobalamin) Folic acid

12–34 48–202 44–68 32–96 44–68 No data No data No data

23–40 120–170 280–300 27–35 60–110 No data 0.0007–0.2 0.017

20–43 106–200 330–460 17–70 71–100 1.5–4.9 0.3–0.57 0.13-7.5

Buttermilk has received increased interest, as food science and nutrition research turns to develop products with not only increased nutritional value but also health-promoting properties. This by-product of butter-making can be a source of highly valuable functional ingredients, from both the technological and nutritional point of view. The MFGM is complex in composition as well as in its supramolecular structure. Buttermilk can be employed to isolate MFGM material and to prepare valuable ingredients (Zanabria Eyzaguirre and Corredig, 2011). Conway et  al. (2014) investigated the effects of buttermilk consumption on blood pressure and on markers of the renin-angiotensin-­ aldosterone (RAS) system in humans. Obtained results were promising. Buttermilk consumption significantly reduced systolic blood pressure (2.6 mm Hg), mean arterial blood pressure (1.7 mm Hg), and plasma levels of the angiotensin I-converting enzyme (10.9%) compared with the placebo, but had no effect on plasma concentrations of angiotensin II and aldosterone (Conway et al., 2014). Furthermore, Jiménez-Flores et al. (2009) reported that sphingomyelin could help in the prevention of colon cancer and that phosphatidylcholine could interfere with the development of hepatic diseases. Although the biochemical and physiological mechanisms leading to such benefits are not yet fully understood, there is a growing need to produce fractions enriched in these components to further study their individual effects on metabolism under controlled conditions and to manufacture enriched foods and beverages for the benefit of the consumer (Jiménez-Flores et al., 2009). Wong and Kitts

Chapter 8  Whey and Buttermilk—Neglected Sources of Valuable Beverages   237

(2003) reported about efficiency of the buttermilk powder at producing an antioxidant effect by acting as a reducing agent to scavenge peroxide and hydroxyl radical, and sequestering both Fe2+ and Fe3+ (Wong and Kitts, 2003). Thus, as well as whey, buttermilk is also nutritionally valuable coproduct that has numerous potentially beneficial effects on human well-being. The production of buttermilk beverages should therefore be one of key points when considering the future of milk-based beverages.

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Further Reading Liutkevičius, A., Speičienė, V., Alenčikienė, G., Mieželienė, A., Narkevičius, R., Kaminskas, A., Abaravičius, J.A., Vitkus, D., Jablonskienė, V., Sekmokienė, D., 2016. Fermented buttermilk-based beverage: impact on young volunteers’ health parameters. Czech J. Food Sci. 34, 143–148. Tratnik, L., Božanić, R., 2012. Mlijeko i mliječni proizvodi (Milk and Dairy Products). Hrvatska mljekarska udruga Croatian Dairy Association, Zagreb, Croatia.

CANAPA SATIVA L. AND MORINGA OLEIFERA AS NATURALLY FUNCTIONAL BEVERAGES: INNOVATIVE TRENDS

9

Martina Musarra⁎, Rita Jirillo†, Mattia Rapa⁎, Giuliana Vinci⁎ ⁎

Department of Management, Sapienza University of Rome, Rome, Italy, Department of Economics and Enterprises, Università della Tuscia di Viterbo, Viterbo, Italy †

9.1 Introduction Functional beverages include nutrients and bioactive compounds used for improving the health performance. The nutritive substances used in the functional beverages preparation are minerals, vitamins, amino acids (AA), and omega-3 (ω-3) and omega-6 (ω-6) fatty acids in different percentages, according to the product ingredient composition. Furthermore, another important group of elements added in the functional beverages are the antioxidant compounds. An interesting category is represented by “naturally functional beverages,” composed of foods that naturally contain nutrients and bioactive compounds and contribute to the improvement of health benefits for the consumers, by having positive effects on immune defence system, mental energy, cholesterol management, and other benefit associated with specific organs such as heart, liver, and eyes. Canapa sativa L. and Moringa oleifera are officinal and medical herbs that are contemplated in the category of “naturally functional foods,” and can be also considered as “naturally functional beverages” for the composition in nutritive principles. In fact, the C. sativa L. seeds have a high nutritional value, containing approximately 25% protein, 27% carbohydrates, 36% lipids, and considerable amounts of fibers, vitamins, and minerals (Callaway, 2004); the M. oleifera seeds contain approximately 39% carbohydrates, 27% protein, and 17% lipids, and fibers, vitamins, and minerals ­(Al-Juhaimi et al., 2016). Both the C. sativa L. and M. oleifera seeds contain in different percentages: essential amino acids (AAEs) ­necessary Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00009-2 © 2019 Elsevier Inc. All rights reserved.

243

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for protein synthesis; polyunsaturated essential fatty acids (EFAs), essential for the functioning of muscles, nerve receptors, and many glands in our body; vitamins; mineral salts (calcium, magnesium, and potassium) and antioxidant substances. C. sativa L. also contain unsaturated fatty acids (ω-3 and ω-6) in an optimal aspect ratio for the regulation of metabolic activities and all the eight AAEs: a regular intake of ω-3 and ω-6 in functional drinks offers various health benefits like improved cognitive function (especially for elderly and children), joint health, mental health, lowered incidence of heart failure and irregular heartbeat, and lowered blood triglyceride levels. In the food sector, hemp seeds are considered edible by the Circular of the Ministry of Health of 22/05/2009. Studies and research conducted by different authors have shown that hemp seeds possess a high nutritional value as they consist of about 25% protein, 27% carbohydrates, 36% lipids, and considerable amounts of fiber, vitamins, and mineral salts. In relation to the protein composition, "hemp" seeds are a high-value biological, rich, and complete food consisting of all eight AAEs (leucine, isoleucine, phenylalanine, lysine, methionine, threonine, tryptophan, and valine) required for protein synthesis. AAEs cannot be synthesized by the organism, so they must be introduced with the diet. These AA are needed for the formation of cellular membranes, for the proper development and functioning of the brain and nervous system, and for the production of eicosanoids, regulators of many organic functions including blood pressure, blood viscosity, vasoconstriction, and immune and inflammatory responses. In the food market containing "hemp," the largest market share is of flour and oil; drinks such as tea, coffee, and alcoholic beverages (beer and spirits) occupy a small market niche. M. oleifera food and beverage market is less developed than the hemp market, but the contents of antioxidant, proteins, vitamins, and minerals is important especially regarding its effects on h ­ uman health. In fact, M. oleifera is used for treating widespread conditions such as inflammation-related diseases, diabetes, arthritis and rheumatism, allergies and asthma, constipation, stomach pains and diarrhoea, fluid retention, bacterial, fungal, viral, and parasitic infections.

9.2  Canapa sativa L. Hemp is a genus of plant that is part of the Cannabaceae family and comprises three main species: C. Sativa L., Cannabis indica, and Cannabis ruderalis. Originally grown in the Central Asian countries, it has also spread to Europe and America.

Chapter 9  CANAPA SATIVA L. AND MORINGA OLEIFERA AS NATURALLY FUNCTIONAL BEVERAGES   245

C. sativa L. or hemp, to be processed in order to produce different market goods that can be sold in the market, contains specific quantities (≤0.2%) of tetrahydrocannabinol (THC), an illegal psychotropic substance (Musarra et al., 2018). The hemp has already been used in the Ancient Roman times, in 600 AD, for military equipment (ropes for boats) for its characteristic robustness and resistance, but the real affirmation took place in the first centuries of the Middle Ages, around the 11th century, when cultivation and processing was widespread in the North of the country, specifically in the Po Valley, Emilia Romagna and particularly in Bologna, at that time the largest production center in Italy. The interests of the Italian inhabitants for the cultivation started to grow as well as the importance of this commodity for the economy of the single city and a series of laws supported the construction of the hemp industry by creating a market-oriented agricultural production. In particular, the main regions which registered an effort for the regulation of the supply chain related to the agricultural cultivation and its transformation was Piemonte (Carmagnola) and Liguria (Genoa) where lively regional trade and important exports of fibers and artefacts occurred. During the 17th century, hemp culture became increasingly prestigious for its agronomic characteristics, diversity of application, and positive effects on human health. In the 21st century, Italy was the second nation in the world to produce hemp of renowned best quality. The first place was always held by Russia (Table 9.1). The decline began from 1954, which ended with the sunset of one of the textile fibers that contributed to the economic development of the Italian growth. The crisis started in 1938 in the Northern regions, reaching the South in 1964, causing difficulties also in terms

Table 9.1  World Hemp Production in 21 Century Russia Italy Hungary France Japan Serbia Romania Bulgaria

Land Cultivated (ha)

Quantity Produced (q)

753,114 79,477 65,192 17,214 13,518 14,025 5678 3015

3,737,628 795,000 587,954 147,266 94,893 67,025 19,035 9769

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of unemployment in many sectors. The reasons that caused the cultivation to stop were essentially two closely linked ones: the delay of industrialization and the prohibition. The delay in the industrialization techniques that accelerate the transformation process of the hemp had an effective role considering the enlargement of international economies and the changes in the international trade, where a high demand for goods defined a reduction in time of transformation. In fact, the Italian manufacturing sector presented a lack of investing capital, differently from the United States and England where the industrial capitalism arose in the factories and started changing the economic asset. In the Anglo-Saxon countries the large textile industry developed rapidly, and the cotton completely substituted the hemp cultivations. In addition to the ruthless competition of the new fiber, hemp consumption also declined due to the competition with other non-European fibers, such as the jute and the abaca of the metal cables used in the shipbuilding industry, and later on with the appearance of the synthetic fibers. The second important factor leading to the disappearance of hemp was prohibition for recreational usage. The first nation to forbid it was Egypt in 1879, followed by Greece the following year. With the advent of 20th century, drug-prohibition policies were introduced in other states, and in Italy the first law against its use was introduced in 1923. In 1961 hemp was completely associated with cannabis and the United Nations through the "Single Convention Drug Act" began to promulgate repressive laws and apparatus against cannabis, with the aim of extinguishing the cultivations in 25 years. The prohibition of marijuana contributed to the disappearance of hemp in the world economy, causing heavy consequences on Italian economy for the reduction in surface hemp dedicated. Until the 1970s, Italy was the second biggest hemp producer in the international scenario, but the regulatory restrictions on THC content in inflorescences (Law N. 685 of December 22, 1975) prohibited the cultivations throughout the territory. But at the end of 1980s scientific studies demonstrated the strengths of the cultivation under a perspective of sustainable development, such as the integration of environment, economic and social dimensions and in 1996 the hemp cultivated surface was 11,300 hectares but in 1997 the surface reached 22,000 hectares with the main producers being France and Spain, Austria, England, Germany, the Netherlands, and Portugal. Since 2000, the European Commission (EC) is working to regulate the hemp sector, defining laws and norms both for cultivations and for the transformation and sale of its derived products (EC Regulation 1673/2000, EC Regulation 73/2009), as well as in the content of THC. The efforts would allow the development of the supply chain in different market sectors within the European single market.

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In Italy, the Draft Law 2144/2015 of the 11/11/2015 adopted by the Chamber of Deputies currently under the examination of the Senate would promote the cultivations and agroindustry hemp chains for food and cosmetics; semifinished products (fiber, oils and fuels); organic material for bioengineering, bio-building, and ­phytodepuration; as well as for the promotion of research activities. The trend of industrial hemp cultivation, therefore, is growing continuously for its multiplicity of uses. In particular, the agri-food sector is the most interested in the growth prospects of the market, mainly because of the nutritional properties present in the products obtained from the transformation of hemp seeds. Scientific studies (Pojić et al., 2015; Bertoli et al., 2010; Callaway, 2004; Rodriguez-Leyva and Pierce, 2010) demonstrated a high nutritional value of hemp-based products by content of high biological protein (presence of high percentage of AAEs); fatty acids (in particular EFAs), vitamins; mineral salts; and antioxidant substances. Therefore, "hemp" food products can be labeled as "naturally functional food."

9.2.1  Chemical and Nutritional Characteristics and Effects on Heath The main product of industrial hemp in food are the hemp seeds, coming from the inflorescence of the plants and were usually transformed into hempseed oil and hempseed flour. Hemp seeds are “akenes” and contain 22%–25% proteins, 30%–35% lipids, 35%–37% carbohydrates (of which only 3% sugar), 15% insoluble fiber, carotene, phosphorous, potassium, magnesium, sulfur, calcium, iron, and zinc as well as vitamin E, C, B1, B2, B3, and B6. The hempseed oil yield production is very high, from 1 kg of hemp seeds 300 mL of hempseed oil (around 25%–30%) could be extracted. The average oil content of hemp seed from different agro-ecological regions could vary. The average oil content of hemp seed from different agro-ecological regions of Pakistan (28.87%) was slightly lower than that reported from Germany (30.00%) and Turkey (31.79%). However, the oil content of hempseed indigenous to Pakistan was considerably lower than that reported from different cultivation areas of Russia (30%–35%). Such variation in oil yield of hemp seed across countries might be attributed to the agro-climatic conditions of the regions. The range (26.90%–31.50%) of hempseed oil content from different agro-ecological regions as compared with those of some conventional and nonconventional oilseed crops was found to exceed those of cottonseed (15.0%–24.0%), soybean (17.0%–21.0%), and olive (20.0%–25.0%) grown in the United States, Brazil, China, and other Asian and European countries. It was

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c­ omparable to that of Salicornia bigelovii (27.2%–32.0%) but lower than that of M. oleifera (33.23%–40.90%). Hemp seed is a natural source of polyunsaturated fatty acids (PUFAs) and the main chemical contents are linolenic acid (C18:2 ω-6) and α-linolenic acid (C18:3 ω-3). The contents of these two fatty acids are, respectively, around 50%–70% (linoleic acid) and 15%–25% (α-linolenic acid), with a ratio of the two being 3:1, a value which is suggested as optimal for human nutrition (Scorletti and Byrne, 2013). The high content of ω-6 and ω-3 fatty acids and the relatively high phytosterol content of hemp make them beneficial to cardiovascular health. Polyunsaturated for saturated fats can reduce the risk of sudden cardiac arrest and fatal cardiac arrhythmia as well as reduce blood cholesterol levels and decrease the cellular proliferation associated with atherosclerosis. It is also a good source of gamma linoleic acid (GLA). The GLA and vitamin D of hemp may be beneficial in preventing and treating osteoporosis. These compounds are also known as EFAs because they are essential for humans or other animals for good health, since they cannot synthesize them (Willett, 2012). The EFAs have been found capable of reversing scaly skin disorder, rheumatism, inflammation, diabetes, excessive epidermal water loss, itch, and poor wound and beneficial for atopic eczema and psoriasis. Traditional hemp formulas were applied topically to treat abscesses, boils, pimples, and swellings. The contents of palmitic and stearic acids in the hempseed oils ranged from 5.75% to 8.27% and 2.19% to 2.79%, respectively. The oils were found to contain a high level of unsaturation (89.03%–91.39%). The contents of linoleic acid (18:2n6) ranged from 56.50% to 60.50%, followed by α-linolenic ­(18:3n-3) and oleic acids (18:1n-9), with ranges of 16.85%–20.0% and 10.17%–14.03%, respectively. A small amount of γ-linolenic acid (18:3n-6), ranging from 0.63% to 1.65%, was also detected. Literature reports have shown that hempseed oil contains a variety of FA, with linoleic (18:2) and linolenic (18:3) acids predominating (Callaway, 2004). Rumyantseva and Lemeshev (1994) reported that 18:2 and 18:3 usually account for approximately 50%–70% and 15%–25%, respectively, of the total FA content of the hempseed oil. Also, γ-linolenic acid (1.20%), an unusual FA was found. The occurrence and distribution of γ-linolenic acid in the plant kingdom may have chemotaxonomic significance in some families. γ-Linolenic acid is highly appreciated and is of considerable interest for its dietary uses and medicinal attributes. γ-Linolenic acid is one of the important FA used as both a health nutrient and a therapeutic agent, and only recently its potential physiological benefits have been extensively investigated (Xiao et al., 2006). The high content of EFA of nutraceutical value present in hempseed oil ensures the regulation of membrane fluidity by stabilizing the lipid bilayer, and it might be useful in reducing cholesterol in the blood and thus agonistic against atherosclerosis (Teh and Birch, 2013). However, a high degree

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of unsaturation renders hempseed oil extremely sensitive to oxidative rancidity. Because heat or light accelerates the degradation, the oil is unsatisfactory for frying or baking, although moderate heat for short periods is probably tolerable. In addition to EFAs hempseed oil also contains antioxidant, another category of important functional compounds. Antioxidant may reduce the risk of cardiovascular diseases, cancer, and age-­related macular degeneration (Leger, 2000); they also prevent the oxidation of unsaturated fatty acids. The specific extinctions at 232 and 270 nm, which reveal the oxidative deterioration and purity of the oils (Da Porto et al., 2015), ranged from 3.50 to 4.18 and 0.95 to 1.43, respectively. These specific extinction values were somewhat higher than those of some nonconventional oils such as M. oleifera and S. bigelovii seed oils. The average induction period (Rancimat: 20 L/h, 120°C), which is a characteristic of the oxidative stability of oils and fats (García-Cruz et  al., 2012), of hemp oil from different agro-­ ecological regions was 1.50 h (range 1.35–1.72 h). Because of the high content of PUFA, hempseed oil is fairly unstable and becomes rancid quickly unless preserved. In addition, tocopherols, a category of antioxidant compounds, were found. The average levels of α-, γ-, and δ-tocopherol in the oils from different agro-ecological regions were 52.07 (range 41.80–60.40), 665.00 (range 600.00–745.00), and 40.97 mg kg−1 (range 35.00–45.60 mg kg−1), respectively (Wilson, 1979). Among the tocopherols, the α-homolog shows the highest vitamin E activity, whereas the δ-isomer exhibits potent antioxidant activity. This suggests that hempseed would be a good source of important tocopherols. The hemp seed has some pharmacological effects both due to the presence of antioxidant compounds (e.g., for rheumatoid arthritis) and due to its fatty acid composition (e.g., hypercholesterolemy), therefore its dietary assumption is highly recommended. Compared with conventional oilseed crops, the protein content of hemp seed was higher than those of safflower (20%–22%), sunflower (16.50%–19.60%), and cottonseed (19.40%) but comparable to those of linseed (24%), sesame seed (20%–25%), and mustard seed (25%–35%) (20). Hempseed protein is readily digestible, as it is primarily composed of edestin and albumin, which are components of human blood plasma. However, heat-treating whole hemp seed denatures this protein and renders it insoluble, possibly affecting digestibility. The high protein content allows the hemp to carry all the nine AAEs: phenylalanine, isoleucine, histidine, leucine, lysine, methionine, threonine, tryptophan, and valine. Different characterizations were carried out in the literature for the AA composition of hemp. Some studies found that hemp was mainly composed of protein (90.5%), moisture (2.8%), ash (2.4%), and other components (e.g., carbohydrate). The amino acid

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compositions are rich in glutamic acid, aspartic acid, serine, arginine, and leucine. Although the sulfur-containing AA (Met and Cys) might be to some extent destroyed by the method used in the study. All the AAEs were found and the proportion of AAEs to the total AA (E/T) for was significantly higher, suggesting that the hemp have a good nutritional amino acid value. The moisture content of the hemp seed in the present analysis was comparable to those of sunflower (6.0%–9.0%), palm (5.9%–8.5%), and rapeseed (6.0%–9.0%). The fiber content was lower than that of cottonseed (22.6%) but significantly higher than those of soybean (4.8%), sesame seed (12.0%), and sunflower seed (13.2%–15.7%). The values determined for iodine (154.00–165.00 g of iodine/100 g of oil), refractive index at 40°C (1.4698–1.4750), density at 24°C (0.9180–0.9270), saponification value (184.00–190.00 mg of KOH/g of oil), and unsaponifiable matter (0.70%–1.25%). The iodine value of hempseed oils was, however, higher than those of cottonseed (99–119 g of iodine/100 g of oil), soybean (120–143 g of iodine/100 g of oil), and sunflower oils (110–143 g of iodine/100 g of oil) but lower than that of linseed oil (155–205 g of iodine/100 g of oil). The refractive index at 40°C was higher than that of most vegetable oils reported in the literature. The saponification value was within the range of cottonseed, olive, pumpkin seed, and safflower oils. The color (0.50–0.80 R + 27.00–32.00 Y) of the hempseed oils investigated was lower in yellow and red units than those of some other nonconventional vegetable oils. The intensity of the color of vegetable oils depends mainly on the presence of various pigments, such as chlorophyll and carotenoids, which are effectively removed during the degumming, refining, and bleaching steps of oil processing. Vegetable oils with minimum color index values are more suitable for edible and domestic purposes. The present investigation revealed that hemp could be utilized successfully as a valuable source of EFA (18:2n-6, 18:3n-3) of nutraceutical value. It could also be used in the preparation of various food commodities because of its nutritional and therapeutic attributes, and could be used with other high-oleic vegetable oils for the preparation of nutritionally balanced oil blends.

9.3  Moringa oleifera The M. oleifera is a plant belonging to the Moringaceae family, widespread in much of the tropical and equatorial area of the planet. Actually, the known species of M. oleifera are 14. The geographical area of distribution is identified in Eastern India, but the species is widely spread and cultivated throughout the tropical fascia of the planet, such as Ethiopia, Kenya because of its drought–resistant properties. In fact, the plant is adaptable to a wide variety of soil, even poor and sterile

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soil. Moreover, it does not have soil preference in terms of pH (acidic or alkaline soils), tolerating pH values from 4.5 to 9.0; it grows and can fruitfully grow in the first year of planting with abundant leaf growth. The whole plant is edible and has a remarkable nutritional interest for its protein content and the AA, making the plant interesting from humanitarian point of view, as it has great potential for fighting hunger, malnutrition, and poverty. The leaves can be eaten and are very rich in proteins, vitamins, and mineral salts. They have a slightly spicy and pleasant taste even in the raw state. They can be used in salads or can also be cooked like spinach. They contain 25% more protein than eggs and twice as much as cow milk, quadruple in carotene vitamin A and nearly eight times the vitamin C of oranges, three times the potassium of bananas. Such a protein contribution suggests that such nutrition can be a useful support for pregnant and lactating people in conditions of poverty and difficulty. Regarding fruits, the most frequent modality is the boiling of immature pods. Even flowers are edible and are usually used in salads. In addition, moringa is melliferous plant, and honey may be produced from its flowers. The seeds contain 30%–50% of oil (for comparison, the olives contain 8%–20%). The extracted oil contains 65%–76% of oleic acid, which is the same as unsaturated fat of olive oil. The oil is perfectly suited to human nutrition. Extracts of oil from the seeds contain 60% of precious protein. This is a huge amount if we consider that the residual analogous soybean residue, a product of fairly high protein quality, produces from 30% to 35% of proteins, whose range of AA, as with the vast majority of other known plants, is incomplete. Protein obtained from the residual pasta is suitable for human nutrition. Its highly nutritious properties make it a very important source of food, especially in developing countries, so the WHO considers it a possible means of fighting malnutrition. It is an important source of essential elements (K, Ca, P, Fe), vitamins (A, D, and C), flavonoids, carotenoids, AA, and proteins. Moringa is also used in traditional medicine against various pathologies: inflammation, infections, cardiovascular, gastrointestinal, hepatic, diabetes, cancer, HIV, AIDS, and so on. The benefit of these remedies is the absence of side effects, typical of drugs (Raaz et  al., 2014). Another Moringa application is the treatment of water purification by the coagulating and antimicrobial action of the powdered seeds. This is a very important operation, especially in developing countries, where drinking water is often not easily accessible (Kansal and Kumari, 2014). Other Moringa uses include biomass, animal feed, biogas, and fertilizer production. Seed oil is also used in the kitchen, cosmetics, and lubricants; it is also often called "Tree of Life" or "Miracle Tree."

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9.3.1  Chemical and Nutritional Characteristics and Effects on Heath The leaves were high in protein content (26.3%), which was within the limits reported in the literature (Paliwal et al., 2011). As per a published report (18), the daily safe protein requirement for a 70-kg adult is 58.1 g (0.83 g.kg–1.day–1). Therefore, about 100 g of dry M. oleifera leaves can provide 45.3% of the required safe protein intake. Some variations can be caused by weather variations, crop management, if they are cultivated or wild, the state of maturity of the plant at the time of collection, and the type of post-collection processing. AA are organic compounds that combine to form proteins; as such, they influence the quantity and quality of protein (Sena et al., 1998). AA are classified as essential and nonessential, and each one has a specific function in the human body. In general, AA are required for the production of enzymes, immunoglobulins, hormones, growth, and repair of body tissues, and they form the structure of red blood cells as well. The total AA concentration was 2234.1 (± 19.8) mg.100 g–1 of dry matter (DM). All essential AA were present and constituted 53.8% of the total AA. All the essential AA were present in M. oleifera dried leaves and made up to >50% of the total AA content, since the quality of a protein is proportional to its content in essential AA. The wide range of the concentration of AA reported for Moringa (Zapata et al., 2007) may be due to differences in environmental conditions, cultural practices (mainly fertilization), age of the trees, stages of maturity of leaves, or varieties and methods used for analysis. About 100 g of dry M. oleifera leaves can provide 10.6% of the daily requirement of histidine, 5.8% of isoleucine, 7.7% of leucine, 6.2% of lysine, 25.4% of methionine + ­cysteine, 11.3% of phenylalanine + tyrosine, 8.8% of threonine, 18.8% of tryptophan, and 6.2% of valine (Saini et al., 2014). It could be p ­ ossible that the variations in the amino acid composition of the leaves may be influenced by the quality of the protein and the origin of the plant (cultivated or wild). Considering both protein content and the essential AA patterns of its leaves, M. oleifera can be a good source of protein and essential AA. Therefore, Moringa could be incorporated into the human diet, particularly for children to prevent or cut malnutrition. For the antioxidant compound, the dried leaves of M. oleifera contained 4512.2 (±79.1) mg 100 g–1 DM of total phenols and 1264.2 (±25.1) mg QE.100 g–1 DM of flavonols. Phenolic compounds or polyphenols are derived from the secondary metabolism of plants. These compounds are commonly found in plants and have been extensively exploited because of their multiple biological activities, including antioxidant effects. Flavonoids and phenolic acids are receiving increased attention as potential antioxidants, mainly due to their strong presence in a significant number of consumer foods (García-Cruz et al., 2012).

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In phenolics and flavonoids, at least, one hydroxyl ion is substituted with an aromatic ring forming chelate complexes with metal ions, thus are readily oxidized. They, therefore, serve as great units to donate electrons. The antioxidant activity of the phenolic compounds in the above reports is shown to be mainly due to their redox properties, allowing them to act as reducing agents, hydrogen donors, or singlet oxygen quenchers (Sankhalkar, 2014). It turns out that most researches conclude there is a correspondence between phenolic compounds and antioxidant activities in plants. The high phenol and flavonol contents of M. oleifera leaves can contribute to a healthy diet, since they have important biological effects such as high antioxidant activity, inhibition of platelet aggregation, antimicrobial activity, antitumor activity, and finally, anti-inflammatory action. The myricetin, quercetin, and kaempferol concentrations were 649.8 (±22.6), 77.2 (±3.7), and 37.2 (±1.2) mg.100 g–1 DM, respectively. Some studies have established that myricetin is one of the most active antioxidants and a potent antimutagen and anticarcinogen agent. Quercetin is a powerful antioxidant, contributing to the prevention of atherosclerosis, enhancing the antiproliferative activity of anticancer agents, and inhibiting the growth of transformed tumorigenic cells; helps in the relief (as suppressing chemopreventive and chemotherapeutic agent) of local pain caused by inflammation, headache, and stomach ulcer; and reduces the carcinogenic activity of several mutagens that exist in cooked food. One of the most important factors that determine the antioxidant activity of the polyphenols is the degree of hydroxylation and the position of the hydroxyls in the molecule. The flavonoids due to oxygen heterocycle are more active than non-flavonoid molecules. In turn, solubility and steric effects of each molecule may be affected by the type of structure of such molecules, as glycosylated derivatives of other adducts can increase or decrease the antioxidant activity (Jahan et al., 2015). The flavonoid compounds are commonly found in plants as glycosides, but the action of enzymes or some processes can release the corresponding aglycone. The activity of phenolic acids is also based on the hydroxyl groups of the aromatic ring and the binding of these compounds to organic acids and sugars to form esters. The mechanisms by which these compounds act vary depending on the concentration and types of compounds present in the foods (Zapata et al., 2007; Jahan et al., 2015). These results suggest the potential of Moringa as a functional ingredient in foods that may also aid in the prevention of illnesses related to oxidative stress. The fat content of dried leaves was 4.67%–15.00% DM. The great variations in the concentration of fatty acids among the reports in the literature may be due to varietal differences, environmental c­ onditions, and cultivation methods. The content of saturated fatty acids (SFA) was 28.33% (C16:0 at 17.92%, followed by C18:0, C22:0, C14:0, C20:0,

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and C10:0 at 6.17%, 2.12%, 1.34%, 0.67%, and 0.11%, respectively). The monounsaturated fatty acids (MUFA) made up another 8.54% (C18:1 at 7.46%, followed by C14:1, C16:1 at 0.71% and 0.37%, respectively), while the polyunsaturated (PUFA) content was 61.27% (C18:3 at 52.24% followed by C18:2 at 9.03%). No trans fatty acids were detected. The PUFAs are important for human and animal health. They are of interest because they are precursors of the long-chain ω-3 PUFA in the eicosanoids’ biosynthesis, which are important bioregulators of many cellular processes. The PUFAs are also linked to the development and functionality of the immune system. Consumers prefer food low in saturated fatty acids because these acids are associated with increased risk of cardiovascular diseases and some kinds of cancer. In addition, nutritionists urge consumers to increase the intake of PUFA, particularly ω-3 at the expense of ω-6 (Jahan et al., 2015). The PUFA/SFA ratio of 1.21 is recommended. Saini et al. (2014) reported a PUFA/SFA ratio of 2.34 and PUFA/MUFA ratio of 9.64 in M. oleifera leaves. In the present study, PUFA/SFA ratio was 2.16 and PUFA/MUFA ratio 7.2. High PUFA/SFA ratio and oleic acid content are desirable traits (Melesse, 2011). The high leaf fatty acid unsaturation (membrane lipids) found during this study is related to stress caused by growing in cool periods or moderate temperatures (herein in September) and drought stress (herein sparse irrigation) (Maldini et  al., 2014; Dollah et  al., 2014). The occurrence of PUFAs was increased by 96% as compared to monounsaturated fatty acids. The consumption of PUFAs caused decreased levels of the total and the low-density lipoproteins (LDL) cholesterol, having a cardioprotective role of these compounds. That effect is b ­ ecause they are antiarrhythmic agents that improve vascular ­endothelial function and descend blood pressure, which inhibits platelet aggregation. It is associated with an impediment to the formation of plaques on the inside of blood vessels and adherence to endothelium. It has been observed that people whose diets are rich in PUFAs show a low incidence of cardiovascular disease. Taking into account the LARN (2014) for healthy individuals from 19 to 70 years old, for whom daily dietary intake of ω-3 fatty acids is 1.1–1.6 g, about 100 g of dry M. oleifera leaves can provide 181.25%–263.6% of the appropriate intake of ω-3, whereas it may not be a good source of ω-6 fatty acids as 100 g of dried leaves can provide only 2.9%–3.6% of the recommended intake (14–17 g). The total ash content of the dry leaves was 12.0% (±0.2). Ca was the predominant mineral with 1712.6 mg.100 g–1 DM, followed by K, Mg, and P (1002.9, 460.4, and 194.2 mg.100 g–1 DM, respectively). Mn, Na, Fe, Zn, and Se were also present in lower concentrations. These values could vary due to the availability of soil nutrients, which were low for most macronutrients and sufficient for micronutrients, and could be addressed by the applying fertilizers to the soil or directly on

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leaves. Based on the LARN (16) for healthy individuals 19–7 years old, about 100 g of dry M. oleifera leaves can provide 131.7%–171.3% of the daily intake of Ca, 133.3% of Cu, 223.9%–503.8% of Fe, 339.1%–433.3% of Mn, 109.6%–148.5% of Mg, 27.7% of P, 21.3% of K, 1.9%–2.2% of Na, 2,000% of Se, and 34.5–47.5% of Zn. Thus M. oleifera leaves can be a good source of minerals in human diet. From these results, it can be concluded that Moringa could help to prevent diseases related to malnutrition. The dietary fiber content of M. oleifera dried leaves was 34.1% (± 0.9). Dietary fiber improves laxation, reduces risk of coronary heart disease, and is essential to maintain body weight and composition, blood sugar levels (low glycemic index), triglycerides, and cholesterol (bound with fiber components and increased excretion). The dietary fiber content of M. oleifera dried leaves appeared higher than that reported by others (8.51%–30.97%) (Coppin et  al., 2013; Förster et  al., 2015). Taking into account the LARN (2014) for healthy individuals from 19 to 70 years old, for whom a daily dietary intake of 21–38 g is recommended, ~100 g of dry M. oleifera leaves can provide 89.7%–161.9% of the daily recommended intake. The nonstructural carbohydrates (which account for sugar and starch) content was 22.0% (±0.3). Since a daily dietary intake of 130 g is recommended (9), ~100 g of dry M. oleifera leaves can provide only 16.9% of the daily appropriate intake, making the M. oleifera dried leaves a low-carbohydrate food, appropriate for a low-calorie nutrition program. The M. oleifera leaves had a high carotenoid content. In particular, lutein, zeaxanthin, and β-carotene were detected at 10.03 (±0.47), 1.52 (±0.09), and 2.02 (±0.12) mg.100 g–1 DM, respectively. Carotenoids are related to a lower risk of cancer, cardiovascular disease, age-related macular degeneration, and the formation of cataracts. In addition, β-carotene is converted into retinol and is thus referred to as provitamin A carotenoid, while lutein and zeaxanthin have no vitamin A activity. M. oleifera leaves had a high carotenoid content. The variations in the concentrations of carotenoids among the reports in the literature may be due to varietal differences, environmental conditions, and cultivation methods. However, the consumption of M. oleifera leaves will promote health as part of a healthy and balanced diet. Vitamin C in the Moringa leaves was 203.1 (±24.8) mg.100 g–1 DM, while vitamin E concentration was 98.6 (±3.9) mg α-tocopherol.100 g–1 DM and 5.4 (±0.8) mg γ-tocopherol.100 g–1 DM. The antioxidant properties of tocopherols (vitamin E) are well established, and their role is of greater importance as human body mass increases during adolescence. Vitamin C is involved in the synthesis of connective tissues (i.e., collagen). Therefore, it is considered as an important nutrient during adolescent and development; vitamin C also increases iron absorption in the body. Taking into account the LARN (2014) (where a daily

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dietary intake of 75–90 mg.d–1 for vitamin C and 15 mg.d–1 for vitamin E is recommended), about 100 g of dry M. oleifera leaves can provide 225.7%–270.8% of the appropriate daily intake of vitamin C and 693.3% of vitamin E (both α- and γ-tocopherol). Therefore, M. oleifera leaves can be a good source of vitamins C and E in human diet.

9.4  Food Markets and Perspectives 9.4.1 Hemp The C. sativa L. species has specific characteristics and properties that determine its ease of cultivation, increased soil fertility, and the economically and ecologically sustainable production of fiber and grain, elements that, together with the ability to adapt to difficult conditions, allow the development of its derivative product market closely related to the territory. Worldwide (Europe, Asia, and North and South America) total cultivation of hemp in 2011 was around 85,000 hectares (ha), of which about 60,000 ha were dedicated to fiber (mainly in China and Europe) and 25,000 ha dedicated to seeds (especially in Canada, China, and Europe). China produces more quantities of hemp and is the largest exporter, especially to the United States. The European Union (EU) has a highly active hemp market, with distributed production between France, the UK, Romania, Hungary, Austria and Denmark being among the most significant. In general, the market for hemp seeds is growing: in Europe in 2013, almost 9000 tonnes were produced; in 2014, crops affected a total area of 18,000 ha; in 2015 22,000 ha; and in 2016 25,000 ha. In Canada, however, in 2015 more than 36,000 ha were harvested (+ 25% compared to 2013) and are expected to reach 50,000 ha (+ 28%) over the next few years (Mordor Intelligence Report, 2016). Hemp seeds are mainly destined for 80% for the feed industry and only 20% is used for the production of foodstuffs. Regarding the market of hemp beverages and food products, the geographical distribution is expansive, but is not uniform, involving North America, Europe, Asia, the Middle East, Africa, and Latin America. In North America, the highest growth peak of hemp beverages and food products was recorded in the market in 2015 due to the consumer's particular attention to the nutritional properties of these products. Europe follows North America, ranking second in the spread and growth of the market for hemp beverages and food products; Asia is also a growing market, mainly due to the progressive westernization of the food habits of the population. Finally, Latin America is still a potential market, with a share to increase in medium- to long-term prospects.

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Therefore, the hemp beverages and food products markets are extremely competitive, with the participation of a large number of different suppliers competing with each other in terms of product differentiation, quality, price, innovation, distribution, and promotion of the brand. The key players operating in the international market are: Hemp co., Naturally Splendid, Mettrum Originals, and Manitoba Harvest. Other minor players in the market are: Canada Hemp Foods, Braham and Murray, Elixinol, Nutiva, Healthy Brands Collective, Laguna Blends, Hemp Foods Australia, and The Cool Hemp Company. These are mostly large companies that dominate the market thanks to huge investments in production facilities in different countries. However, the global supply of hemp beverages and food products is also characterized by the presence of many small emerging regional producers. In particular, the European market carries out food production and marketing activities, research and development studies, innovation centers, in order to expand production capabilities, meet the growing demands of consumers, to introduce new products with the goal of remaining competitive at global level. Italy since 1930 was the second largest producer of hemp (14%) after Russia (58%) with an average annual production of around 550,000 tonnes, and the largest exporter with about 47,400 tonnes reaching 57% of production. In fact, since 1900, hemp cultivation in the Italian state played an important role mainly in the production of textile fibers destined for the overseas market: the regions producing the highest amount of hemp cultures were Veneto, Emilia-Romagna, and Campania. Italian hemp production has generally been tending to growth until 1943, the year after which a crisis led to the progressive disappearance of hemp cultivations. The main reasons for the reduction in Italian hemp production and the subsequent disappearance are mainly due to the industrialization of the cotton production process, which conquered the international market thanks to the spread of intensive agriculture, in contrast to hemp production, family, and crafts. Subsequently, in the 1970s, a certain international prohibition has sanctioned the illegality of hemp due to the THC content present in the inflorescences; Italy also with Law No. 685 of December 22, 1975 has implemented such restrictions on cultivation in the territory. Only in the 1990s the EU has reformed the organization of the common market, reintroducing hemp cultivation, but limiting it to textile fiber production: growth in demand for plant fibers from European countries has allowed reintroduction of hemp cultivation in Italy with the Circular of the Ministry of Agriculture and Forestry of 2/12/1997, which defined the incentives provided by the European Economic Commission (EEC) for industrial hemp crops (in Italy approximately 1,300,000 lire for every cultivated hectare): among the Italian regions more participative in the initiative are Piemonte, Emilia-Romagna, Tuscany, the Marches, and Campania.

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The varieties of C. sativa L. permitted for cultivation purposes within the community area are listed in Annex XII to EC Regulation 2860/2000, specifying the THC content in inflorescences of less than or equal to 0.2% and expanding the areas of destination for processing and use. In fact, the Italian hemp market has experienced a general growth, especially for the production of seeds for food purposes.

9.4.1.1  Hemp Tea and Coffee Hemp tea and infusions are common in the Italian market, and the hemp flowers are used for the production of a scented and relaxing herbal tea with reduced value of THC but a high value of cannabidiol (CBD), one of the many active ingredients contained in the hemp leaves and inflorescences. The CBD is the healing principle of hemp that has sedative, anticonvulsant, antioxidant, and anti-inflammatory effects. It has also been shown to be able to regulate blood pressure and is a promising antispasmodic, but most of the research shows an effective antitumor activity. The varieties of legal hemp used in Italy and present on the Italian market particularly rich in CBD can help treat a variety of medical symptoms, including chronic pain, inflammation, multiple sclerosis, arthritis, anxiety, and muscle spasms among others. Regarding coffee, hemp seeds are added to the mixture of roasted coffee (90% Arabica, 10% Robusta) with the aim to ameliorate the nutritional values and the effects of human health. The idea was born at Fitness Coffee GVM, an Italian company that for 12 years is in the business of the hemp food and beverage market, creating and producing hot drinks such as coffee, tea, and barley. In 2004, the company filed the first patent for the production of roasted coffee (not soluble), with herbs and spices. The patent was granted in 2009 and from that date any coffee produced with herbs and spices (not with extracts) is the exclusive product of the company. From 2009 the company started producing different types of coffee: Fitness Coffee (with 16 different herbs), Sensual Coffee, Fitness Barley and Cannabissimo. The company exports the coffee mixture to 30 countries from Australia to Qatar, passing through Guatemala and the United States, but the hemp coffee is not commonly found in European bars and restaurants because of the protectionism laws implemented by EU concerning the imports of coffee and chocolate. The properties of hemp seeds are maintained and mixed with the roasted coffee, contributing to add the beneficial effects to the mixture.

9.4.1.2  Hemp Milk Hemp milk is obtained by grinding the seeds. It is the same variety used to obtain the flour pastry, having sweet flavor, and oil. Rich in protein and vitamins such as A and E, it is a viable alternative to cow

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milk not only for those who want to change the diet in a healthy way or have made a vegan choice but also for lactose intolerants. Being free from sugar naturally contained in animal milk it is more digestible. The hemp milk contains about 30% of the recommended daily vitamin D ratio and a good amount of calcium, two important substances for the robustness of the skeleton that are present in cow milk but naturally absent in vegetable ones (almond, coconut, oats) to which they are usually added. The hemp drink is an excellent source of minerals such as magnesium, potassium, and iron. As hemp milk is derived from hemp seeds, the positive effects of this product on human health depend on the amount of linolenic acid (C18:2 ω-6) and α-linolenic acid (C18:3 ω-3). The properties of high amount of PUFAs are beneficial for all the population, by reducing the accumulation of bad cholesterol, regulate the pressure activate neurons, and promoting mental efficiency.

9.4.1.3  Energy Drinks The energy drinks produced by hemp combines the high quality of the typical energy drink ingredients with healthy properties derived from this commodity. Energy drinks are produced by the transformation of hemp seeds, giving to the drink all the properties related to the content of protein (25%), carbohydrates (27%), lipids (36%), and considerable amounts of fibers, vitamins, and minerals. The energy drinks based on hemp seeds are produced with water and processed hemp seeds, with addition of taurine and caffeine, besides the normal properties of gluten free and lactose free.

9.4.1.4  Hemp Beer In the past, many breweries had tried to put together these two elements, but most of the commercial attempts had not come to an end. The first experiment was conducted in Berlin in 1996. Turn was launched in the market, it was a very short-lived hemp beer that disappeared from supermarket shelves in a short time. Only in 2001 Cannabis Club Suds gained the industry's first major success. Produced by the Bavarian brewery Weissenohe, this beer defined the quality standards that would then be followed by all the other beers in hemp, from 2001 to the present. Returning to the history of beers in hemp, the market marked an important turning point in 2005, when the Czech Republic decided to produce this beer. Since then, its fame has begun to spread everywhere, also thanks to the ever less restrictive rules on Cannabis use. Today, it has become a good business opportunity for any invader, and even the smallest and most independent breweries have decided to move in this direction, hoping to offer the most distinctive flavors and aromas.

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Czech beers, such as Hemp Valley Beer, KonoPi, and Cannabis Club Suds are the most important producers of hemp beer in the European market, and their popularity is growing because of the recent reforms on the legalization. For instance, new brewery factories such as those in Colorado, which specialize in the commercial production of this drink, are beginning to rise. An example that we could consider is Redhook Ale Brewery, the joint-venture producer and distributor of "Joint Effort Hemp Ale," sold exclusively in the state of Washington.

9.5 Moringa M. oleifera is gaining considerable scientific interest for its many beneficial properties. Some work in the literature deals with the use of Moringa seeds in water purification for their coagulant and antimicrobial properties. Various experiments of turbidimetry and cytotoxicity have been performed for this purpose. However, the mechanism of action of this process has not yet been clarified. Numerous studies have attributed the coagulant properties to a water-soluble cationic protein which, by binding to the anionic species present in the water, allows them to agglomerate in flakes and facilitate elimination (Kansal and Kumari, 2014). Instead, the antibacterial action can be traced back to the aromatic glucosinolates present in the seeds (Förster et al., 2015). Many studies have focused on the antioxidant properties of this plant: by LC-MS experiments on leaf extracts it was possible to identify quercetin, 3-O-glucoside quercetin (isoquercetin), 3-O-rutinosyl quercetin (routine) 3-O-(6'-malonylglucosyl) quercetin, kaempferol, 3-doducosyl kaempferol (astragaline), 3-O-(6'-malonylglucosyl) kaempferol, chlorogenic acids, gallic acid, and ferulic acid (Verma et al., 2009; Coppin et al., 2013; Singh et al., 2009; Vongsak et al., 2013). Other researchers have evaluated, by means of GC-MS experiments, the fatty acid composition of the different parts of Moringa after their transformation into corresponding methyl esters, in the leaves α-linolenic acid was the most abundant, followed by palmitic and linoleic acids and low concentrations of palmitoleic, stearic, oleic, and erucic acid. In the fresh pods and in the flowers, palmitic and linoleic acids were found to be much greater than those of the leaves. High concentrations of oleic, palmitic, and stearic acids were found in seed oil. Finally, high levels of oleic acid and low concentrations of linoleic acid and linolenic acid were found in the seeds compared to those of fresh flowers and pods. The M. oleifera food and beverages products are growing their presence in the market. Moringa, a plant virtually unknown until a few years ago, from 2002, is raising its market rate, especially for its good properties on human health. At the same time, because the market of M. oleifera products is relatively young, there is the possibility to buy

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low-quality products. In fact, a large number of products present in the market do not have the proper quality control and even if these products can be economically accessible, they cannot reflect the label information.

9.5.1.1  Moringa Tea The only beverage product available on the international food and beverage market is the Moringa tea. Moringa tea is composed of its natural leaves, and does not contain caffeine, thanks to the properties of decaffeinated leaves obtained from the Moringa plant. Present in Asia and Africa, Moringa is associated with various health benefits and contains several vitamins, minerals, and antioxidants. This tea is incredibly nutritious: each 1.5-g sachet contains 0.4 g of protein and 0.5 g of fiber, along with various vitamins, minerals, and antioxidants. The Moringa tea generally comes from Sri Lankan plantations and it has a high antioxidant content, as well as high contents of oily substance that lubricates and nourishes the skin. To take advantage of this, moringa leaves are used to brew tea by steeping the dried, preserved leaves in hot water, which releases special chemical compounds—very similar to the way green tea is made. Dried moringa leaves are also ground to create a long-lasting powder, or potent extracts are taken from the leaves to be used in the formation of concentrated moringa capsule supplements. Aside from the valuable leaves, the pods of the moringa tree also contain seeds that hold a healing type of oil. Oil from moringa seeds can be used to cook or put directly onto the surface of the body. Several popular uses of moringa oil are to help retain skin’s moisture, speed up wound healing, and soothe dry or burnt skin.

9.6 Conclusions The food and beverage market for C. sativa L. and M. oleifera is still developing. Even if in the past hemp cultivations were common and widespread, after the prohibition period the cultivation rate rapidly decreased. Only in the recent period, academic studies and research have shown that hemp seeds own a high nutritional value as they consist of about 25% protein, 27% carbohydrates, 36% lipids, and considerable amounts of fiber, vitamins, and mineral salts. In relation to the protein composition, hemp seeds are a high-value biological, rich, and complete food of all eight AAEs (leucine, isoleucine, phenylalanine, lysine, methionine, threonine, tryptophan and valine) required for protein synthesis. These AA are needed for the formation of cellular membranes, for the proper development and functioning of the brain and nervous system, and for the production of eicosanoids, regulators of many organic functions including blood pressure,

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blood viscosity, vasoconstriction, and immune and inflammatory responses. The beneficial effects of hemp are shown by scientific literature and only from 2002 the hemp food and beverage market are growing its share. Flour and oil are the most sold in the market, but drinks such as tea, coffee, milk, and alcoholic beverages (beer) are also raising their positions. Concerning M. oleifera, even though this plant is not known as the hemp, its chemical properties and its effectiveness on human health is considerable. The amount of antioxidant properties, fatty acid composition, α-linolenic acid by palmitic and linoleic acids, and low concentrations of palmitoleic, stearic, oleic, and erucic acids are important to preventing and defeat some health conditions, such as inflammation-related diseases, diabetes, arthritis and rheumatism, allergies and asthma, constipation, stomach pains and diarrhoea, fluid retention, and bacterial, fungal, viral, and parasitic infections.

References Al-Juhaimi, F., Ghafoor, K., Hawashin, M.D., Alsawmahi, O.N., Babiker, E.E., 2016. Effects of different levels of Moringa (Moringa oleifera) seed flour on quality attributes of beef burgers. CYTA—J. Food 14 (1), 1–9. Bertoli, A., Tozzi, S., Pistelli, L., Angelini, L.G., 2010. Fibre hemp inflorescences: from crop-residues to essential oil production. Ind. Crops Prod. 32 (3), 329–337. Callaway, J.C., 2004. Hempseed as a nutritional resource: an overview. Euphytica 140 (1–2), 65–72. Coppin, J., Xu, Y., Chen, H., Pan, M., Hoc, C., Juliani, R., Simon, J., Wu, Q., 2013. Determination of flavonoids by LC/MS and anti-inflammatory activity in Moringa oleifera. J. Funct. Foods 5, 1892–1899. Da Porto, C., Decorti, D., Natolino, A., 2015. Potential oil yield, fatty acid composition, and oxidation stability of the hempseed oil from four Cannabis sativa L. cultivars. J. Diet Suppl 12 (1), 1–10. https://doi.org/10.3109/19390211.2014.887601. Dollah, S., Abdulkarim, S., Ahmad, S., Khoramnia, A., Ghazali, H., 2014. Physicochemical properties and potential food applications of Moringa oleifera seed oil blended with other vegetable oils. J. Oleo Sci. 63 (8), 811–822. Förster, N., Ulrichs, C., Schreiner, M., Müller, C., Inga, M.I., 2015. Development of a reliable extraction and quantification method for glucosinolates in Moringa oleifera. Food Chem. 166, 456–464. García-Cruz, L., Salinas-Moreno Y., Valle-Guadarrama S., 2012. Betalaínas, compuestos fenólicos y actividad antioxidante en pitaya de mayo (Stenocereus griseus H.). Rev. Fitotec. Mex.[online] 35(5), 1-5. Jahan, M.S., Zawawi, D.D., Abdulkadir, A.R., 2015. Effect of chlorophyll content and maturity on total phenolic, total flavonoidcontents and antioxidant activity of Moringa oleiferaleaf (Miracle tree). J. Chem. Pharm. Res. 7 (5), 1147–1152. Kansal, S., Kumari, A., 2014. Potential of M. oleifera for the treatment of water and wastewater. Chem. Rev. 114, 4993–5010. Leger, C.L., 2000. La vitamine E et la prevention cardiovasculaire. Ann. Biol. Clin. 58, 524–540. Livelli di Assunzione di Riferimento di Nutrienti ed energia (LARN), 2014. Società Italiana di Nutrizione Umana.

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Maldini, M., Maksoud, S.A., Natella, F., Montoro, P., Luigi, G., 2014. Moringa oleifera: study of phenolics and glucosinolates by mass spectrometry. J. Mass Spectrom. 49 (9), 900–910. Melesse, A., 2011. Comparative assessment on chemical compositions and feeding values of leaves of Moringa stenopetala and Moringa oleifera using in vitro gas production method. Ethiopian J. Sci. Technol. 2, 31–41. Musarra, M., Rapa, M., Vinci, G., 2018. Canapa Sativa in the food sector: nutritional characteristics and market prospects. Ind. Aliment. 57 (589), 15–21. Paliwal, R., Sharma, V., Pracheta, S., 2011. A review on horse radish tree (Moringa oleifera): a multipurpose tree with high economic and commercial importance. Asian J. Biotechnol. 3, 317–328. Pojić, M., Dapčević Hadnadev, T., Hadnadev, M., Rakita, S., Brlek, T., 2015. Bread supplementation with hemp seed cake: a by-product of hemp oil processing. J. Food Qual. 38 (6), 431–440. Raaz, K., Maheshwari, R., Khan, M., Pandey, M., Khan, S., Lal, B., Jat, B., Singh, B., Rani, B., 2014. Enthralling drum stick tree for fascinating Human reassure and socio-­ economic protract. JPBR 2 (1), 102–114. Rodriguez-Leyva, D., Pierce, G.N., 2010. The cardiac and haemostatic effects of dietary hempseed. Nutr. Metabol. 7. Art. No. 32. Rumyantseva, L.G., Lemeshev, N.K., 1994. Current state of hemp breeding in the. C.I.S. J. Int. Hemp Assoc. 1, 49–50. Saini, R.K., Shetty, N.P., Prakash, M., Giridhar, P., 2014. Effect of dehydration methods on retention of carotenoids, tocopherols, ascorbic acid and antioxidant activity in Moringa oleifera leaves and preparation of a RTE product. J. Food Sci. Technol. 51 (9), 2176–2182. Sankhalkar, S., 2014. Antioxidant enzyme activity, phenolics and flavonoid content in vegetative and reproductive parts of Moringa oleifera Lam. Am. J. Pharmatech. Res. 4 (3), 255–270. Scorletti, E., Byrne, C.D., 2013. Omega-3 fatty acids, hepatic lipid metabolism, and nonalcoholic fatty liver disease. Ann. Rev. Nutr. 33, 231–248. Sena, L.P., Vanderjagt, D.J., Rivera, C., Tsin, A.T.C., Muhamadu, I., 1998. Analysis of nutritional components of eight famine foods of the Republic of Niger. Plant Food Hum. Nutr. 52, 17–30. Singh, B., Singh, R., Singh, R.L., Prakash, D., Dhakarey, R., Upadhyay, G., Singh, H.B., 2009. Oxidative DNA damage protective activity, antioxidant and anti-quorum sensing potentials of Moringa oleifera. Food Chem. Toxicol. 47, 1109–1116. Teh, S.S., Birch, J., 2013. Physicochemical and quality characteristics of cold-pressed hemp, flax and canola seed oils. J. Food Compos. Anal. 30 (1), 26–31. Verma, A., Vijayakumar, M., Chandra, S., Rao, C., 2009. In vitro and in vivo antioxidant properties of different fractions of Moringa oleifera leaves. Food Chem. Toxicol. 47, 2196–2201. Vongsak, B., Sithisarn, P., Mangmool, S., Thongpraditchote, S., Wongkrajang, Y., Gritsanapan, W., 2013. Maximizing total phenolics, total flavonoids contents and antioxidant activity of Moringa oleifera leaf extract by the appropriate extraction method. J. Indust. Crops and Products 44, 566–571. Willett, W.C., 2012. Dietary fats and coronary heart disease. J. Intern. Med. 272 (1), 13–24. Wilson, J.M., 1979. Drought resistance as related to low temperature stress. In: Lyons, J.M., Graham, D., Raison, J.K. (Eds.), Low Temperature Stress in Crop Plants: The Role of the Membrane. Academic Press, New York, pp. 47–66. Xiao, Z.S., Park, S.H., Chung, O.K., Caley, M.S., Seib, P.A., 2006. Solvent retention capacity values in relation to hard winter wheat and flour properties and straight-dough breadmaking quality. Cereal Chem. 83, 465–471. Zapata, L.M., Gerard, L., Davies, C., Schvab, M., 2007. Estudio de los componentes antioxidantes y actividad antioxidante en tomates. Cienc. Docencia Tecnol (35), 173–193.

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Further Reading Amaducci, S., Gusovius, H.-J., 2010. Hemp—Cultivation, Extraction and Processing. Ind. Appl. Nat. Fibres, 109–134. Bennett, R., Mellon, F., Foidl, N., Pratt, J., Dupont, S., Perkins, L., Kroon, P., 2003. Profiling glucosinolates and phenolics in vegetative and reproductive tissues of the multi-purpose trees Moringa oleifera L. (Horseradish tree) and Moringa stenopetala L. J. Agric. Food Chem. 51, 3546–3553. Duyvejonck, A.E., Lagrain, B., Pareyt, B., Courtin, C.M., Delcour, J.A., 2011. Relative contribution of wheat flour constituents to solvent retention capacity profiles of European wheats. J. Cereal Sci. 53, 312–318. Finnan, J., Styles, D., 2013. Hemp: a more sustainable annaul energy crop for climate and energy policy. Energy Policy 58, 152–162. Gaines, C.S., 2000. Report of the AACC committee on soft wheat flour. Method 56-11. Solvent retention capacity profile. Cereal Foods World. 45, 303–306. Hrušková, M., Hofmanová, T., Švec, I., 2011. Hodnocení vybraných druhů kompozitní mouky. Mlynářské noviny 2, 10–12. Korus, J., Witczak, M., Ziobro, R., Juszczak, L., 2017a. Hemp (Cannabis sativa subsp. sativa) flour and protein preparation as natural nutrients and structure forming agents in starch based gluten-free bread. J. Diet Suppl 84, 143–150. Korus, J., Witczak, M., Ziobro, R., Juszczak, L., 2017b. Hemp (Cannabis sativa subsp. Sativa) flour and protein preparation as natural nutrients and structure forming agents in starch based gluten-free bread. Food Sci. Technol. 84, 143–150. Lemeshev, N., Rumyantseva, L., Clarke, R., C., 1994. Maintenance of Cannabis germplasm in the Valilov Research Institute Gene Bank—1993. J. Int. Hemp Ass. 1 (1), 1–5. Maheshwari, R., Jat, B., Chaudhary, K., Verma, N., 2014. Legitimacy & awesomeness of drumstick tree (Moringa oleifera Lam.) for healthcare & socio-economic perspective. IJCPS 2 (12), 1420–1430. Matthäus, B., Brühl, L., 2008. Virgin hemp seed oil: an interesting niche product. Europ. J. Lipid Sci. Tech. 110 (7), 655–661. Millward, D.J., 2012. Amino acid scoring patterns for protein quality assessment. Br. J. Nutr. 108, 31–43. Moyo, B., Masika, P.J., Hugo, A., Muchenje, V., 2011. Nutritional characterization of Moringa (Moringa oleifera Lam.) leaves. Afr. J. Biotechnol. 10, 12925–12933. Newman, R.K., Newman, C.W., 2008. Barley for Food and Health. Wiley Inc. Publication, New Jersey, pp. 178–194. Petretto, G., Foddai, M., De Nicola, G., Chessa, M., Pintore, G., 2014. Moringa oleifera: study of phenolics and glucosinolates by mass spectrometry. J. Mass Spectrom. 49, 900–910. Rijavec, T., Janjic, S., Acko, D.K., 2017. Revitalization of industrial Hemp Cannabis sativa L. var, sativa in Slovenia: a Study of Green Hemp Fibres. Text Tilec 60 (1), 36–48. Rosell, C.M., Santos, E., Collar, C., 2009. Physico-chemical properties of commercial fibres from different sources: a comparative approach. Food Res. Int. 42, 176–184. Saini, R.K., Shetty, N.P., Giridhar, P., 2014a. GC-FID/MS analysis of fatty acids in Indian cultivars of Moringa oleifera: potential sources of PUFA. J. Am. Oil Chem. Soc. 91, 1029–1034. Saini, R., Shetty, N., Giridhar, P., 2014b. Carotenoid content in vegetative and reproductive parts of commercially grown Moringa oleifera Lam. Cultivars from India by LCAPCI-MS. J. Eur Food Res. Technol. 238, 971–978. Saini, R., Shetty, N., Giridhar, P., 2014c. GC-FID/MS analysis of fatty acids in Indian cultivars of Moringa oleifera: potential sources of PUFA. J. Am. Oil Chem. Soc. 91, 1029–1034.

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Sánchez-Machado, D.I., Núñez-Gastélum, J.A., Reyes-Moreno, C., Ramírez-Wong, B., López-Cervantes, J., 2010. Nutritional quality of edible parts of Moringa oleifera. Food Anal. Methods 3, 175–180. Smeriglio, A., Galati, E.M., Monforte, M.T., Lanuzza, F., D’Angelo, V., Circosta, C., 2016. Polyphenolic compounds and antioxidant activity of cold-pressed seed oil from Finola cultivar of cannabis sativa L. Phytother. Res. 1307, 1298–1307. Švec, I., Hrušková, M., 2014. Evaluation of model wheat/ hemp composites. Potravinárstvo 8, 8–14. Vongsak, B., Sithisarn, P., Wandee Gritsanapan, W., 2014. Simultaneous HPLC quantitative analysis of active compounds in leaves of Moringa oleifera lam. J. Chromatogr. Sci. 52, 641–645.

HOPS: NEW PERSPECTIVES FOR AN OLD BEER INGREDIENT

10

Júlio C. Machado, Jr, Miguel A. Faria, Isabel M.P.L.V.O. Ferreira Department of Chemical Sciences, Laboratory of Bromatology and Hydrology, Faculty of Pharmacy, University of Porto, Porto, Portugal

10.1  What Are Hops? Hops (Humulus lupulus L.) is a perennial climbing plant of the Cannabaceae family. Annually it grows during spring and summer, but has an important wintering period of 6–8  weeks of dormancy with temperatures below 4.4°C. It is a photoperiodic plant, needing around 15 h of daylight, and prefers 6–8 hours of sunshine, in both vegetative growth and flowering stages. Access to water is also very important, but not necessarily from rain, since the water absorption is done through the roots that cannot stay soaked. Hops prefer the soils around the river margins in the cold zones between latitudes 30° and 55°. The best thriving geographical region is between 40° and 50° of the Northern and Southern hemispheres, in Europe, center and north of the United States (USA), Central Asia, Southern Africa, Argentina, and south of Oceania (Hieronymus, 2012; Eyck and Gehring, 2015). Besides the common hop, the Humulus genus includes two other species, Humulus japonicus Siebold & Zucc and Humulus yunnanensis Hu, but only H. lupulus is of industrial and medicinal importance (Hieronymus, 2012). Hop is a dioecious plant, separated into male and female, but only the female ones develop cones (Fig. 10.1). Hop flowers or cones resemble pine cones but are composed of thin, green, papery, leaf-like bracts. Bracts and bracteoles (small bracts) are leaflike structures that surround the entire cone, attached to a central axis. Underneath the bracteoles are the lupulin glands that contain the total resins and essential oils. Besides lupulin, hops cones are composed mainly of cellulose, lignin, water, proteins, monosaccharides, pectins, amino acids, lipids, and wax (Hough et al., 1982). The hop cones being one of the four main beer ingredients, its chemical composition from both wild and cultivated varieties has been Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00010-9 © 2019 Elsevier Inc. All rights reserved.

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Fig. 10.1  . Different views of the hop plants: in intensive production field (A); cones ready to harvest (B); and hop flower exposing lupulin glands (C).

widely studied (Prencipe et al., 2014; Kankolongo Cibaka et al., 2015; Salanţă et al., 2015a). Hydrophobic compounds from hop cones present bitterness, mainly due to α- and β-bitter acids, whereas the characteristic hoppy aroma is provided by the essential oils (Van Opstaele et al., 2011), which are concentrated in lupulin. Consequently, hop is responsible for the bitterness and the specific flavors and aromas of different beer styles. Hop cones also contain biologically active phenolic compounds, which contribute to the preservation and stabilization of the organoleptic characteristics of the beverage, mainly due to its antioxidant, anti-microbiological, and foam stabilization properties. Different fractions can be extracted from hop cones and categorized according to their physicochemical properties (Fig.  10.2). The essential oils are, by definition, the fraction of hops that can be ­isolated by steam distillation. The monoterpene myrcene and the sesquiterpenes, α-humulene and β-caryophyllene, make up the bulk of the essential oil, together with great number of others terpenes, as linalool, farnesene, limonene, pinene, and geraniol among other alcohols, acids, ketones, and aldehydes which contribute to the beer flavor and are quality parameters, and trade preferences of different cultivars of the plant (Eri et al., 2000). Nonvolatile hop resins are characterized by their solubility in cold methanol and diethyl ether. They can be divided according to their solubility in hexane. The insoluble portions are the hard resins, which contain prenylated chalcones and flavanones, such as xanthohumol and prenylnaringenin. However, oxidation products

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Fig. 10.2  Scheme summarizing the separation of hop fractions extracted from hop cones.

derived from α- and/or β-acids were also identified as hard-resin components (Taniguchi et al., 2014). Soft resins are soluble in hexane and contain mainly prenylated phloroglucinol derivatives, such as the α- and β-acids (Steenackers et al., 2015). Commercially hops are usually classified according to the concentration of α-acids. Bitter purpose hops contain more than 5% of α-­acids, whereas aroma hops, appreciated mainly by their aromatic profile, present, on average, an amount of α-acids up to 5%. If the amount of α-acids exceed 10% by weight the bitter varieties are classified as high α (Palmer, 2006). Some bitter hops are also rich in flavor compounds, these varieties have been classified as dual purpose hops, because they have been used to bitter and also to add aroma to beers (Roberts and Wilson, 2006). The majority of the hop crops are used in the brewing industry, as the ingredient that gives characteristic bitterness and aroma to beer. However, its health-promoting effects are well known and hop is used in folk medicine from ancient times. Likewise, the wide range of pharmacological properties described for hop justify that besides brewing, hops and their derivatives are also of interest to the pharmaceutical industry. In addition to antioxidant, anti-inflammatory, and ­anticancerrelated properties, particular attention is being paid to ­prenylflavonoids (xanthohumol, isoxanthohumol, and 8-prenylnaringenin) from hard resin that occur almost exclusively in hops and are considered as the most active phytoestrogens known (De Keukeleire et al., 2001). Hop oils and resins present sedative and other neuropharmacological properties. The main compounds responsible for sedative effects are bitter resins and essential oils. Interesting antibacterial and antifungal

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activities were also reported for β-bitter acids and lupulones, which present a strong antibacterial effect (Čermák et al., 2015). Recent studies describe the effects of α-bitter acids blocking the development of a number of complex lifestyle diseases that are collectively named as “metabolic syndrome” (Karabín et al., 2016). Hops is therefore an interesting and rich source of compounds with applications either in the food industry or in the improvement of human health, due to its pharmacological properties. A brief description of the most relevant groups of compounds is presented below.

10.1.1 Soft Resins: The Bitter Compounds Soft resins are the most studied compounds of hops and assume a paramount importance concerning the bitterness intensity of hops and beer. They are constituted mainly by the prenylphloroglucinols, humulone, and lupulone, together with their derivatives, also known as α- and β-acids, respectively (Chadwick et  al., 2006; Zanoli and Zavatti, 2008). Bitter compounds from the soft resins are described as the main source responsible for the beer bitterness, although nowadays it is not clear whether additional hop components are required to the perception of the complex bitter profile of beer. This issue is presently one of the main active areas within beer research community. Humulones, also known as α-acids, are part of the soft resins and consist of diprenylated phloroglucinol derivatives with variable acyl side. While n-humulone, cohumulone, and adhumulone are the major α-acids in all hop cultivars, other different derivatives have been identified, such as posthumulone, prehumulone, and adprehumulone, whose molecular structures are shown in Fig. 10.3 (Briggs et al., 2004). The α-acids are direct precursors of the main bittering compounds in beer. During the wort boiling of brewing process, they thermally isomerize into iso-α-acids via an acyloin-type ring contraction, resulting in the generation of two epimeric isomers: cis-iso-α-acids and trans-iso-α-acids. Iso-α-acids are mainly responsible for the typical bitter taste of beer, as well as the stability of beer foam and beer preservation properties, due to the antibacterial properties presented by isohumulones (Kowaka and Kokubo, 1976; Clark et  al., 2013; Urban et al., 2013; Almaguer et al., 2014; Steenackers et al., 2015). The residue obtained after isolating the α-acids from a hop extract contains the β-acids fraction that presents a structure highly similar to the α-acids, consisting of triprenylated analogues of the α-acids (Fig.  10.3). The term lupulone is used to identify individual β-acids; a nomenclature similar to that used for the α-acids is used to account for their varying acyl side chains, such as colupulone, n-lupulone, and adlupulone (Steenackers et al., 2015). The β-acids are considered virtually irrelevant for the brewing industry. Having an extra isoprenyl

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Fig. 10.3  Chemical structures of some soft resin components, α- and β-bitter acids, and their isomerization (worth boiling) and oxidation (natural peroxidation) products.

side chain they are significantly more hydrophobic than the α-acids, and practically insoluble in aqueous media, which is the beer matrix (Briggs et al., 2004). However, the β extract can be used as a raw material for the production of industrial bittering components, either by the transformation of the β-acids into the synthetic iso-α-acids or by their oxidation into the hulupones. Humulinones and hulupones are other two important groups of compounds that are formed by the oxidation of α- and β-acids, respectively. Although they were discovered a long time ago (Cook and Harris, 1950; Spetsig and Steninger, 1960), the interest in these compounds returned. Recent findings have demonstrated that humulinones and hulupones have a great potential for bitterness, even though less bitter than iso-α-acids, they are more polar, therefore more soluble in beer, therefore present a significant impact on beer bitterness (Algazzali and Shellhammer, 2016; Oladokun et al., 2016). The concentration of α-acids varies from values, as low as 2%–5% of total dry weight to up than 10% reaching values as high as 14%–20%

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in the high α varieties. β-acids generally appear in concentration lower than α-acids, on average ranging about 4%–6% of dry weight, however, may vary up to 10%. Humulinones are present in hops most commonly at a concentration of 0.2%–2%, and hulupones less than 0.5% by weight.

10.1.2  Hard Resins: Xanthohumol and Derivatives Compared with the soft resins, the hard resins of hops are composed of more polar compounds, reflecting their insolubility in hexane. They contain a complex mixture of polyphenols, namely, ­proanthocyanidins, flavonol glycosides, prenylchalcones, with xanthohumol and desmethylxanthohumol being the most important molecules of the group, and also prenylflavanones, as isoxanthohumol, 6-prenylnaringenin, and 8-prenylnaringenin (Fig. 10.4). These compounds are recognized as presenting beneficial health properties, in particular antioxidant, anti-inflammatory, anticancer, immunomodulatory, and antimicrobial (Henley et al., 2014; Machado et  al., 2017) properties. Prenylchalcones, particularly, received much attention in the last years due to its potent chemopreventive ­properties. Xanthohumol is a promising anticancer agent, whereas 8-­ prenylnaringenin, the demethylated derivative of isoxanthohumol, has been the target of several research works due to its potent

Fig. 10.4  Chemical structures of prenylflavonoids xanthohumol, isoxanthohumol, desmethylxanthohumol, 6-prenylnaringenin, and 8-prenylnaringenin.

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­ hytoestrogenic activity (Milligan et  al., 1999; Schaefer et  al., 2003; p Stevens and Page, 2004). Dry hops may contain up to 1% of dry weight of xanthohumol while 8-prenylnaringenin is usually present in concentrations lower than 10 mg/100 g. Although beer bitterness is traditionally attributed to the soft resin compounds, some hard resin molecules had recently been ­considered as contributors to the bitter taste of beer. This is the case of xanthohumol and its isomerization product isoxanthohumol as well as desmethylxanthohumol and isomerization products of 8-­ prenylnaringenin and 6-prenylnaringenin, by coactivation of some of the tongue bitter taste receptors (Dresel et  al., 2015a). In fact, it was reported that brewing beer using the isolated hop hard resins fraction was found to give beverages a strong and pleasant bitter character, indicating the presence of additional valuable bitter compounds in the hard resin (Almaguer et al., 2012).

10.1.3 Volatile Fraction The hop aroma is another desirable feature of beer and is directly associated with the presence of the essential oils, formed by a complex group of compounds, where around 440 molecules have already been identified. Nevertheless, more recent analysis using comprehensive multidimensional gas chromatography (GC × GC) with flame ionization detection suggested that more than 1000 compounds can be found in this fraction (Almaguer et al., 2014). The main constituents include a highly diverse group of esters and terpenes. The monoterpene β-myrcene, together with the sesquiterpenes α-humulene and β-caryophyllene are the predominant components in mass terms. Although in smaller amounts, other chemical groups are also present, such as aldehydes, aliphatic hydrocarbons, carboxylic acids, esters, furans, higher alcohols, ketones, phenols and sulfur compounds (Moir, 2000; Gonçalves et al., 2014; Salanţă et al., 2015b; Liu et al., 2017). The noble hop aromas are typically classified by sensorial analysis and olfactometry trials according to specific descriptors, which fall within the categories of citrus, fruity, floral, spicy, resinous (woody aromatic), herbal, and cream caramel or sweet-like (Table 10.1). Over the years the chemical characterization and quantification of the compounds associated with aroma attributes has been performed. Monoterpenes are associated with citric, spicy, resinous, and herbaceous categories; the sesquiterpenes are associated with spices and woods, the esters with fruits and sweets-like odors, ketones with floral notes, and aldehydes with grassy/green attributes (Steinhaus and Schieberle, 2000; Eyres et al., 2007; Van Opstaele et al., 2012; Kankolongo Cibaka et al., 2015). This complexity is tentatively resumed in Fig. 10.5, which gives an overview of the main groups of

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Table 10.1  Common Aroma Descriptors and Odor Qualities Attributed to Hops in Sensorial and Olfactometry Analyses Odour Quality Citrus Fruity

Aroma Descriptors Green fruits Red berries Sweet fruits

Floral Spicy Resinous (woody aromatic) Herbal

Herbal Menthol Green grassy Vegetal

Cream caramel (sweet-like)

Grapefruit, orange, lime, lemon, bergamot, lemongrass, ginger, tangerine Pear, quince, apple, gooseberry, wine white grape Cassis, blueberry, raspberry, blackberry, strawberry, cranberry, red currant, black currant Banana, watermelon, honeydew melon, peach, apricot, passion fruit, lychee, dried fruit, plum, pineapple, cherry, kiwi, mango, guava Elderflower, camomile blossom, apple blossom, lily, lily of the valley, lilac, jasmine, rose, geranium, carnation, lavender Pepper, chilli, curry, juniper, aniseed, liquorice, fennel seed, clove, cinnamon, gingerbread, coriander seed, nutmeg Tobacco, cognac, barrique, leather, tonka, woodruff, incense, myrrh, resin, cedar, pine, earth Lovage, marjoram, tarragon, dill, thyme, rosemary, basil, parsley, fennel, coriander, sage, tea, green tea, black tea, mate tea Mint, melissa, camphor, balm, wine yeast Grass, tomato leaves, green pepper, nettle, hay, cucumber Celery root, celery stock, leek, onion, artichoke, garlic, wild garlic Butter, chocolate, yogurt, honey, cream, caramel, toffee, coffee, tonka bean, vanilla

compounds forming the hops aroma, the principal chemical components, and the odors attributed to each molecule alone. Inside the terpenes group, oxygenated monoterpenoids (citrus and floral), such as linalool, citronellol, and geraniol as well as oxygenated sesquiterpenoids, caryophyllene and humulene-derived epoxides (spices and herbaceous), had received special attention due to their solubility and stability. Although their amounts in hops are low they represent the most relevant compounds that remain in the final beers, especially when hops are introduced in the boiling kettle stage of brewing, which corresponds to the more traditional approach of hop usage (Peacock and Deinzer, 1981; Lermusieau et al., 2001; Takoi et al., 2010). Once they are present in different concentration among the hop varieties, it is not clear if these derivatives are mainly formed by oxidation during hop storage or by chemical transformation during wort boiling (Goiris et al., 2002).

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Fig. 10.5  Main aromatic compounds of hops and the corresponding odor description.

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Late hop addition in the last 5–10 min of boiling enhances beer aroma, but even this technique lead to losses of some aromatic oils that evaporate rapidly in the boil. Greater extraction and retention of volatile compounds in beer is observed when hops are added at the cold stages of brewing (Dresel et  al., 2015b; Schnaitter et  al., 2016), which significantly affects the aroma of those beers. Dry hopping involves adding hops to the fermenter or after fermentation. This technique adds aromatic compounds that are normally lost in the boiling process, but it does not increase beer bitterness. Dry hops are allowed to soak in the finished beer for several days or even several weeks. The result is a great increase in hoppy aroma. Nevertheless, due to the high variation among varieties and the intrinsic complexity of the hop oil, as well as the diversity of brewing processes, together with the lack of standardization of analytical methods for the analysis of individual volatile compounds, it was not possible until now to identify all the individual hop components that impart the noble hop aroma. Moreover, the exact contribution of each compound to the specific sensorial quality of beers is not known, which constitutes another hot subject on hops and beer research.

10.1.4  Hop Varieties Hop is usually propagated via vegetative cuttings, that is, stem/leaf and most commonly rhizomes, following a clonal propagation system for varietal distribution. The female inflorescence or cone is the product of interest for the brewing industry. Male plants are only required for breeding purposes, since male pollen is needed to fertilize the female inflorescence when the search for new plants derived from natural genetic recombination is pretended. Female plants produce cones without pollination, therefore in hop fields there are only female plants (Henning et al., 2015). In fact, the presence of male plants in the surroundings is even undesired as their pollen can be dispersed via air flow and pollinate females, which will produce seeded inflorescences, not desired by brewers. The organoleptic features of the resulting hop will be affected due to the seed compounds. Hops present a high varietal diversity, as observed for most of the cultivated plant species. Hundreds of hop varieties are known nowadays. Some hops received special attention. Typical hops, like the English Goldings and Fuggles, are named as “noble hops,” but some varieties of hops from Hallertau, Spalt, and Hersbruck regions of Germany and the traditional Saaz, grown in the Czech Republic, also became famous and have been largely used. Notwithstanding, due to the actual changes in brewery practices, there has been an intensive search for new varieties of the plant, dubbed “Green Gold.” Therefore, a large number of new varieties have been developed, characterized, and increasingly commercialized. This is the case of the German hops Perle and Herkules,

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the American Centennial, Cascade, Amarillo, Simcoe, Citra, as well as new varieties out of the axis England/Germany/United States, for example, Nelson Sauvin from New Zealand. Fig. 10.6 presents the main hop commercial varieties that are available in the market in the form of pellets, taking into consideration its importance throughout the history and its current or potential market share. Varieties are distributed in a bitter scale (% of α-acids), but information regarding their aroma profile, country of origin, and the most common uses are also added. The selected hops when merged, account for more than 80% of the current world harvest. Besides the sensorial aspects, hops varieties also differ botanically (since different size and forms of leaves and cones can be observed) and agronomically, due to variation in soils adaptation, yields, time of maturity, and resistance against pests and diseases. Qualitative and quantitative differences are observed on chemical composition of different hop varieties. Plants may also present relevant differences when the same variety is cultivated in different regions that have different soil and climate conditions. Moreover, even when planted in the same edaphoclimatic conditions, the hops may present different composition in diverse years of production due to climatic variations. Thus, it is very important, and a common practice after each crop, to perform the chemical characterization of the harvest. The American Society of Brewing Chemists (ASBC) and the European Brewery Convention (EBC) are two main committees that standardize the analytic methods used during the brewing process (namely, wort analysis and microbiological control) to control beer quality, as well as the analytic methods to be applied for the analysis of raw materials, including hops, water, barley, and yeast. One of the most important parameters to be evaluated in hops is the percentage of bitter acids. Since the early 1980s, the analysis of specific acids has been increasingly performed by high-performance liquid chromatography (HPLC), although spectrophotometric and lead conductance titration methods are also largely used (titration based on the reaction of their ionized forms with lead salts). Both committees, ASBC and EBC, describe HPLC as the International Method to provide α- and β-acid concentrations by using the International Calibration Extract (ICE). This is a mixture with known concentrations of α- and β-acids, provided by the ASBC and the EBC, together with the Institute and Guild of Brewing and the Brewery Convention of Japan in collaboration with the hop industry. Thus the individual concentrations of some compounds that are chromatographically separated can be measured, as is the case of cohumulone and colupulone (ASBC Methods of Analysis, 2008b; Analytica-EBC, 2012). Notwithstanding, due to the lack of specific equipment in most of the laboratories used for hop analysis, the most common method used for bitter acid analysis is still the UV spectrometry. Bitter acids

Fig. 10.6  Hop varieties displayed according to the average of α-acids %, including information regarding their aroma profile, country of origin, and the purposes of most common uses. Green, red, and blue represent aroma, bitter, and dual purpose hops, respectively.

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are determined after extraction with an organic solvent. The ASBC method indicates extraction with toluene and further treatment with methanol for the separation of α-acids and an alkaline methanol extraction for β-acids. However, the method suffers interferences from the oxidation products of α- and β-acids, thus, it is proposed to measure the absorbance at the wavelengths of 355, 325, and 275 nm, and undertake mathematical corrections to reduce errors (ASBC Methods of Analysis, 2008c). The Hop Storage Index (HSI) is another important parameter for brewers and is used to determine hop oxidation levels that can occur during hop storage. The HSI increases when inadequate storage conditions are applied. The spectrophotometric method is also used to evaluate HSI, which is calculated throughout the progressive increase in the ratio of absorbance at 275–325 nm in the alkaline methanol extract (ASBC Methods of Analysis, 2008a). Although less used in hops characterization, the measurement of total polyphenols content (TPC) is also important, considering its technological impact and health effects due to their bioactive properties. The TPC is generally determined by spectrophotometry (Analytica-EBC, 2015). However, HPLC is the preferred method to quantify individual flavonoid compounds of hops and also to monitor their progress in hop products and beers. Several methodologies have been developed coupling HPLC with ultraviolet (UV), diode array detection (DAD), and mass spectrometry (MS/MS) (Magalhães et  al., 2007; Intelmann et al., 2009; Kao and Wu, 2013). The composition of essential oils from hops has been extensively studied since Chapman’s early classical chemical techniques (1895–1929). Advances in gas chromatography, including high-resolution capillary columns and the coupling mass spectrometry detector (GC-MS), first reported in 1963, by Buttery, provided more detailed information about the profile. Chromatographic fingerprint analysis of hop ­volatile fraction by gas chromatography and mass spectrometry can be a useful tool for variety authentication and for quality evaluation. Over 400 compounds can be separated and estimated in one single run by GC-MS analysis of essential oils from hops, which enables a comparative study of different plants by chromatographic profiling or quantification (Kovačevič and Kač, 2001; Jorge and Trugo, 2003). The steam distillation method is commonly used to obtain hop essential oil, however, it requires a relatively large amount of sample (50–100 g) and is time consuming (Analytica-EBC, 2002; ASBC Methods of Analysis, 2008b; Ligor et al., 2014). The use of headspace sampling allows the analysis of a high number of samples in a relative short period of time and is easily automated. Different headspace methods can be used, involving minimal sample preparation and rapid enrichment of volatile or semivolatile compounds during the headspace analysis.

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Several headspace techniques were used for the determination of ­volatile compounds in hops (Field et  al., 1996; Van Opstaele et  al., 2012; Zapata et al., 2012). Headspace methods include dynamic sampling method such as in-tube extraction or static methods, namely solid-phase microextraction (SPME) (Socaci et al., 2013). The chemical analyses of the essential oil and resin components evaluate hops quality, and can give valuable information to sustain the botanical identification of hop varieties. However, varietal identification only by the analyses of the chemical composition of hops usually involves detailed statistical treatment by chemometric analyses, in order to distinguish from similar varieties (Mongelli et  al., 2015), and do not provide an unequivocal identification of the varietal due to the phenotypical changes between harvests.

10.2  New Trends of Hop Uses 10.2.1 The Craft Brewery Movement The historical worldwide restrictions on alcohol consumption at the end of the 19th century and beginning of the 20th century, added by the two big world wars, resulted in a drastic drop in beer companies based in traditional beer producing countries. For example, in Belgium, breweries decreased from 3223 before the first war to 755 in 1946; in the United States, breweries decreased from 2300 in 1880 to 160 at the beginning of World War II and to 60 at the early 1960s; whereas in the United Kingdom, there were 6447 breweries in 1900, which reduced to 885 in 1939 and to 358 in 1960 (Morado, 2009). On the one hand, after the World War II, a climate of rebirth emerged in all sectors of society, the world was affected with globalization of markets (remembering that internet began in 1955, and opened the network to commercial interests in 1988), promoting the gigantism of companies and products massification. In the beer market, the brewer’s master became hostage of the marketing departments, product changes were directed expressly to increase sales volume and profits, resulting in the production, in large scale, of the so-called Standard American and International Lager styles with low costs of production, simplicity in flavors, and designed to appeal to mass-market drinkers (Blake et al., 2015). Moreover, there is a growing concern about its environmental sustainability, which induced a change in consumer’s point of view, becoming more and more demanding. Nowadays, consumers look for products that are healthy, ecologically sustainable and present with good quality, paying attention to novelties and sophistications. This is accompanied by the proliferation of small producers offering diversification and experimentations. The brew sector

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observed the European brewery renaissance, stands out the movement Campaign for Real Ale (CAMRA, begin in 1971), and the North American development with a big wave of microbreweries and homebrewers. Rescuing creativity and dynamism from a dormant tradition, since then, different ingredients (species and varieties) and process have been used by brewers to produce new styles of beers and different variations of traditional styles.

10.2.2 Forms of Hop Usage A large increase in hops quantities and varieties was verified in the last decades to produce richer flavored beers. The confirmation of the success of this new phase is the large worldwide consumption of the beer style American India Pale Ale (IPA). In this kind of beer the American varieties of hops are the main components, providing bitterness and floral, fruity, sulfur/iesel-like, citrus, and resinous aromas and flavors. In general, there is an increase of beer recipes where the essential oil of hops becomes very important, together with the concern in transpose the hop aromas to the beer. In this way, it has been noticed that not only hop characteristics impart distinct beer flavor, but also the amount added, the time of addition, and brewing method influence beer flavor (Barth-Haas Group, 2012). Moreover, the old practice of introducing the hops only during the wort boiling is not very efficient to retain hop flavor, since volatile components are evaporated or chemically changed, whereas the dry hopping techniques that add hops after the boiling phase of the brewing process, at cold stages are increasingly been used by the breweries (Blake et al., 2015; Gatza et al., 2017). The extraction of some particular flavors can be a challenge for the brewers, for instance, the fruity aroma of the Australian variety Galaxy is more easily achieved if the hops are added at a later stage during the boiling process and is only lightly noticed if hops are added in dry-hoping, contrary to the expected higher efficiency of dry-hoping in aroma extraction. Another example is the German variety Saphir that can exhibit from low to very strong citrus or even spicy and herbal aromas depending on the type of beer being produced (Barth-Haas Group, 2012). The microbreweries are a new market trend and a promoter for the development of new hop varieties. Microbreweries use about 10 times more quantities of hops per liter when compared with the traditional big beer companies. In addition, microbrewers use a much bigger spectrum of cultivars (Martins, 2015) which is a strong motivation for academic research, hop research institutes, and hop producers and will certainly encourage a bloom in hop varietal new releases in the mid-term.

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Table 10.2  Types of Hop Products Commercialized Nowadays and Respective Preparation Process Hops Products

Process of Prepare

Fresh cones Dried cones Pellets Extracts

Pure state Dried and pressed Dried, ground, and pressed Extracted from pellets or cones by supercritical CO2 extraction, nitrogen-rich atmosphere, ethanol, or distillation methods

10.2.3  Hops Products Hops are commercialized in cones which can be in pure state after the harvest or dried and pressed. However, due to the logistic of transporting and storage, there are smaller and more stable forms, such as hop pellets, produced from dried milled and pressed inflorescence with vegetative content and extract-derived products (Table 10.2). Big breweries, produce mass-market products and generally use hops only to reach bitterness and prefer enriched α-acids obtained from supercritical CO2 extraction. On the other hand, the raw materials used by small breweries are closer to the natural forms, thus provide a higher complexity of flavor to the final product, when compared with hop products derived from extraction, mainly because part of the volatile fraction is lost during the extraction methodologies. This is another aspect that is favoring the cultivation of new hop varieties and the emergence of small farms (Martins, 2015; Rodrigues and Sá Morais, 2015).

10.3 Market According to data from beer sector, hop plantation has been a profitable investment and a factor of regional development, and so, increasingly, countries have invested in this sector. Beer is the alcoholic beverage that is most consumed in the world. Interrupting growth since 1998, it was in 2014 the beer market first registered a drop in world production, down of 0.5% in relation with 2013, when 1.96 billion hectoliters of beers were produced, since then, production has stagnated around this value (Statista, 2017). In addition, it is important to emphasize that the craft beer market, managed by small breweries, has been growing strongly over the past few years. In the United States there are 5234 microbreweries

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(craft breweries), traditional and independent, with a maximal annual production of 6 million barrels (approximately 715.4 million liters) (Brewers Association, 2017), which in 2016 accounted for a growth of 6% in volume of production, already accounting for 12.3% of the total beer market, reaching a financial turnover of US $ 23.5 billion (Watson and Herz, 2017). In the UK, in 2015, microbreweries amounted to 1828 in a total of 1,880 breweries. Data from the same year indicate 717 craft breweries in Germany and, even in countries with strong wine of expression, and little beer expression until recently, such as France and Italy, the number of breweries doubled in the last 5 years, ending in 2015, with 690 and 540 microbreweries, respectively. Switzerland had 280 microbreweries in 2014, 573 in 2015; in Spain the number of microbreweries exploded from 46 to 409 in the same period. In Portugal, the first craft brewery appeared in 2011, and in 2015 there were 60 breweries (The Brewers of Europe, 2016). In Brazil, since 1999, the market has grown around 10%–12% per year, and today there are more than 400 registered microbreweries that produce about 1.3 million hectoliters per year (Barth-Haas Group and Germain Hansmaennel, 2013). During the last 5 years the world beer production remained virtually stable, which could be a concern for hop market, nevertheless, after a long period of decrease, in the last 3 years the global area of hop cultivation increased, and the amount harvested increased 21.4% compared with 2013, although the total production of beer has fallen 0.76% in the same period. These data corroborate the increase in hop ratio per liter of beer, typical of craft brew sector (Hintermeier, 2016). Concerning world hop acreage in 2016, growth was around 9%, an increase of 4,629 ha, amounting to a total area of 56,141 ha of hops plantation. This was the second greatest expansion of acreage in the past 26 years, the greatest was in 2008, when the expansion was about 13.6%, reaching a peak of 57,297 ha. From this year, the next 5 year was decline of plantation, only resuming growth in 2014 (Fig.  10.7) (Barth-Haas Group, 2017). In 2017, the estimated greatest world acreage area of all time was close to 58,000 ha (Economic Commission of IHGC, 2017).

10.3.1 World Production There is a serial of governmental and nongovernmental organizations that give support to the hop growers, like the private company Joh. Barth & Sohn GmbH & Co KG, the Verband Deutscher Hopfenpflanzer e. V. (Association of German Hop Growers), the International Hop Growers’ Convention (IHGC), the Slovenian Institute of Hop Research and Brewing (IHPS) and the National Agricultural Statistics Service (NASS) from United States Department of Agriculture (USDA). The data summarized in this section is a compilation of the last reports (Verband Deutscher Hopfenpflanzer e.V., 2015a, 2015b; National Agricultural Statistics Service, 2016; Barth-Haas Group, 2017).

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Fig. 10.7  World hop production, [····] area in hectares, [½] megatones and [½] beer production in millions of liters. Adapted from Barth-Haas Group, 2017. The Barth Report. Nuremberg.

About 70% of world crops are in the two main hop growing countries, Germany and the United States. During many years Germany was isolated as the main hop-producing country. Confronted a sequence of decline in hop acreage between 2009 and 2013, however, the tendency was inverted in 2014, where 1,192 farms cultivated 17,308 ha of hop. In 2015, the number has increased to 17,855, and to 18,598 in 2016, and in 2017 19,543 ha of hops was estimated to be cultivated. The main hop-producing region is Hallertau in Bayern, in the last year about 83.4% of German hops have been cultivated, in addition, there are four more regions of hop harvest: Elbe-Saale (7.5%), Tettnang (7.0%), Spalt (2.0%), and Rheinpfalz/Bitburg Hochdorf/RHW (0.1%). After long a period of investment, studies, breedings and research, the United States has produced a great number of hop varieties and in 2016 overtook Germany and became the country with the highest number of hectares planted with hops in the world (Fig.  10.8). Although the total production still is lower due the better yield of Germany. There are three main hop-growing regions in the country, Washington represents about 70% of US acreage, Oregon 15%, Idaho 10%, and others states 5%. In both countries, German and United States, there is more emphasis on aroma hops. In Germany around 57% of aroma and 43%

Chapter 10  Hops: New Perspectives for an Old Beer Ingredient   285

Fig. 10.8  Comparison of last 5 years of crops of hops, in hectares, in Germany and United States. Continue, dotted, and dashed lines represent total, aroma, and bitter/high α crops, respectively.

of ­bitter/high α varieties are cultivated, almost no oscillations were noted, only slight consecutive increases in the last 4 years for aroma varieties and in the last 2 years for bitter/high α varieties were observed. The traditional varieties like Perle, Hallertauer Tradition (aroma), Herkules and Hallertauer Magnum (bitter/high α) were predominant. In accordance with the craft brew sector, over the past 5 years the US producers reduced the harvest of bitter/high α varieties and changed to aroma hops (Fig. 10.9). In this period, 3310 ha of bitter/high α varieties have been removed from hop farms, while aroma varieties acreage has grown more than three times, from 5123 ha in 2012 to 16,092 ha in 2016, which represents nearly 80% of the total US hop acreage; it was forecasted have more than 1690 ha of aroma varieties in 2017, keep dropping the bitter/high α varieties (Fig. 10.8). The same tendency in harvest balance of aroma and bitter hops can be observed in the whole world. Czech Republic is the third largest producer of hops, and is the most important producer of Saaz, a famous aroma variety largely used in the Lager Beer Style that dominates the world beer market share. The Saaz crops are about 88%, and other varieties such as Sládek, Premiant (aroma) and Agnus (bitter/ high α) complete the acreage of Czech Republic. The country has planted more than 6000 ha at the beginning of the century, however, it has presented a decline in acreage over the years, to 4319 ha in 2013,

286  Chapter 10  Hops: New Perspectives for an Old Beer Ingredient

Fig. 10.9  Acreage (ha) for the main hops varieties in 2017 in (on top) Germany and (below) United States. Light and dark green colors represent aroma and bitter/high α purposes of varieties, respectively.

Chapter 10  Hops: New Perspectives for an Old Beer Ingredient   287

which represents a decrease of 29%, however, in 2014 the growth was reassumed. The statistics on acreage and production volume in China are based on estimates on the size of the Chinese hop-growing regions of 37 farms in two regions, Xinjiang and Gansu, which together produced 7101.4 mt in 2639 ha, keeping China in the top yield list, and in fourth colocation on the rank of world production. Estimates indicate that the main production, more than 60%, is of the bitter variety Tsingtao Flower. Poland and Slovenia added to the four main producers constitute over 90% of hop harvest in the world (Fig. 10.9). In Poland producers are particularly investing in the aroma varieties Lublin and Sybilla. For bitter/high α varieties, there is still interest in the Hallertauer Magnum variety, however, there is a year-on-year increase in recent Polish high α varieties Marynka and Magnat. Slovenia also through a growing moment in hop production, with great success on the fine aroma varieties such as Celeia, Aurora, Savinjski Golding, and Bobek. The year 2016 marked the end of 4 years of decline in hop crops in England. Old aroma varieties, well known to make ingredients for the production of historical English Ale Beer Styles, mainly Golding, First Gold, East Kent Golding, Fuggle, Progress, Sovereign and Challenger, in addition to other aroma varieties, domain the plantations with more than 75% of harvested area. Target and Pilgrim are the high α varieties that were more cropped. In Oceania high α Galaxy™, Super Pride, Pride of Ringwood, and Topaz™ are the main varieties found in Australia together with the aroma variety Ella™, and the new aroma variety Enigma™ (BarthHass Group, 2015). New Zealand cultivation is dominated by Nelson Sauvin, Motueka, and Wakatu varieties, mostly organic harvest, designated to fresh uses with the objective of impairing higher aroma quality (Donelan, 2017). The number of hop growers in Spain has been declining since 2011, however, there is an inventiveness to introduce hop growing in new regions. A project is already taken place in the provinces of Galicia and Catalonia. The main hops cultivated in Spain are Nugget, Columbus, and Hallertauer Magnum. There is low cultivation of aroma varieties. The sum of hop production by other hop-producing countries does not reach 5% of the total world hop volume (Fig. 10.10). The most popular aroma varieties of South Africa are Southern Aroma, Southern Passion, and J17-African Queen. Other varieties that have also been developed in the country include Southern Brewer, Southern Star, Southern Dawn, and Southern Promise. Alsace dominates the hop cultures in France, having a little production also in the north of France. Aroma hops are predominant, Strisselspalt, Aramis, Triskel. and the recent Barbe Rouge are the main varieties. There is scarce ­information

288  Chapter 10  Hops: New Perspectives for an Old Beer Ingredient

Germany USA

21570

Czech Republic

4775

China

2639

England Australia

948 540

South Africa

864 395

New Zealand

794 412 772 459 479 249 380 380

Austria Ukraine* Turkey Japan

Russia Belgium

198 147

Slovakia

187 147

Romania

180 260

Canada*

155 137 86 58 40 22

Belarus Bulgaria* Switzerland Portugal Netherlands

7101

261 297 245 133 232 167 214 300

Argentina

7712

2476 1484 1424 920 1105 546

Spain

France

40206

3044 1475

Poland Slovenia

42766

18598

29 17 14 12 2 2

Fig. 10.10  World hop production in megatons (dark bars) and acreage (light bars) in hectares. Data from 2016, estimation. Adapted from Barth-Haas Group, 2017. The Barth Report. Nuremberg; Economic Commission of IHGC 2017. Summary Reports, Int. HOP Grow. Conv. Yakima.

concerning Ukrainian hop plantations; Zagrava, Promin, Magnat, and Clone-18 are the well-known hops grown in Ukrainian (Ukrainian Academy of Agrarian Sciences, Institute of Plant Production n.a. V.Y. Yuriev and National Centre for Plant Genetic Resources of Ukraine, 2008; Peacock, 2011). In general, worldwide high α acids acreage has been reduced while aroma acreage is increasing. In 2017, the estimation is that cropped hops will be around 58,000 ha of acreage, this being more than 67% of aroma varieties.

Chapter 10  Hops: New Perspectives for an Old Beer Ingredient   289

In Portugal the hop acreage has reduced to 12 ha around of the city of Bragança, in the northeast region of the country, which produced 13.7 mt of hops in 2016, representing only 2.5% of the country's need. However, the region has shown great interest to become again a leading producer of hops, as it was in the past decades. The peak of hop production was in 1976, 205.8 ha were cultivated which produced 438.1 mt of hops, which generated self-sufficiency in Portugal producing 100% of the needs for breweries and still left to export. Recent history showed that the Northern Portugal has ecological potential to compete with productivity and quality in the international market of the largest producers of hops in the world. In this sense, actions have been taken to sensitize farmers, entrepreneurs, and authorities with regard to the restructuring of the hop sector. There are some initiatives in development, and projects for the selection of new cultivars adapted to the region, demonstrating that there are conditions to attract new producers of hops (Rodrigues and Sá Morais, 2015).

10.3.2  Hops Business The growth of craft beer movement promoted that the aroma varieties are the most valued in the market, however the market prices of high α varieties continue to rise, which can be justified by the fact that the volume of α varieties produced has not been sufficient to meet the demand. The influence of microbreweries is again unnoticed, once the characteristic of this brew sector favors more flavored beers, beer produced by craft beer can be more aromatic and also more bitter than the beer produced by the big companies. Thus, even in the absence of growth of beer production, in the last years the rate of α-acids per ­hectoliter of beer rose from 4.68 g (in 2013) to 5.61 g (in 2017), promoting the demand of α-acids, however, the world supply along the years, provided mainly German high α-acids hop, which has been insufficient to compensate US hop plantation changes (Barth-Haas Group, 2017). The annual high demands of hops, all varieties, have increased the prices, and made the plant, more and more, a profitable crop, being common to have forward contracts between the hop growers and purchasers. In Germany and in other countries of the European Union (EU) normally the trade is with hops dealers, whereas in the United States the activity is directly with the brewers (Barth-Haas Group, 2017). Table  10.3 summarizes trade prices to highlight the differences in 2 years of market. There was a considerable rise in the prices in the market, being aroma varieties more valued than bitter, and the American varieties presenting higher prices. Another difference in the two biggest markets is that in the EU the contracts have long periods of extension, normally reaching more than 5 years forward, and growers trade practically the full production,

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Table 10.3  Trade Prices of Hops Market in 2014 and 2016 (Barth-Haas Group, 2015, 2017) High alpha varieties Nugget Hallertau Magnum Aroma varieties Hallertau Mittelfrueh Tettnang Hersbruck Spaet Perle Spalt Select and Saphir Saaz Lublin Aurora Celeia Savinjski Golding Cascade Centennial Average EUR per kg of α acids High α varieties High α varieties Average growers returns in aroma varieties (EUR/ha) Public Registered and trade marked

Origen (Production)

Forward contracts (EUR/kg)

Spot market (EUR/kg)

2014 4.50 4.50

2016 5.00 6.35

2014

2016

Germany Germany Germany Germany Germany Germany Germany Czech Republic Poland Slovenia Slovenia Slovenia USA USA

7.50 8.00 6.00 5.3 5.50 7.60 4.75 3.80 4.20 6.40 9.50 11.90

13.00 15.00 7.50 7.00 7.50 10.00 6.50 6.00 7.50 9.00 14.25 17.50

7.00 9.00 6.00 4.80 5.50 9.00 5.90 9.00 9.00 9.00 15.80 23.80

12.00 12.50 7.50 6.70 8.30 10.90 7.00 8.00 9.00 10.00 11.60 17.50

Germany USA

43.55

45.25

39.50

45.50 49.50

USA USA

18,000 21,600

32,500

having short marge for spot market, only if there is a good crop, with a high yield. While in the United States, normally contracts are not so long and there are more hops for spot market (Table 10.4).

10.4  New Discoveries in Hops Research 10.4.1 Bioactivity Hops has been used as a medicinal plant for more than 2000 years against leprosy, constipation, foot odor, and to purify the blood (Koetter and Biendl, 2010). The bioactivity of several hop compounds

Chapter 10  Hops: New Perspectives for an Old Beer Ingredient   291

Table 10.4  Forward Contract Rates Predicted for 2018–2020 Germany Czech Republic Slovenia Poland England France USA Australia

2018 (%)

2019 (%)

2020 (%)

95 95 85 75 90 90 90 80

90 95 75 65 90 80 65 50

85 90 70 60 90 70 40 40

Adapted from Barth-Haas Group, 2017. The Barth Report. Nuremberg.

present in hard and soft resins is, thus, well known and widely studied, giving rise to some good revision works on the subject (Hudcová et al., 2014; Karabín et  al., 2016). Beneficial effects on the human health are mainly related to the antioxidant (polyphenols and bitter acids), antimicrobial (bitter acids, polyphenols and essential oils), and sedative (resins and oil) effects, as well as, for the prevention of neurodegenerative (naringenin, xanthohumol) and cardiovascular disorders (polyphenols) and to estrogenic (8-prenylnaringenin), antiproliferative (xanthohumol, kaempferol, 8-prenylnaringenin), antiangiogenic (xanthohumol and isoxanthohumol), and antinflamatory (xanthohumol and 8-prenylnaringenin) activities (Karabín et al., 2016; Machado et al., 2017). Notwithstanding, in the last few years, some newly discovered molecules have been described and their effects on health have been studied as promising phytotherapeutic agents reaffirming the high potential of the plant as a source of new molecules. One of those classes of new compounds are the humulinones (Fig.  10.4), naturally formed by the oxidation of α-acids in the hop cone, which occurs promptly during storage. Hops with higher HSI are rich in humulinones (Maye et  al., 2016). Bitter acid oxidation products had already been obtained by chemical oxidation of isolated α- or β-acids but their occurrence in hop cones have remained uncertain until recently (Taniguchi et  al., 2013). Chemically, humulinones are hydroxylated iso-α-acids, thus, more polar and soluble in beer, and were reported to be between 0.2% and 0.5% by weight, in several hop pellets and whole leaf, whereas hop extracts contain none. Although with lesser bittering intensity than iso-α-acids they can contribute to

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the beer overall bitterness when used in dry hopping since over 87% of all the humulinone molecules will dissolve in the beer after 2–3 days of extraction (Maye et al., 2016). Besides its importance in bitterness, humulinones probably present high biological activity due to their similarity with the molecules of α-acids, notwithstanding, their potential health benefits are not well understood (Taniguchi et al., 2015). The most important metabolites of α-acids were identified as humulinones and hulupones. Interestingly, the phase I metabolites are highly similar to the oxidative degradation products in hops and beer (Cattoor et  al., 2013). These findings show a first insight into the metabolites of hop-derived bitter acids and may have practical implications in the bioavailability of these compounds, following ingestion of hop-based products (Cattoor et al., 2013). Hulupones are formed from the oxidation of β-acids (Fig. 10.4), in the hop cone as well as during boiling, however in a small amounts, and also contribute to the bitter taste (Haseleu et  al., 2009). Hulupones are also promising bioactive substances as they derive from β-acids to which several physiological effects had been attributed, particularly, their antiproliferative action in cancer cells (Machado et al., 2017). Other putative α- and/or β-acid-derived oxidation products remain probably undiscovered (Taniguchi et al., 2015) for reasons unknown, taking into consideration the recent advances on compounds identification on the hop plant and their putative biological activity, research efforts should be directed not only in the continuity of the discovery of new compounds but also on the evaluation of their bioactivity, bioavailability, and mechanisms of action of the molecules. Moreover, the optimization of analytical methods targeting these molecules should also be pursued as essential tools for the evaluation of the amounts present in hops and beers as well as to assist in bioavailability assays. Besides bitter acid-derived oxidation products other hop metabolites were recently identified. In the cones of the variety “Cascade,” cultivated in the Northern Italy, researchers discovered very recently two new prenylated phloroglucinols (4-hydroxycolupulone and cascadone) and humudifucol, the first example of prenylated dimeric phlorotannin found in nature (Fig.  10.11). These compounds were evaluated for their potential bioactivities on two enzymes related to inflammation (prostaglandin E2 synthase and 5-lipoxygenase) involved in pain, atherosclerosis and tumorigenesis. In addition, 4-­hydroxycolupulone presented the highest inhibitory activity over the referred targets being comparable to the well-known anti-­ inflammatory action of xanthohumol itself. These findings concerning the newly discovered molecules confirm that hops should be regarded as a further source of molecules associated with anti-inflammatory and cancer chemopreventive activities.

Chapter 10  Hops: New Perspectives for an Old Beer Ingredient   293

Fig. 10.11  Molecular structure of the newly discovered molecules 4-hydroxycolupulone, humudifucol, and cascadone.

10.4.2 Research on New Varieties There are nowadays over 250 known hop varieties well characterized worldwide (Healey, 2016) although the most commercially relevant can be around 150 as indicated in recent publications provided by hop-related companies: 146 varieties (Barth-Haas Hops Companion, 2016) and 170 (More Beer, 2015) listed and described concerning the most relevant characteristics for brewers as aroma profiles, bitter acids contents, etc. These include new commercial cultivars, as well as, established varieties that have been brought back due to their potential adaptation capabilities to today’s expansive and demanding brewing environment. The number of varieties has increased exponentially in the last years duplicating (from 81 to 146) in the last 7 years (BarthHaas Hops Companion, 2016). New hop cultivars are being released with a strong incidence in the United States, however, the same trend is verified in other locations worldwide with new hop cultivars coming from Germany, United Kingdom, Australia, New Zealand, France, Czech Republic, Slovenia, and Ukraine. This proliferation of varieties is beneficial to the beer overall evolution, since they are quality and differentiated products. The increasing number of hops will create a challenge to brewers, breeders, growers, and suppliers, namely, the supply security concerns, once less acreage is allocated to each variety, and also because the demand for a particular variety can change in a few years, making it difficult for the growers to define their planting plans. Notwithstanding the search for new varieties with more pest and disease resistance, as well as strong commercial qualities, mainly at the aroma profile, bitterness, yield and storage attributes, will pursue due to the vitality of the current beer environment. Most of the

294  Chapter 10  Hops: New Perspectives for an Old Beer Ingredient

v­ arieties presently used were directly developed from domestication of wild ancestor plants, while modern agricultural breeding techniques rely on precise crossing using well-known male and female plants to develop new varieties. In fact, hop research institutes and big hop producing companies are investing in the development and release of new hop varieties with valuable agronomic characteristics, as referred, but principally focused on the organoleptic characteristic valued by modern brewers. The modern development and release of a new variety involve a huge amount of work, as well as, financial resources and specific facilities, and takes not less than 11 years to finalize. It starts with the parental selection, that is, choosing the males and females that will be used as germplasm sources. They are selected based on the characteristics required for the new plants and considering that some will be present in the new plants. However, due to the uncertainty about which selected features will be expressed in the new plants, about 40,000 genotypes are usually tested during the selection process (https://ychhops.com). After the parental choice, seeds are germinated and the following 7–8 years are dedicated to early, intermediate and advanced selection throughout the use of tools that will permit the narrowing of plants down to one or two varieties that best represent the original breeding objectives. The last 2 years of the selection process are then spent in field trials, expanded to more cultivated area. The last step compromises the test of some hops in experimental brewing before the final release of the variety. The large efforts to develop new varieties imply the necessity of resorting to commercial protection strategies, which will be reflected on the hops price and make that variety more valuable, hence a target to unscrupulous dealers who can create an authenticity issue in hops trade. A big concern of growers and brewers is the varietal authenticity of the plants used. Therefore, some hops identification has been increasingly applied, the molecular DNA-based techniques being claimed as methods of choice to identify or differentiate wild hops found in the nature, commercialized varieties, or new varieties released (Patzak et al., 2010; Horreo et al., 2014). These techniques are developed at some hop research labs and institutes worldwide and can be used for plant certification. The DNA analysis has the advantage of permitting the identification of the variety from any part of the plant that contains DNA, both grown in the field and in dried and processed forms, and can detect as little as 5% of another variety (Moir, 2000). Currently the most consensual technology for varietal discrimination of hops is based on the use of 25 microsatellite DNA markers that can assure accurate genotyping, that is, the complete discrimination of the known varieties (Henning et  al., 2015). However, this methodology requires advanced and expensive equipment and reagents

Chapter 10  Hops: New Perspectives for an Old Beer Ingredient   295

which motivates the search for more expedite techniques that can be used in laboratories with less technological means and financial resources. In this direction some authors proposed the use of single nucleotide polymorphism (SNP) analysis using equipment as real-time polymerase chain reaction (PCR) available at most genetic analysis laboratories to analyze a set of seven markers proposed as a battery capable of discrimination of the known cultivated varieties. This is a very promising method, notwithstanding, it requires the previous validation of the set of markers using qPCR equipment before it can be used as a standardized tool to evaluate hops germplasm collections and authenticate commercial samples.

10.5 Conclusion The present work revises the most relevant traded hop varieties, their chemical, biological, and brewing characteristics, as well as the analytical methods used to assure hop quality and authenticity. The current international hop market was characterized and trends of hops trade developments were approached. It is irrefutable that the hop market is on the threshold of fundamental change which is being driven by the internationally growing preference for differentiated beers, in which more hops are produced, mainly sustained by the craft brew sector. This movement has led to an increasingly search for new flavors in beer, therefore new hops providing these flavors were required which motivated the search for the new “green gold.” Several new varieties are being developed and will be released in the next few years which will promote the development and enlargement of studies about their behavior in beer considering also the new forms in which hops are used. Moreover, the increase in hop usage, either in quantity or on the number of differentiated varieties simultaneously used will predictively increase the bioactivity of the beer that by its hand will motivate more studies in the area. Considering the exposed along the chapter the overall research on hop is presently gaining a new breath which will certainly contribute to an increment in the beer quality and consumer’s awareness of the beverage beneficial health properties, which is of major relevance to the economic sustainability of the beer sector both at large and microscale production. Besides the advancements for brewing, agronomic research that utilizes cutting-edge technologies to identify superior traits in the hop genome is being carried out to grow stronger, healthier and more sustainable hop varieties and new applications for hops are being searched.

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References Algazzali, V., Shellhammer, T., 2016. Bitterness intensity of oxidized hop acids: humulinones and hulupones. J. Am. Soc. Brew. Chem. 74 (1), 36–43. Almaguer, C., Gastl, M., Arendt, E.K., Becker, T., 2012. Contributions of hop hard resins to beer quality. Brew. Sci. 65 (7–8), 118–129. Almaguer, C., Schoenberger, C., Gastl, M., Arendt, E.K., Becker, T., 2014. Humulus lupulus—a story that begs to be told. A review. J. Inst. Brew. 120 (4), 289–314. Analytica-EBC, 2002. EBC 7.10: hop oil content of hops and hops products. Eur. Brew. Conv. Brussels. Analytica-EBC, 2012. EBC 7.7: alpha and beta acids in hops and hops product by HPLC. Eur. Brew. Conv. Brussels. Analytica-EBC, 2015. EBC 7.14: total polyphenols in hops and hops pellets. Eur. Brew. Conv. Brussels. ASBC Methods of Analysis, 2008a. Hops 12: Hop Storage Index (HSI). Am. Soc. Brew. Chem. St. Paul, MN, USA. ASBC Methods of Analysis, 2008b. Hops 13: total essential oils in hops and hop pellets by steam distillation. Am. Soc. Brew. Chem . St. Paul, MN, USA. ASBC Methods of Analysis, 2008c. Hops 14: α-acids and β-acids in hops and hop extracts by HPLC (international method). Am. Soc. Brew. Chem . St. Paul, MN, USA. Barth-Haas Group, 2012. The Barth Report. Nuremberg. Barth-Haas Group, 2015. The Barth Report. Nuremberg. Barth-Haas Group, 2017. The Barth Report. Nuremberg. Barth-Haas Group and Germain Hansmaennel, 2013. In: Heinrich Meier, G. (Ed.), Beer production—market leaders and their challengers in the top 40 countries in 2012. Joh. Barth & Sohn GmbH & Co. KG, Nuremberg. Barth-Haas Hops Companion, 2016. A Guide to the Varieties of Hops and Hop Products, third ed. John I. Haas, Inc., Washington, DC. Blake, D., Feltus, A., Fitzpatrick, T., Linsner, M., Zainasheff, J., Beechum, D., Belanger, C., Harting, D., Hayes, A., Jankowski, B., Korty, A., Nadeau, L., Shawn Scott, W., Smith, R., Strong, L., Symons, P., Tonsmeire, M., Winnie, M., Wheeler, T., Daniels, R., Deschner, R., Garvin, R., Grmela, J., Hall, B., Hieronymus, S., Mahut, M., Pattinson, R., Piatz, S., Rail, E., Smith, N., Vřes, P., Vřes, M., Eichhorn, B., Mitchell, D., and Wilcox, M. 2015. Beer style guidelines. Beer judge Certif. Progr. Edited by G. Strong and K England. Brewers Association, 2017. What Is Craft Beer? Cr. Beer. Available from: https://www. craftbeer.com/the-beverage/what-is-craft-beer. (Accessed November 5, 2017). Briggs, D.E., Boulton, C.A., Brookes, P.A., Steven, R., 2004. Brewing: Science and Practice. Woodhead Publishing Limited, Cambridge, England, p. 881. Cattoor, K., Dresel, M., De Bock, L., Boussery, K., Van Bocxlaer, J., Remon, J.P., De Keukeleire, D., Deforce, D., Hofmann, T., Heyerick, A., 2013. Metabolism of hop-­derived bitter acids. J. Agric. Food Chem. 61 (33), 7916–7924. Čermák, P., Palečková, V., Houška, M., Strohalm, J., Novotná, P., Mikyška, A., Jurková, M., Sikorová, M., 2015. Inhibitory effects of fresh hops on helicobacter pylori strains. Czech J. Food Sci. 33 (4), 302–307. Chadwick, L.R., Pauli, G.F., Farnsworth, N.R., 2006. The pharmacognosy of Humulus lupulus L. (hops) with an emphasis on estrogenic properties. Phytomedicine 13 (1–2), 119–131. Clark, S.M., Vaitheeswaran, V., Ambrose, S.J., Purves, R.W., Page, J.E., 2013. Transcriptome analysis of bitter acid biosynthesis and precursor pathways in hop (Humulus lupulus). BMC Plant Biol. 13 (1), 12. Cook, A. H. and Harris, G. 1950. The chemistry of hop constituents. Part I. Humulinone, a new constituent of hops, J. Chem. Soc., 0, 1873–1876.

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De Keukeleire, D., Milligan, S., Kalita, J., Pocock, V., De Cooman, L., Heyerick, A., Rong, H., 2001. Prenylated hop flavonoids are key agents in relation to health-beneficial ­properties of beer, in 28th Int. Congr. Eur. Brew. Conv, Budapest. Donelan, D., 2017. 2017 Harvest info. Richmond. Dresel, M., Dunkel, A., Hofmann, T., 2015a. Sensomics analysis of key bitter compounds in the hard resin of hops (Humulus lupulus L.) and Their Contribution to the Bitter Profile of Pilsner-Type Beer. J. Agric. Food Chem. 63 (13), 3402–3418. Dresel, M., Praet, T., Van Opstaele, F., Van Holle, A., Naudts, D., De Keukeleire, D., De Cooman, L., Aerts, G., 2015b. Comparison of the analytical profiles of volatiles in single-­hopped worts and beers as a function of the hop variety. Brew. Sci. 68 (1–2), 8–28. Economic Commission of IHGC, 2017. Summary Reports, Int. HOP Grow. Conv, Yakima. Eri, S., Khoo, B.K., Lech, J., Hartman, T.G., 2000. Direct thermal desorption−gas ­chromatography and gas chromatography−mass spectrometry profiling of hop (Humulus lupulus L.) essential oils in support of varietal characterization. J. Agric. Food Chem. 48 (4), 1140–1149. Eyck, L.A.T., Gehring, D., 2015. The Hop Grower’s Handbook: The Essential Guide for Sustainable, Small-Scale Production for Home and Market. Chelsea Green Publishing, White River Junction, VT. Eyres, G.T., Marriott, P.J., Dufour, J.P., 2007. Comparison of odor-active compounds in the spicy fraction of hop (Humulus lupulus L.) essential oil from four different varieties. J. Agric. Food Chem. 55 (15), 6252–6261. Field, J.A., Nickerson, G., James, D.D., Heider, C., 1996. Determination of essential oils in hops by headspace solid-phase microextraction. J. Agric. Food Chem. 44, 1768–1772. Gatza, P., Swersey, C., Skypeck, C., and Rabin, D. 2017. Beer Style Guidelines, Brew. Assoc. Edited by C. Papazian. Boulder, CO. Goiris, K., Ridder, M., Rouck, G., Boeykens, A., Opstaele, F., Aerts, G., Cooman, L., Keukeleire, D., 2002. The oxygenated sesquiterpenoid fraction of hops in relation to the spicy hop character of beer. J. Inst. Brew. 108 (1), 86–93. Gonçalves, J.L., Figueira, J.A., Rodrigues, F.P., Ornelas, L.P., Branco, R.N., Silva, C.L., Câmara, J.S., 2014. A powerful methodological approach combining headspace solid phase microextraction, mass spectrometry and multivariate analysis for profiling the volatile metabolomic pattern of beer starting raw materials. Food Chem. 160, 266–280. Haseleu, G., Intelmann, D., Hofmann, T., 2009. Structure determination and sensory evaluation of novel bitter compounds formed from β-acids of hop (Humulus lupulus L.) upon wort boiling. Food Chem. 116 (1), 71–81. Healey, J., 2016. The Hops List: 265 Beer Hop Varieties From Around the World. Melbourne. Available from: http://www.hopslist.com/. Henley, T., Reddivari, L., Broeckling, C.D., Bunning, M., Miller, J., Avens, J.S., Stone, M., Prenni, J.E., Vanamala, J., 2014. American India Pale Ale matrix rich in xanthohumol is potent in suppressing proliferation and elevating apoptosis of human colon cancer cells. Int. J. Food Sci. Technol. 49 (11), 2464–2471. Henning, J. A., Coggins, J., and Peterson, M. 2015. Simple SNP-based minimal marker genotyping for Humulus lupulus L. identification and variety validation., BMC Res. Notes, 8, 542. Hieronymus, S., 2012. For the Love of Hops: The Practical Guide to Aroma, Bitterness, and the Culture of Hops. Brewers Publications, Boulder, CO, p. 321. Hintermeier, P., 2016. Market Report April 2016, Dtsch. Hopfenwirtschaftsverband e.V, Paris. Horreo, J.L., Peredo, E.L., Olmedo, J.L., Valladares, J.E., García, E., Revilla, M.A., 2014. Genetic diversity inferred from microsatellites of wild hops in Galicia (Spain). Brew. Sci. 67 (11–12), 132–136.

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Hough, J.S., Briggs, D.E., Stevens, R., Young, T.W., 1982. The chemistry of hop constituents. In: Hough, J.S., Briggs, D.E., Stevens, R., Young, T.W. (Eds.), Malting and Brewing Science. Springer, Boston, MA, pp. 422–455. Hudcová, T., Bryndová, J., Fialová, K., Fiala, J., Karabín, M., Jelínek, L., Dostálek, P., 2014. Antiproliferative effects of prenylflavonoids from hops on human colon cancer cell lines. Inst. Brew. Distill. 120, 225–230. Intelmann, D., Haseleu, G., Hofmann, T., 2009. LC-MS/MS quantitation of hop-derived bitter compounds in beer using the ECHO technique. J. Agric. Food Chem. 57 (4), 1172–1182. Jorge, K., Trugo, L.C., 2003. Discrimination of different hop varieties using headspace gas chromatographic data. J. Braz. Chem. Soc. 14 (3), 411–415. Kankolongo Cibaka, M.-L., Gros, J., Nizet, S., Collin, S., 2015. Quantitation of selected terpenoids and mercaptans in the dual-purpose hop varieties Amarillo, Citra, Hallertau Blanc, mosaic, and Sorachi Ace. J. Agric. Food Chem. 63 (11), 3022–3030. Kao, T.H., Wu, G.Y., 2013. Simultaneous determination of prenylflavonoid and hop bitter acid in beer lee by HPLC-DAD-MS. Food Chem. 141 (2), 1218–1226. Karabín, M., Hudcová, T., Jelínek, L., Dostálek, P., 2016. Biologically active compounds from hops and prospects for their use. Compr. Rev. Food Sci. Food Saf. 15 (3), 542–567. Koetter, U., Biendl, M., 2010. Hops (Humulus lupulus): a review of its historic and medicinal uses. J. Am. Bot. Counc. 44–57. Kovačevič, M., Kač, M., 2001. Solid-phase microextraction of hop volatiles. Potential use for determination and verification of hop varieties. J. Chromatogr. A 918 (1), 159–167. Kowaka, M., Kokubo, E., 1976. Composition of bitter substances of hops and characteristics of beer bitterness. Am. Soc. Brew. Chem. 35, 16–21. Lermusieau, G., Bulens, M., Collin, S., 2001. Use of GC-olfactometry to identify the hop aromatic compounds in beer. J. Agric. Food Chem. 49 (8), 3867–3874. Ligor, M., Stankevičius, M., Wenda-Piesik, A., Obelevičius, K., Ragažinskienė, O., Stanius, Ž., Maruška, A., Buszewski, B., 2014. Comparative gas chromatographic– mass spectrometric evaluation of hop (Humulus lupulus L.) essential oils and extracts obtained using different sample preparation methods. Food Anal. Methods 7 (7), 1433–1442. Liu, Z., Wang, L., Liu, Y., 2017. Analyzing differences in freshness of SA-1 hops by headspace solid-phase microextraction gas chromatography—mass spectrometry combined with chemometrics. J. Am. Soc. Brew. Chem. 75 (3), 193–200. Machado, J.C., Faria, M.A., Melo, A., Ferreira, I.M.P.L.V.O., 2017. Antiproliferative effect of beer and hop compounds against human colorectal adenocarcinome Caco-2 cells. J. Funct. Foods 36, 255–261. Magalhães, P.J., Guido, L.F., Cruz, J.M., Barros, A.A., 2007. Analysis of xanthohumol and isoxanthohumol in different hop products by liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry. J. Chromatogr. A 1150 (1–2), 295–301. Martins, A., 2015. Um futuro para a produção de lúpulo em Portugal. In: Rodrigues, M.Â., Morais, J.S., de Castro, J.P.M. (Eds.), Jornadas lúpulo e cerveja novas oportunidades negócio. Livro atas. Instituto, Bragança, p. 118. Maye, J.P., Smith, R., Leker, J., 2016. Humulinone formation in hops and hop pellets and its implications for dry hopped beers. Tech. Q. 53 (1), 23–27. Milligan, S.R., Kalita, J.C., Heyerick, A., Rong, H., De Cooman, L., De Keukeleire, D., 1999. Identification of a potent phytoestrogen in hops (Humulus lupulus L.) and beer. J. Clin. Endocrinol. Metab. 84 (6), 2249–2252. Moir, M., 2000. Hops: a millennium review. J. Am. Soc. Brew. Chem. 58 (4), 131–146.

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Mongelli, A., Rodolfi, M., Ganino, T., Marieschi, M., Dall’Asta, C., Bruni, R., 2015. Italian hop germplasm: characterization of wild Humulus lupulus L. genotypes from Northern Italy by means of phytochemical, morphological traits and multivariate data analysis. Ind. Crop. Prod. 70, 16–27. Morado, R., 2009. Larousse da Cerveja, first ed. São Paulo. More Beer, 2015. The largest list of brewing hops. morebeer.com. Available from: https:// www.morebeer.com/articles/homebrew_beer_hops. (Accessed November 14, 2017). National Agricultural Statistics Service, 2016. National Hop Report: 2016 Hop Production Up 11 Percent From Last Year. United States Dep Agric, Washington, DC. Oladokun, O., Tarrega, A., James, S., Smart, K., Hort, J., Cook, D., 2016. The impact of hop bitter acid and polyphenol profiles on the perceived bitterness of beer. Food Chem. 205, 212–220. Palmer, J.J., 2006. How to Brew: Everything You Need To Know To Brew Beer Right The First Time: John J. Palmer. Brew. Publ. Patzak, J., Nesvadba, V., Henychová, A., Krofta, K., 2010. Assessment of the genetic diversity of wild hops (Humulus lupulus L.) in Europe using chemical and molecular analyses. Biochem. Syst. Ecol. 38 (2), 136–145. Peacock, V., 2011. Ukrainian hops. In: Oliver, G. (Ed.), Oxford Companion to Beer, first ed, p. 920. Oxford. Peacock, V.E., Deinzer, M.L., 1981. Chemistry of hop aroma in beer. J. Am. Soc. Brew. Chem. 39 (4), 136–141. Prencipe, F.P., Brighenti, V., Rodolfi, M., Mongelli, A., Dall’Asta, C., Ganino, T., Bruni, R., Pellati, F., 2014. Development of a new high-performance liquid chromatography method with diode array and electrospray ionization-mass spectrometry detection for the metabolite fingerprinting of bioactive compounds in Humulus lupulus L. J. Chromatogr. A 1349, 50–59. Roberts, T.R., Wilson, R.J.H., 2006. Hops. In: Priest, F.G., Stewart, G.G. (Eds.), Handbook of Brewing. second ed. CRC Press, Boca Raton, FL, pp. 181–285 (p. 831). Rodrigues, M.Â., Sá Morais, J., 2015. A cultura do lúpulo em Bragança. Aspetos agronómicos inovadores e potencial e expansão. In: Rodrigues, M.Â., Morais, J.S., De Castro, J.P.M. (Eds.), Jornadas lúpulo e cerveja novas oportunidades negócio. Livro atas. Instituto, Bragança, pp. 63–70. Salanţă, L.-C., Tofană, M., Socaci, S., Mudura, E., Fărcaş, A., Pop, C., Pop, A., Odagiu, A., 2015a. Characterisation of hop varieties grown in romania based on their contents of bitter acids by HPLC in combination with chemometrics approach. Czech J. Food Sci. 33 (2), 148–155. Salanţă, L., Tofană, M., Socaci, S., Mudura, E., Pop, C., Pop, A., Fărcaş, A., 2015b. Evaluation and comparison of aroma volatile compounds in hop varieties grown in Romania. Rom. Biotechnol. Lett. 20 (6), 11049–11056. Schaefer, O., Hümpel, M., Fritzemeier, K.-H., Bohlmann, R., Schleuning, W.-D., 2003. 8-Prenyl naringenin is a potent ERα selective phytoestrogen present in hops and beer. J. Steroid Biochem. Mol. Biol. 84 (2), 359–360. Schnaitter, M., Kell, A., Kollmannsberger, H., Schüll, F., Gastl, M., Becker, T., 2016. Scale-up of dry hopping trials: importance of scale for aroma and taste perceptions. Chemie-Ingenieur-Technik 88 (12), 1955–1965. Socaci, S.A., Socaciu, C., Tofanǎ, M., Raţi, I.V., Pintea, A., 2013. In-tube extraction and GC-MS analysis of volatile components from wild and cultivated sea buckthorn (Hippophae rhamnoides L. ssp. Carpatica) berry varieties and juice. Phytochem. Anal. 24 (4), 319–328. Spetsig, L.O., Steninger, M., 1960. Hulupones, a new group of hop bitter substances. J. Inst. Brew. 66 (5), 413–417. Statista 2017. Beer production worldwide from 1998 to 2016 (in billion hectoliters). Available from: https://www.statista.com/statistics/270275/worldwide-beer-production/ (Accessed 5 November 2017).

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Steenackers, B., De Cooman, L., De Vos, D., 2015. Chemical transformations of characteristic hop secondary metabolites in relation to beer properties and the brewing process: A review. Food Chem. 172, 742–756. Steinhaus, M., Schieberle, P., 2000. Comparison of the most odor-active compounds in fresh and dried hop cones (Humulus lupulus L. variety spalter select) based on GColfactometry and odor dilution techniques. J. Agric. Food Chem. 48 (5), 1776–1783. Stevens, J.F., Page, J.E., 2004. Xanthohumol and related prenylflavonoids from hops and beer: To your good health! Phytochemistry 65 (10), 1317–1330. Takoi, K., Itoga, Y., Koie, K., Kosugi, T., Shimase, M., Katayama, Y., Nakayama, Y., Watari, J., 2010. The contribution of geraniol metabolism to the citrus flavour of beer: synergy of geraniol and β-citronellol under coexistence with excess linalool. J. Inst. Brew. 116 (3), 251–260. Taniguchi, Y., Matsukura, Y., Ozaki, H., Nishimura, K., Shindo, K., 2013. Identification and quantification of the oxidation products derived from αlpha acids and beta acids during storage of hops (Humulus lupulus L.). J. Agric. Food Chem. 61, 3121–3130. Taniguchi, Y., Taniguchi, H., Yamada, M., Matsukura, Y., Koizumi, H., Furihata, K., Shindo, K., 2014. Analysis of the components of hard resin in hops (Humulus lupulus L.) and structural elucidation of their transformation products formed during the brewing process. J. Agric. Food Chem. 62 (47), 11602–11612. Taniguchi, Y., Matsukura, Y., Taniguchi, H., Koizumi, H., Katayama, M., 2015. Development of preparative and analytical methods of the hop bitter acid oxide fraction and chemical properties of its components. Biosci. Biotechnol. Biochem. 79 (10), 1684–1694. The Brewers of Europe, 2016. Beer Statistics, 2016th ed. The Brewers of Europe, Brussels. Ukrainian Academy of Agrarian Sciences, Institute of Plant Production n.a. V.Y. Yuriev, and National Centre for Plant Genetic Resources of Ukraine, 2008. Country Report on the State of Plant Genetic Resources for Food and Agriculture Ukraine. Kharkiv. Urban, J., Dahlberg, C.J., Carroll, B.J., Kaminsky, W., 2013. Absolute configuration of beer’s bitter compounds. Angew. Chem. Int. Ed. 52 (5), 1553–1555. Van Opstaele, F., De Rouck, G., De Clippeleer, J., Aerts, G., De Cooman, L., 2011. Analytical and sensory assessment of hoppy aroma and bitterness of conventionally hopped and advanced hopped Pilsner beers. Cerevisia 36 (2), 47–59. Van Opstaele, F., De Causmaecker, B., Aerts, G., De Cooman, L., 2012. Characterization of novel varietal floral hop aromas by headspace solid phase microextraction and gas chromatography-mass spectrometry/olfactometry. J. Agric. Food Chem. 60 (50), 12270–12281. Verband Deutscher Hopfenpflanzer e.V. 2015a. Hopfenmarktbericht Nr. 1 vom 16. September 2015. Wolnzach. Verband Deutscher Hopfenpflanzer e.V. 2015b. Hopfenmarktbericht Nr. 8 vom 17 November 2015. Watson, B., Herz, J., 2017. National Beer Sales & Production Data. Brew, Assoc. Available from: https://www.brewersassociation.org/statistics/national-beer-salesproduction-data/. (Accessed November 5, 2017). Zanoli, P., Zavatti, M., 2008. Pharmacognostic and pharmacological profile of Humulus lupulus L. J. Ethnopharmacol. 116 (3), 383–396. Zapata, J., Mateo-Vivaracho, L., Lopez, R., Ferreira, V., 2012. Automated and quantitative headspace in-tube extraction for the accurate determination of highly volatile compounds from wines and beers. J. Chromatogr. A 1230, 1–7.

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Further Reading Analytica-EBC, 2004. EBC 7.9: iso alpha acids and reduced iso alpha acids in hop products by HPLC. Eur. Brew. Conv. 1–5. Brussels. Analytica-EBC, 2005a. EBC 7.11: iso alpha, alpha and beta acids in isomerised hop pellets by HPLC. Eur. Brew. Conv. Brussels. Analytica-EBC, 2005b. EBC 7.8: iso alpha, alpha, and beta acids in hop and isomerised hop extracts by HPLC. Eur. Brew. Conv. Brussels. ASBC Methods of Analysis, 2008d. Hops 6: α- and β-acids in hops and hop pellets by spectrophotometry and by conductometric titration. Am. Soc. Brew. Chem. St. Paul, MN, USA. ASBC Methods of Analysis, 2008e. Hops 9: isomerized hop extracts. Am. Soc. Brew. Chem. St. Paul, MN, USA. ASBC Methods of Analysis, 2009. Hops 16: Iso-α-, α-, and; Β-acids in hop extracts and isomerized hop extracts by HPLC. Am. Soc. Brew. Chem. St. Paul, MN, USA. Burroughs, L., Williams, P., 1999. A single HPLC Method for Complete Separation of Unmodified and Reduced Iso-Alpha-Acids. Eur. Brew. Conv, Cannes. Nord, L.I., Sørensen, S.B., Duus, J.Ø., 2003. Characterization of reduced iso-α-acids derived from hops (Humulus lupulus) by NMR. Magn. Reson. Chem. 41 (9), 660–670.

FRUIT AND VEGETABLE-BASED BEVERAGES—NUTRITIONAL PROPERTIES AND HEALTH BENEFITS

11

Marian Butu*, Steliana Rodino*,† *

National Institute of Research and Development for Biological Sciences, Bucharest, Romania, †Research Institute for Agriculture Economy and Rural Development, Bucharest, Romania

11.1 Introduction Fruit and vegetable-based beverages are part of a balanced diet that ensures the health and the vigor of the body. They participate actively in cellular regeneration, detoxification, and treatment of many diseases, being recommended by nutritionists for a healthy lifestyle. The usage of fruit and vegetable beverages for the detoxification, regeneration, and healing of the body is recommended for two good reasons: the first is that the essential part (both for vegetables and fruits) is in their sap, which is obtained in the form of juice and the second is that the juice of raw vegetables and fruits is assimilated in the body in about 10–15 min and is used almost entirely for feeding and regenerating tissues with a minimal effort of the digestive system. However, there are beverages that are beneficial for health through the ingredients they contain and harmful beverages that are nothing but liquids that provide excess sugars and almost no essential nutrients. This is why scientific evidence on the chemical composition and the possible health benefits of various fruits and vegetables are needed whenever a nutritional plan is required. Natural fruit and vegetable beverages are tasty, nourishing, and rich in vitamins, minerals, and phytonutrients, more precisely natural bioactive compounds that interact positively with food fibers and other substances taken from food. Nutritionists from the University of California (Los Angeles) have also created a top of the healthiest beverages, the top five being occupied by pomegranates, cranberries, acai, noni, and cherries. Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00011-0 © 2019 Elsevier Inc. All rights reserved.

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A very good way to introduce important nutrients into the diet is through vegetable juices. They are deeply detoxifying and regenerating and improve metabolism. They contain all the necessary amino acids, minerals, salts, enzymes, and vitamins, provided they are fresh, raw, preservative-free, and properly extracted from vegetables (the best option is the centrifuge juicer designed specifically for extracting these juices). Fibers in all vegetable juices quickly induce the feeling of satiety and improve digestion. The reason vegetables are the healthiest is that they have the lowest amount of sugar in their composition and provide fewer calories than fruit juices. The only inconvenience is the higher sodium content.

11.2  The Health Benefits of Consuming Fruits and Vegetables Juices As early as 2003, the WHO published a research report whose conclusions recommended a daily portion of 400 g of either fruit and vegetables (excluding potatoes and starchy tubers) for the prevention of occurrence of possible chronic diseases, and for the prevention of micronutrient deficiencies (WHO, 2003). More recently, the general recommendations are to consume five portions of fruits and vegetables a day. Moreover, the fruits represent one of the components of the national programs of healthy nutrition that are implemented in the schools in most of the European countries, together with the dairy products. The result of a study which assess the average fresh and frozen fruit and vegetables and frozen consumption and the effect on nutrient intakes across gender and age categories, based on combined data from the National Health and Nutrition Examination Survey 2011–2014 and the Food Pattern Equivalents Database 2011–2012 is presented in Fig. 11.1 (Storey and Anderson, 2017). Although fruit and vegetable consumption is highly recommended for a healthy and balanced diet, several European countries do not meet these recommendations. For example, in Italy, only 45% of young people are consuming at least one portion of vegetables per day (Menozzi et al., 2015). According to the Eurostat data, in 2014, 60% of the EU population consumed at least one portion of fruit and vegetables daily. Only 14.1% of the interviewed individuals consumed more than five portions a day. In the United Kingdom, one-third (33.1%) of the population consumed more than five daily portions; in Denmark, it was 25.9%; and in the Netherlands 25%. The opposite was found in Romania, where almost two-thirds (65.1%) of the population did not consume any fruit or vegetables daily (De Cicco, 2017). Data made

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

Fig. 11.1  Total fruit and vegetable consumption across age groups (1cup equivalents/day).

public by the European Food Information Council (EUFIC) show that consumption of fruit across Europe ranged from 577 g/day in Poland to 196 g/day in Iceland, and vegetable consumption varied from a minimum of 109 g/day in Norway to a maximum of 284 g/day in Cyprus (Menozzi et al., 2015). People who want to strengthen their immune system and reduce blood pressure and cholesterol levels can regularly drink beverages made from beets, carrots, celery, currants, spinach, grapes, cherries, or watermelons, with garlic and ginger supplementation. Studies have shown that beverages can affect the cardiovascular risk factors by lowering blood pressure through antioxidant effects and improvement of the cardiovascular system (Binia et al., 2015; Zheng et al., 2017). In order to treat deficiency in potassium, magnesium, or calcium, beverages based on melon, apricots, peaches, or broccoli are beneficial. Heart disease can be prevented with pineapple and ginger, pear, and parsley beverages. On the other hand, carbonated drinks, fruit cocktails, and energy drinks are among the most harmful beverages. Some authors consider that the consumption of fruit and vegetables represents a prerequisite of higher-quality diets. It was reported that a diet rich in fruit is associated with a lower risk of cardiovascular disease (CVD) events and mortality (Wang et al., 2014). However, less information is provided on the benefits of the consumption of fruit and vegetable juices to diet quality. Based on these considerations, Francou et al. released a survey (almost 2000 individuals) on the consumption patterns of fruit and vegetable juice among population in France. The mean total consumption of fruits and vegetables was 2.6 servings/day for children and 3.8 servings/day for adults. In the same

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time, the values for fruits and vegetables 100% beverages were 83 mL/ day for children and 54.6 mL/day for adults, which are far less than the recommended values (Francou et al., 2015). Therefore, fruit and vegetable-based beverages may provide important beneficial effects on human health. They contain a wide range of biological active compounds, such as polyphenols, oligosaccharides, fiber, and nitrate, which may induce an antioxidant, antimicrobial, and antiviral effects. Although the juice-based diets are becoming more and more popular, some authors consider there is a lack of scientific evidence of their health benefits (Henning et al., 2017). Nevertheless, there are various studies investigating the chemical composition of fresh or cooked vegetables and fruits, and some of them will be overviewed throughout these book chapters. For example, it was demonstrated that vegetables like broccoli and cauliflower provide flavonoid, phenolic compounds, carotenoids, quercetin, and ascorbic acids, with high antioxidant activity (dos Reis et al., 2015; Koh et al., 2009). On the other hand, care should be taken, and extreme behavior should be avoided (such as consuming one kind of fruit or vegetable species in excess). According to Fabbri et al., vegetables may also contain several antinutrients, as follows: potatoes contain alkaloid solanine, arsenic, and nitrite; green leafy vegetables present toxic oxalates; and peas contain phytic acid, protease inhibitors, and tannins (Fabbri and Crosby, 2016). According to the European Quality Control System (EQCS), the minimum analyses for authenticity investigations are (Table 11.1): Other analysis could be: • delta 18O water at NFC (not from concentrate) juice, • SGF (Spin Generated Fingerprint) profiling as prescreening, • risk oriented: flavor analysis (if special flavors are advertised), • risk oriented: general safety parameters like heavy metals + arsenic, patulin, ochratoxin A, pesticides, …, • risk oriented: spoilage parameters like ethanol, lactic acid,…, • vitamins if there is a special request, • Risk oriented further analysis: 13C and other sugars. Among the many fruit and vegetable beverages recommended for their beneficial effects on the human health, the most used and the most powerful evidence-based effects are presented briefly in the following pages, in alphabetical order.

11.2.1 Acai Acai berries (Euterpe oleracea), originating from South America, considered as a “superfruit,” are extremely high concentrated in anthocyanins, which help a balanced cholesterol levels and acting as

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Table 11.1  Investigations for Authenticity Parameters Parameter

Determination Method

Relative density 20/20 Brix (table) Soluble solids Glucose Fructose Sucrose Titrat. acidity expr. as tart. acid pH 7.0 Titrat. acidity expr. as citric acid pH 8.1 Sulfur dioxide, total Quinic acid L-malic adic Tartaric acid Citric acid Isocitric acid L-ascorbic acid Sodium Potassium Calcium Magnesium Nitrate Phosphate Sulfate Sorbiotol Formol number Proline Water-soluble pectins Lactic acid Anthocyan-finger print Oxalic acid D-mannitol

IFU 1 IFU 3 IFU 3 Enzymatic Enzymatic Enzymatic IFU 3 IFU 3 IFU 7a IC/HPLC Enzymatic IFU 65 Enzymatic Enzymatic IFU 17 AAS AAS AAS AAS IFU 48 IFU 36 IFU 50 enzymatic IFU 30 IFU 49 IFU 26 IFU 53 HPLC

antioxidants in the body, are rich in plant sterols providing cardioprotective benefits, and help the organism to maintain the cells healthy (Barbosa et al., 2016; Feio et al., 2012).

11.2.2 Apple Apples (Malus domestica) are the fruits specific to the fall season, but also some of the healthiest ones out there. They are loaded with

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powerful antioxidants, including quercetin, catechins, phlorizin, and chlorogenic acids that protect against the onset of breast cancer, colon cancer, and help to prevent kidney stones and help to balance the cholesterol. Studies have found that people who eat at least two apples per week can reduce the risk of developing asthma and type 2 diabetes and stimulate lung health. Other authors demonstrated that apple polyphenols are able to influence glucose uptake in the small intestine by inhibiting the activity of glucose transporters (Manzano and Williamson, 2010).

11.2.3 Apricots Apricots are the fruits of Prunus armeniaca. This fruit provides to the body substantial amounts of vitamin A or beta-carotene (Mezzomo and Ferreira, 2016). In the body, this precious antioxidant is converted into vitamin A, which helps to maintain skin health, night vision, and supports the body's natural defenses (Aschoff et al., 2015a; dos Reis et al., 2015). Apricots have from moderate to significant amounts minerals like calcium, phosphorous, manganese, iron, and copper, which can ensure the healthy growth and the development of bones, or act as preventing some age-related disease, like osteoporosis.

11.2.4 Avocado Avocado (Persea americana) is an excellent source of healthy monounsaturated fats, oleic acid, which balance cholesterol and protects against breast cancer. It is rich in carotenoid called lutein, namely vitamin E (Mezzomo and Ferreira, 2016), whose presence inside a healthy avocado fruit inhibits the development of prostate cancer. Avocado has very high potassium content which is linked to reduced blood pressure.

11.2.5 Blackberries Blackberries are juicy fruits, which are in the form of a group of small berries growing in bushes or vineyards climbing. Consumption of blackberries gives the body multiple nutritional benefits. Phenolic acids and flavonoids are phytochemicals common in all species of berries, and especially in blackberries, and may be the compounds that give this fruit its specific health-promoting effect (Jakobsdottir et  al., 2013). The compound with antioxidant activity contained by blackberries (Wolfe et al., 2008) help the human organism to fight against infectious diseases. Blackberries are usually used as topping for ice cream, yogurt, and desserts, are part of the composition of fruit beverages and jams, but can also be eaten fresh.

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

11.2.6 Blueberry Blueberry (Vaccinium corymbosum) is in the top specialists' preferences when recommending a health promoting, natural beverage. One cup (250 mL) has a total antioxidant capacity of 13,427—including vitamins A, C, and flavonoids (like quercetin and anthocyanidin). The proportion exceeds 10 times the recommendation of the nutritionists, so, consuming wild berries for sure we can assure the necessary intake of vitamins and antioxidants. In cultivated blueberries, the antioxidants level is around 9000 per cup, but the vitamins proportion is preserved. Beverages prepared from blueberry are useful for vascular system and brain (Rodriguez-Mateos et al., 2012), for blood pressure and arterial stiffness (Johnson et al., 2015), also in the fight against urinary tract infections, CVDs, and in improving memory. As an ingredient of a natural beverage, blueberry will exert an anti-­ inflammatory and protective action for the retinal structure (Song et al., 2016; Tremblay et al., 2013).

11.2.7 Broccoli Broccoli (Brassica oleracea) has a good reputation for fighting cancer because it contains large amounts of antioxidants and fiber (dos Reis et al., 2015; Popolo et al., 2017). Broccoli exhibits a high content of flavonoid, phenolic compounds, carotenoids, quercetin, and ascorbic acids, with high antioxidant activity (Koh et al., 2009). Due to its content of carotenoids, this vegetable has also been recommended for cataract prevention. The best vegetables to be used for juice extraction should be green, without yellow or dry spots, they should also be firm to touch and not soft. The strain can also be squeezed because it contains plenty of minerals and vitamins.

11.2.8 Brussels Sprouts Cabbage is rich in vitamins A and C, but Brussels sprouts (B. oleracea var. gemmifera) exhibit a high concentration of glucozinol, the substance that struggles against cancer and gives these vegetables, their distinctive flavor. A recent study suggests that Brussels sprouts could be protective against Aβ-induced neurotoxicity, possibly due to the antioxidative capacity of its major constituent, kaempferol (Kim et al., 2013).

11.2.9 Cabbage Cabbage (B. oleracea) is the only vegetable in which vitamin B12 is found, which is recognized for its well-functioning nervous system. Cabbage juice is considered as one of the most effective remedies for

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healing vitamin C deficiency. Beverages obtained from cabbage juice have a high content of vitamins, calcium, magnesium, iodine, manganese, sulfur, phosphorus, and copper, and have strong anticancer effects. It is a powerful blood purifier, it is recommended for ulcers, constipation and eruptions of the skin, eczema, colitis, and headache, regulates glycemia as indicated in case of diabetes, balances the nervous system, purifies the intestinal tract, nourishes the tissues in depth, and prevents early aging. Cabbage juice is a food medicine that rebalances the proper functioning of the body. The most well-known beverage obtained from cabbage is the Sauerkraut. This is a fermented juice, used as a form of preservation of cabbage. It contains a large quantity of lactic acid and tyramines, as well as vitamins and minerals, and has few calories (Raak et al., 2014). Moreover, Licznerska et al. investigated the chemopreventive activity of cabbage against breast cancer. The aim of the study was to evaluate the effect of raw cabbage and sauerkraut juices of different origins (industrial or organic farming) and their major indole components (I3C—indole-3-carbinol and DIM—diindolylmethane) on aromatase expression in two breast cancer cell lines. The results suggest that chemopreventive activity of cabbage against breast cancer may be partly explained by inhibition of the aromatase expression (Licznerska et al., 2013, 2016).

11.2.10 Carrots The carrot (Daucus carota subsp. Sativus) is rich in beta carotene (it has a role in regulating immune processes) and has special effects in the treatment of liver diseases: viral hepatitis, chronic hepatitis, and hepatobiliary insufficiency. Carrot juice is the most effective therapeutic form of carrot. Carrot contains calcium, copper, iodine, iron, magnesium, manganese, phosphorus, potassium, sodium, sulfur, vitamins A, B, C, D, E, G, and K, and pectins. It is an excellent tonic for many kind of illness. It can be consumed at discretion and in large quantities. It is particularly effective in preventing cataracts and other ocular problems, providing energy and helping to cure certain illnesses quickly. Carrot juice stimulates the immune system helps to treat anemia, circulatory problems, and skin disorders. It is helpful in digestive problems and is an excellent remedy for ulcer, asthma, and liver problems. It helps to prevent dental caries and gum disease. Carrot juice is often used as a base ingredient when preparing mixed beverages juices because it is easy to digest and can be consumed in large quantities. Some indications of this valuable juice: anemia, gastric and duodenal ulcers, colitis, enteritis, diarrhea or, conversely, constipation, hepatobiliary disorders, intoxication, and dermatoses. Other studies show the effect on colon cancer

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(Mazewski et al., 2018). Several medical studies conducted in Denmark under the leadership of Kirsten Brandt, of the Danish Institute of Agricultural Sciences, have shown that carcassing slows tumor growth and even prevents their formation. The most powerful antitumor substance that the carrot contains is falcarinol. It was studied as an inhibitor for a protein involved in breast cancer (Tan et al., 2014). In other studies on both cancer cell cultures and laboratory animals, it has been observed that under the influence of this anticancer substance, the growth of various types of malignant cells is inhibited.

11.2.11 Cauliflower Cauliflower (B. oleracea, familia Brassicaceae) is rich in vitamins K and C and fiber (dos Reis et al., 2015). Like other cruciferous vegetables, cauliflower glucosinolates help to prevent the formation of certain types of cancer and their treatment (Popolo et al., 2017). Unlike other vegetables, leaves and stems cannot be eaten, but the bouquets can be served raw or cooked.

11.2.12 Celery Celery (Apium graveolens) juice, both from the leaves and root, can be used as such or combined with carrot, lemon, or apple and has numerous therapeutical indications. Celery juice is a liver and kidney drain, tonic of the nervous and adrenal system, depurative, antirheumatic and anti-gout, antiseptic, and regulates blood pressure in hypertensive patients (Nicklas et al., 2015; Tanasawet et al., 2017). Celery juice is best known for its properties to ease rheumatic pain and arthritic inflammation. It is advisable to consume celery juice if you recover from certain diseases and especially after colds or flu, supplementing the lost minerals with celery juice. Due to the rich content of iron and magnesium, it is precious for purifying the blood. Celery juice contains anticancer substances— phthalide and polyacetylene, which are antioxidants. It is also rich in potassium and sodium and helps to normalize blood pressure and contains the same anti-ulcer and anticancer agents contained in cabbage juice. Potassium from celery helps to lower blood pressure and effectively strengthens the stomach, liver, and kidneys. The main components of celery juice are carotene, vitamins B1, B2, B6, C, and K, niacin, pantothenic acid, folic acid, magnesium, potassium, calcium, very valuable sodium, phosphorus, silicon, iron, manganese, copper, molybdenum, zinc, selenium, and sulfur. Celery juice is a diuretic and stimulates the elimination of residues through the kidneys, fluidizes the lymphatic system, purifies the digestive tract, and combats hypertension and edema, has a powerful

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s­ timulating effect on the brain and metabolism. Successfully treats sleep disorders. Celery juice has curative effects in combination with carrot juice and apple juice.

11.2.13  Cherries and Sour Cherries Sweet cherries (Prunus avium) and sour cherries (Prunus cerasus) contain a high level of antioxidants: anthocyanins that support antioxidant activity and quercetin that help to regulate blood pressure. A recent study shows the antidiabetic potential of sweet cherries (Gonçalves et al., 2017). They are also a good source of fiber, potassium, and vitamins A and C. In addition to the consistent intake of antioxidants, cherry juice is also beneficial by its anti-inflammatory properties at the muscle level (Alvarez-Suarez et al., 2017).

11.2.14 Corn Sweet corn (Zea mays convar. saccharata var. rugosa) is a subspecies of regular maize with a high sugar content. Even if it is commercially available throughout the year, corn must be consumed especially fresh in the summer. Like other whole grains, it is rich in complex carbohydrates. Sweet corn contains protein and fiber, potassium and vitamin C, and carotenoids (zeaxanthin) but also a variety of minerals (Butnariu et al., 2014). Fresh corn cobs should be preserved covered with leaves that protect the beans from dry air and provide important information about its freshness. If corn has green and damp leaves, it is fresh. The silk from the top of the cob should be dark brown (otherwise it is an indication that the corn was picked up too early). Sweet corn should be consumed immediately after the leaves were removed, so that it does not dry out.

11.2.15 Courgette/Zucchini The courgette (Cucurbita pepo var. cylindrica) is rich in starch and a cup of this vegetable contains only 29 calories. It contains lutein, ­beta-carotene, zeaxanthin—antioxidants that improve vision, but also nutrients such as potassium, magnesium, manganese, fiber, acid folic acid, and vitamins A and C (Deng et al., 2013; Zhou et al., 2013). Nutrients used for prevention of diabetic heart disease and atherosclerosis.

11.2.16 Cranberry Cranberries species (Vaccinium erythrocarpum, Vaccinium macrocarpon, Vaccinium microcarpum, and Vaccinium oxycoccos) are fruits commonly found in the months from October to November and have a lot of unique nutritional properties for the body. A half cup of fresh

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

cranberries contains 2 g of fiber (mostly insoluble); 9% of recommended daily intake of vitamin C. Cranberries carefully selected, put in plastic bags, and keep in the refrigerator up to 7 days. For long-term storage, place it in the freezer. Cranberries contain about 8900 antioxidants and are especially rich in vitamin C and polyphenols. They are especially recommended for urinary infections because they have been shown to significantly reduce the level of Escherichia coli in the urine (Harich et al., 2017). In addition, treatment with cranberry juice treats urinary tract infections and prevents the accumulation of bacteria in the urinary tract (Mathison et al., 2014; Takahashi et al., 2013). Also, cranberry seems to reduce the formation and activity of the mutagens streptococci, thus being important adjuvants in the specialized treatment. The proven ability of cranberries to fight bacteria is an additional stimulus to consume these fruits. Rich in vitamin C, cranberry juice has a significant restorative effect on the immune system. Cranberries based beverages are quite sour and are used for their medicinal benefits rather than for their taste; can be mixed with apple, pear, or grape juice to sweeten.

11.2.17 Cucumbers Cucumbers (Cucumis sativus) contain ~95% water: a cup of cucumbers slices thirst in the same proportion as a glass of water. There are various varieties of cucumbers. This vegetable contains low amounts of fiber, minerals, and vitamins and beverages prepared with cucumber ingredients are used extensively in skin revitalization, but also helps in digestive problems. Being a good source of potassium (>100 mg/100 g), cucumber-based beverages are taking part in balancing electrolyte levels, in case of dehydration.

11.2.18 Eggplant Eggplants (Solanum melongena) contain phytonutrients with an antioxidant role. They are important in the fight against cancer, have an antimicrobial, antiviral role, and reduce bad cholesterol. The eggplant fruits contain phenolic compound, the most abundant being the chlorogenic acid (Deng et al., 2013). They have a beneficial effect in the heart and contain in their bark a phytonutrient called nasunin anthocyan which gives the specific black color. Nasunin is known as a powerful antioxidant and an aid in the fight against free radicals that protect cell membranes. Small portions of eggplant can be used as ingredients in the mixture for fruit and vegetable smoothies.

11.2.19 Figs Figs fruits (Ficus carica) are a great source of iron, calcium, phosphorus, and fiber (when dry). They are sometimes added in a ­seasonal

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salad with apples and almonds. Fig fruits have been used all over the world to treat various health disorders such as gastric problems, inflammation, and cancer. Phytochemical studies on the leaves and fruits of the plant have shown that they are rich in phenolics, organic acids, and volatile compounds (Mawa et  al., 2013). According to Badgujar et al., F. carica represents an important source of biochemically active compounds, with practical applications in the prevention and treatment of various ailments such as anemia, cancer, diabetes, leprosy, liver diseases, paralysis, skin diseases, and ulcers (Badgujar et al., 2014). Fig fruits can be used as an ingredient for fresh smoothies.

11.2.20 Kiwifruit The kiwifruit (Actinidia chinensis) is also named kiwi or Chinese gooseberry. These small fruits contain plenty of antioxidants and phytonutrients that protect the DNA. Maintain blood glucose levels under control, protect the heart and colon (Wang et al., 2014), prevent asthma, and fight against macular degenerative diseases. They can also reduce the risk of blood clots. Kiwi are very tasty, eaten as such or can be added to salads, along with cold soups or in fruit tart composition. The fruit is ripe and ready to be eaten when it is slightly soft under a slight pressure exerted by the finger. If it is very soft, it is too ripe and is no longer good for eating.

11.2.21 Leek Related with onion, leek (Allium ampeloprasum) is available throughout the year, although its flavor is the deepest spring and autumn. Leek, like onion, is a rich source of prebiotics that helps to regulate bowel function. Leek is an excellent source of vitamin K. Also, it contains vitamins B6, C, and A, manganese, copper, iron, and folate.

11.2.22 Lemon Studies have shown that citrus fruits can attenuate the progression and onset of cancer and CVDs, although not many reports address the effects they have on vascular remodeling. Other study shows that the juices containing Citrus iyo presented a stronger inhibitory effect on neointima formation than the one containing Citrus unshiu, but overall proving that citrus fruit juices have inhibitory effects on oxidative stress, thus attenuating vascular remodeling (Ohnishi et al., 2015). It is a good white cell activator, an excellent anti-inflammatory, and a good liver decongestant. It is used with good results in the treatment of jaundice, liver congestion, liver, and pancreatic insufficiency. Also, it can be used in the management of diabetes (Aruoma et al., 2012).

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

11.2.23 Mango Mango (Mangifera indica) is a fruit that naturally has a cool effect in the body. Beverages prepared from mango will have an important content of vitamins A and C and beta-carotene, which were reported to be useful in preventing cancer (Bunea et al., 2008) and support skin health.

11.2.24 Mushrooms They are rich in niacin and riboflavin, vitamin B (less common in other foods). Helps in the growth and production of red blood cells and treats high cholesterol levels. Lentinan is a type of sugar molecule found in the composition of shiitake mushrooms, which can slow the growth of some form of cancer (Ina et al., 2016).

11.2.25 Oranges Oranges (Citrus sinensis) are considered to be the fruits of winter and are found from December to April in groceries. An average orange, 5.5 cm diagonal, contains: 3.5 g of fiber (soluble and insoluble); 11% of recommended daily intake of vitamin B1 and folic acid; and 107% of recommended daily intake of vitamin C. Oranges resist long enough at room temperature, but if kept in the refrigerator, it can last up to 3 weeks. Oranges can be used in many ways and almost all parts of it, including the peel, can be used. But most often they are consumed without peel, fresh or in the form of juice. Rich in vitamin C, fiber, calcium, and vitamin D, orange juice contains essential nutrients and fortifying substances for the bone system. Peel oranges is often put in drinks made from other fruits. Aschoff et al. compared the bioavailability of β-cryptoxanthin from either fresh navel oranges (C. sinensis L. Osbeck) or pasteurized orange juice. From their studies, orange juice represents a more bioavailable source of β-cryptoxanthin than fresh oranges (Aschoff et  al., 2015b). In others studies on content from freshly squeezed, flash-pasteurized, and pasteurized juices (Aschoff et al., 2015a) assumed that the higher hesperidin level in orange fruits compared to orange juice offers only a limited nutritional benefit.

11.2.26 Parsley The parsley (Petroselinum crispum) is effective in rickets. The parsley also has essential properties in oxygen metabolism, in maintaining the normal functioning of the adrenal and thyroid, in maintaining the health of the blood vessels, especially the capillaries, is excellent for genitourinary tracts, a great help for kidney and gallbladder stones; is

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effective in eye disorders, regularly consumed also has effects to prevent premature aging. Parsley juice is an excellent antiseptic of both the blood and intestines, and some therapists consider it as a very good preventative of cancer. Parsley juice or parsley-based beverages can be obtained from two splashes of well-washed parsley and a glass of water. The whole mixture is mixed for 2 min and then allowed to macerate 10 min before being consumed on the empty stomach. Parsley juice is a powerful immune and liver function stimulant, has antibiotic and antiviral effects. Recent studies have shown that parsley has an unusual effect in fighting against viruses that attack the liver. Hepatitis A, B, and C patients are recommended to make a 4  weeks cure with fresh parsley leaf juice. Can be used successfully and parsley root in salads or juice. The parsley root juice is obtained with the centrifugal electric juicer. Drink 50 mL (one quarter of cup) a day in combination with carrot juice. Treatment activates the immune system, helping the body to fight against hepatitis viruses and, moreover, has a direct action of inhibiting the multiplication of these viruses.

11.2.27 Pears Even if there are more autumn fruits, some types of pears are also found in the winter months. Pears contain more fiber than apples, a comparable level of vitamin C, few calories, and carbohydrates. The risk of stroke can be reduced by daily intake of fiber-rich food like pears with up to 50%. Pears can be kept at room temperature, but because they ripen very quickly, it is preferable to store them in the refrigerator, which is designed to stop the ripen. The pears contain antioxidant and flavonoid which can induce anti-inflammatory effects in the body generated by arthritis, rheumatic conditions, gout, and similar conditions (Baiano and Del Nobile, 2016). The pears mineral content is high and includes magnesium, calcium, manganese, phosphorus, and copper. These mineral aids in reducing bone mineral loss being useful in conditions like osteoporosis (Carluccio et al., 2016).

11.2.28 Peaches With the exception of amazing aroma, peaches are rich in vitamins A and C and potassium. Potassium-rich beverages are known to help in the reduction of blood pressure (Binia et  al., 2015). Peaches are an important source of antioxidants, beta-carotene (the one that offers yellow color), and flavonoids, which can help to slow the aging process by reducing the risk of certain types cancer and CVDs. The beta-­carotene also nourishes and protects the retina (Mezzomo and

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

Ferreira, 2016). Also is helping to prevent age-related macular degeneration and cataracts. In addition, each peach has only 60 calories, is rich in fiber and is fat-free. Choose scented peaches and avoid the very soft ones. The red color does not necessarily mean that the peach is very ripe, and this is only specific to certain varieties. Avoid green or very hard peaches.

11.2.29 Pepper/Capsicum Pepper (Capsicum sp.), green, yellow, or red gives a touch of color and taste in our food. The taste of this vegetable ranging from slightly spicy or very spicy to the refreshing, slightly sweet. Peppers are an excellent source of vitamin C (100 g of hot pepper contains 140 mg of vitamin C). Beta carotene (vitamin A) levels of hot pepper are very high, reaching up to 1300 μg, being slightly lower in sweet pepper. The mixture of vitamin C and beta carotene may be useful for cataract prevention as well as cardiovascular system diseases (Aschoff et al., 2015a).

11.2.30 Pineapple Pineapple (Ananas comosus) is a warm seasonal fruit, has a dense texture, is rich in vitamins, enzymes, and antioxidants (Hossain et al., 2015). Pineapple has an anti-inflammatory effect, protects against colon cancer (Gani et al., 2015), macular degeneration, and arthritis. One of the enzymes that pineapple contains is bromelain. Bromelain is a cysteine protease found in pineapple tissue with anti-­inflammatory and anticancer activities. Also has the ability to induce apoptotic cell death (de Lencastre Novaes et al., 2016).

11.2.31 Plum The plums are fruits of the tree Prunus domestica. These fruits contain many fiber and a natural laxative, called sorbitol. In addition, plum juice also provides antioxidants (Wolfe et  al., 2008), iron, potassium, fluoride, phosphorous, magnesium, calcium, and zinc. The plums contain vitamins A, B1 (thiamine), B2 (riboflavin), B3 (niacin), B-6, vitamin C (ascorbic acid), vitamin E (alpha-tocopherol), vitamin K (phylloquinone), and folate. They also offer very low calories without any harmful fats.

11.2.32 Pomegranate Pomegranate is one of the most nutritious fruits of the autumn-­ winter period (October-December). One pomegranate contains: 1 g of fiber (mostly insoluble); 12% of recommended daily intake of vitamins

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B6 and C and potassium. Pomegranate can be kept at the room temperature for a week or for 2 weeks if you keep it in the refrigerator. Fruits that bring multiple health benefits, pomegranates are rich in antioxidants that can reduce the risk of cardiovascular complications such as heart attacks (Wang et  al., 2014). Also, pomegranates may help in the prevention of breast cancer (Mandal et al., 2015) or colon. Despite the numerous calories they provide, pomegranate juice offers a very generous amount of antioxidants that protect brain cells and have anticancer properties (Wolfe et  al., 2008). Recommended for both therapeutic and aesthetic reasons, pomegranate juice is beneficial for heart health, but also for treating cancer or inflammation. It also contributes in maintaining cell health, which is important for people who want to keep their young look as long as possible. Some studies on human prostate cancer cells show the effectiveness of the pomegranate extract against prostate cancer (Wang et al., 2014).

11.2.33 Pumpkin The pumpkin is rich in alpha and beta carotene that can be converted into retinol, which helps to improve vision and increase cells (Deng et al., 2013). Pumpkin seeds are a good source of alpha-linoleic acid, a fatty acid omega 3 that could be useful for people suffering from CVD, hypertension, high cholesterol, or liver cancer (Shen et al., 2017).

11.2.34 Red Beetroot The main components of red beet juice are carotene, vitamins A, B1, B2, B6, C, and E, folic acid, niacin, pantothenic acid, choline, calcium, silicon, magnesium, phosphorus, potassium, oxalic acid, zinc, cobalt, molybdenum, lithium, selenium, manganese, rubidium, aminoazines, flavonoids, and betanin. Red beet juice has strong healing effects, being a precious adjunct with antibacterial, anti-sclerotic effects to stimulate the immune system. It also helps to stimulate diuresis and restore intestinal flora. According to Singh (Bhupinder and Bahadur, 2014), betalains and phenolic compounds that exist in red beetroot have been reported to increase the resistance of low-density lipoproteins (LDL) to oxidation and to prevent cancer and CVDs by reducing the oxidative effect of free radicals on lipids. Other studies confirmed also the beetroot content of betaxanthins and betacyanin of the betalain family, betalains as health protective molecules in beetroots. Therefore, betalains are related to anti-­ oxidative stress, anti-inflammation, and antitumor effects of beetroots (Ninfali and Angelino, 2013). It is also indicated in case of anemia, demineralization, tuberculosis, neurosis, and menopausal disorders. Due to its strong taste, it must be mixed with other juices. The curative effect of beet juice

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

can be enhanced by combining red beet juice with carrot juice, celery, or apple juice. Within this context, red beetroot (Beta vulgaris L.) is preferred as a rich source of betacyanin, having the group of reddish to violet betalain pigments which are majorly composed of betanins and isobetanins (Guldiken et al., 2016). Red beet stimulates hematopoiesis (red blood cell formation, white blood cells, and platelets), remineralizes the body, and stimulates the conversion of glucose into glycogen in the liver. It was experimentally demonstrated that beetroot has the potency to preserve bone marrow integrity and stimulate the differentiation of HSCs (hematopoietic stem cells) against ionizing radiation (Cho et al., 2017). Red beet juice has a strong effect on the body and should be consumed in small quantities and mixed with other fruit and vegetable juices. It is an excellent blood purifier and is effective in cleansing the liver, kidneys, and arteries. Kujawska et al. investigated the implication of beetroot juice in protection of Wistar rats from oxidative stress induced by carbon tetrachloride (CCl4). They observed that the beetroot juice reduced plasma protein carbonyls and DNA damage in blood leukocytes (Kujawska et al., 2009). Red beet juice provides energy because of the high levels of natural sugars it contains, although it should be avoided by those who suffer from diabetes. It is also indicated for digestive problems such as constipation, and strengthens the bones, which is very useful for older people whose bones become more fragile. It is also helpful in treating liver disease (Clifford et al., 2015). Red beet juice should be consumed in combination with other vegetable juices (preferably carrot), in appropriate proportion to avoid any negative reactions of the body. For example: a portion of beets juice (50 mL), two or three parts carrot juice (100 or 150 mL), and lemon juice to correct the taste.

11.2.35 Red Grapes There are currently more than 300 studies that cite the beneficial effects found to be induced by the consumption of natural grape juice, as well as vegetal oils obtained from grape seeds or the skin of these fruits. Red grapes contain many types of antioxidants, mainly flavonoids such as anthocyanins and catechins that are of medical importance in the treatment of diabetes and CVDs (Li et al., 2014). Studies have concluded that if grape-derived products are administered to laboratory animals, a reduction in the tendency for vascular thrombosis may occur. And these results have recently been extrapolated to human subjects. This observation is the basis of the “French paradox,” a theory published in the early 1990s, which was based on

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the observation that the French suffer from fewer cardiac conditions than the rest of the European population. Initially, the explanation seemed incredibly, but in time it was proved to be true: the protective effect against these diseases is due to the consumption of red wine in moderation. It is known that the French are used to drink a glass of red wine at the table, and it is that keeps their vascular tonus in normal parameters for longer time (Galinski et al., 2016). In addition to reducing platelet aggregation, polyphenols in grapes also have other benefits, such as: • significantly reduce the susceptibility of endothelial lesions; • reduce angiotensin activity, an endogenous substance that can cause vasoconstriction and hypertension (Neto et al., 2017); and • increases production of vasodilators, especially nitric oxide. The content of antioxidants in grapes is very important. Resveratrollike substances (an antioxidant polyphenol) have been correlated in many studies with protective effects against various neoplasias, cardiovascular disorders (Blumberg et  al., 2015), neurodegenerative disorders including Alzheimer's disease, and viral infections. This antioxidant seems to have beneficial roles in retarding the aging of the body, reducing the incidence of diseases induced by cellular and tissue degeneration: heart and muscle diseases in particular. Resveratrol is also found in abundance and in berry-like fruits, especially in raspberries and mulberries, not just in red grapes. Many of the types of flavonoids that are found in grapes (both in white and red and in rosé) can be found in both green and black tea, but also in black bitter chocolate. However, the content of these products in antioxidants remains inferior to berries and grapes, and research to determine their bioavailability is still ongoing. Specialists believe that flavonoids favorably stimulate heart function and maintain normal vascular tonus, prevent clotting of clots that may favor acute myocardial infarction or stroke, prevent cholesterol deposition on vessel walls with atherosclerosis, and promote at the same time maintaining the elasticity and flexibility of the vessels for a much longer time (Levantesi et al., 2013). Grape juice has similar antioxidant properties. One study has shown that by consuming a large glass of grape juice every day, LDL cholesterol (the one that negatively influences the health of the body) can be reduced. It also can improve systemic vascular tonus and stimulate normal blood flow. In addition, grape juice does not have the same contraindications as wine and cannot cause negative effects if it is consumed “abusively.” Antioxidant concentration varies significantly depending on the type and species of grapes, and in some cases, grape juice may be richer in vitamins compared to fresh grapes. However, nutrition

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e­ xperts advise that it is best to choose fruit instead of juices, because in juices not only vitamins are more, but also calories. The red grape juice, prepared in its entirety (seeds, pulp, and grains), provides flavonoids and resveratrol, two powerful antioxidant substances, with antitumor and healing effect for a wide range of conditions. Red grape juice consumption reduces the risk of blood clots, lowers cholesterol, and maintains healthy blood pressure (Aubert and Chalot, 2018). An assessment on how are affected the chemical composition (quantitative and qualitative) and the functionality (in  vitro and in vivo) of juices based on the producing region, variety, and farming system of grapes (conventional, organic, and biodynamic) shown that the effects of these variable on the chemical composition (especially phenolic compounds) and functional properties of juices are remarkable (Granato et al., 2016). The basic steps to produce grape juices are shown as a flowchart in Fig. 11.2.

11.2.36 Red Raspberry Succulent, sweet and cool, delicious raspberries (Rubus idaeus L.) can be introduced into the daily diet, fresh, as well as in the c­ omposition

Grapes Sanitization (NaCIO at 50–200 mg/L) Crushing

Hot pressing (T~85°C/60–120 min) Pectinolytic enzymes at 55–60°C Must

Grape pomace

Filtration Pasteurization at 85°C/10 s Juice

Bottling

Fig. 11.2  Steps and unit operations used in hot-pressing method for producing the grape juice.

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of various desserts. Raspberry is rich in fiber, some of which are soluble—in the form of pectin, which helps to lower cholesterol, being an excellent source of vitamin C. The red color of raspberries is provided by the high level of anthocyanins (antioxidants). Known as the “golden fruit,” red raspberry is rich in anthocyanins with documented biological activities of medical importance especially CVD, cancer, all of which share critical metabolic, oxidative, and inflammatory links (Teng et al., 2017). According to Ludwig et al. (2015), red raspberries (R. idaeus L.) are a rich source of polyphenolic compounds, the main components being anthocyanins and ellagitannins.

11.2.37 Spinach Spinach (Spinacia oleracea L.) is a nutrient-rich leafy vegetable. It contains at least 13 different flavonoids that function as antioxidants and anticancer agents (Roberts and Moreau, 2016). Spinach contains vitamin K and carotenoids (Bunea et  al., 2008) useful for bone and heart protection, useful for eye diseases such as cataracts and macular degeneration (occurring with age). Moreover, it protects the brain from oxidative stress and reduces the negative aspects of aging, which contribute to the decline of brain function (Fornaciari et  al., 2014). According to Jiraungkoorskul, spinach may be used in the prevention of Alzheimer's disease (Jiraungkoorskul, 2016). With few calories and rich in vitamins, spinach is one of the most important nutritious foods. A cup of spinach leaves contains more than the recommended daily dose of vitamins K and A, manganese and folic acid, and about 40% of the magnesium body requirement. It is an excellent source, which contains over 20 different nutrients, including dietary fiber, calcium, and protein. And yet, a cup has only 40 calories.

11.2.38 Sea buckthorn Beta-carotene in the sea buckthorn (Hippophae rhamnoides) has synergic action with interferon. Sea buckthorn contains many immunostimulant substances, the use of juice with great results in the treatment of hepatic diseases (hepatitis and cirrhosis), diabetes (Xue et al., 2015), liver cancer (Guo et al., 2017) and contribute to a general improvement of health.

11.2.39 Sweet Potatoes These orange vegetables have the best taste during autumn (their peak season). Like the pumpkin, sweet potatoes (Ipomoea batatas) are rich in beta-carotene, which can prevent vitamin A deficiency, help to maintain vision health and generate retinol production

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(Mezzomo and Ferreira, 2016). Sweet potatoes are also a good source of vitamin C (Deng et  al., 2013). Portions of boiled of oven-cooked sweet potatoes may be used as ingredients for combined smoothies.

11.2.40 Tomatoes Known as the “apple of love,” tomatoes (Solanum lycopersicum) are worthy of this name. They are full of nutrients and are loaded with a special flavor. A fresh medium-sized tomato is an excellent source of vitamins A and C. Seasonal tomatoes contain twice as much vitamin C as those available at other times of the year. Tomatoes contain lycopene and carotenoids, which are helpful in prevention of certain types of cancer, especially prostate cancer. In a study conducted at the Cambridge University Hospitals, a conclusion was that lycopene improves endothelial function in CVD patients (Gajendragadkar et  al., 2014). Cherry tomatoes are delicious served in salads or in snacks composition. Some type of cherry tomatoes has fewer seeds than other varieties and is recommended for cooking sauces and cooked foods. Tomatoes can have different shapes, sizes, and colors. Refrigeration destroys the aroma of tomatoes. Thanks to the sun, tomatoes contain many nutrients and are therefore extremely beneficial to the body. They are excellent for blood and are a good tonic for the nervous system. These are particularly beneficial for people who suffer from anxiety, stress, nervousness, insomnia, and fatigue. The active compounds that this vegetable contain exhibited the ability to remove uric acid from the organism. Tomatoes based beverages are recommended for arthritis, gout, and rheumatism. The red juice, besides vitamins A, B, C, and E, and iron, phosphorus, potassium, and sulfur minerals, contains lycopene, a red dye with antioxidant and antitumor properties. It prevents the development of cancerous cells in prostate cancer, bladder, pancreas, breast, lungs, or skin. There are studies which show that lycopene can be useful in preventing and stopping ovarian, intestinal, cervical, or uterine cancer from evolving. Lycopene is also useful in lowering cholesterol levels (Carluccio et  al., 2016). Tomato juice has detoxifying properties and can help in skin problems such as acne or furuncles. Tomato juice can be consumed simply or in combination with carrot juice, apple, celery, or onion juice.

11.2.41 Watermelon Scented, sweet, red watermelon (Citrullus lanatus) is refreshing and easy to digest. It contains more lycopene that fights cancer per serving, than tomatoes: about 40%. Lycopene present in watermelon is easy to absorb without requiring high-temperature treatment, unlike tomato and is relatively stable when watermelons are stored

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and ­refrigerated. Watermelon is a rich source of vitamins A and C, it contains vitamin B6, beta-carotene (Mezzomo and Ferreira, 2016), thiamine, and potassium. The watermelons you eat must be hard and symmetrical, not cut or with traces of blows. It is a good source of citrulline which participates in lowering blood pressure. In some studies, watermelon juice intake has been linked with reduced insulin resistance, which is helpful to combat the metabolic syndrome and type 2 diabetes (Xue et al., 2015).

11.3  Antioxidants in Fruit and Vegetables Antioxidants are actually natural compounds that can be found in fruits and vegetables and have an important role in stimulating and promoting the health of the body and in helping it to cope with both internal and external environmental attacks. They comprise a large class of compounds, including, vitamins, minerals, and polyphenols (Fig. 11.3). The contribution of natural antioxidants in the prevention and treatment of diseases is of primordial importance. With such allies, the immune system can fight and neutralize the aggression much faster and thus prevent the emergence of imbalances that translate into body homeostasis through illness, inflammation, degenerative processes, aging, and even abnormal cell activations and replications (characteristic of cancers). Experts believe that antioxidants are substances capable of counteracting the harmful effects of toxic metabolites resulting from both endogenous processes (as products that the body needs to discard) but which are also present in the external environment as a result of pollution. These products are called oxygen-free radicals and have a very high chemical reactivity, being able to determine impulsive cellular lesions, culminating even with the death of the cells they act on. The most important free radicals known to date are superoxide and

Fig. 11.3  Main classes of antioxidants.

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hydroxyl. As the name says, they are derived from oxygen, but they get properties that make it very toxic. The oxidation process can evolve in cascade: it is enough for a cell to be prone to the action of these metabolic products, then to expand the process and thus to lay the foundations for disease or even cancer. It is already known that in fact, cancers arise as a result of internal imbalances culminating in the undesirable interaction between these free radicals and cellular DNA, resulting in mutations. Free radicals are also criminalized in the processes of general aging of human organism, as well as in more specific disorders: atherosclerosis, liver disease, pulmonary emphysema, Parkinson's disease, Alzheimer's disease, and schizophrenia. In certain concentrations, free radicals have neutral effects and do not harm the body, not being able to induce serious injuries. In addition, the body seems to have a number of own mechanisms to fight them (mainly represented by enzymes that can neutralize them). But it is very important for our daily diet to offer new and new allies. The most impressive are the antioxidants (Baiano and Del Nobile, 2016). They play the most important role in providing protection against these harmful oxygen species. Most of the time the most important antioxidant action is vitamins A, E, and C and polyphenols. They seem to be able to inhibit oxidation reactions and remove tissue and metabolic intermediates from tissues. Antioxidant compounds found in fruits are: ascorbic acid (vitamin C), vitamin E (tocopherols and tocotrienols), polyphenols (such as flavonoids and resveratrol), and carotenoids. The most important sources of antioxidants are found in nature, in complex forms and never alone. The poly-vitamin complexes provided by fruits and vegetables are very beneficial to the whole body and can help to stimulate the immune system so we can get protection against a wider range of conditions. Over time, specialists have analyzed the antioxidant content of over 100 fruits, vegetables, cereals, nuts, and spices, but the results have always been similar: the richest in antioxidants are berries. Over the time, extensive research work has been done to investigate the antioxidants content in food sources such as fruits, vegetables, edible flowers, and mushrooms. The antioxidant capacities and total phenolic contents of extracts of 56 commonly consumed vegetables were studied by Deng et  al. (2013). Of course, the different species of vegetables investigated exhibited diverse antioxidant capacities. However, the highest antioxidant capacities and phenolic contents were found in Chinese toon bud, loosestrife, perilla leaf, cowpea, caraway, lotus root, sweet potato leaf, soy bean (green), pepper leaf, ginseng leaf, chives, and broccoli, while the values were very low in marrow squash and eggplant

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(­purple). These vegetables species also had a high content of phenolic compounds such as chlorogenic acid, gallic acid, and galangin (Deng et al., 2013). Antioxidants play an important role in recovering free radicals and maintaining a proper balance of human organism. The use of synthetic drugs to maintain the healthy state of the population and for the disease prevention is apparently not an optimal choice. The search for natural antioxidants to replace synthetic antioxidants is not just the trend of pharmaceutical and health industries, but also the demand for nutritionist experts, including the new development direction of the food industry. Antioxidants play an important role in scavenging free radicals and maintaining body balance. Here, we discussed the contribution of natural antioxidants in diseases prevention and treatment. In modern life in which nature is advocated, the application of synthetic drugs for the health care and prevention of diseases apparently is not an optimum choice. Searching natural antioxidants to replace synthetic antioxidants is not only the trend of pharmaceutical and healthcare industries, but also the demand of Food Nutriology, even the new development direction of food industry. Traditional Chinese herbs have attracted more and more attention from scholars at home and abroad, especially, the treatment efficacy of diseases and healthcare functions as well as the bioactive components of these natural herbs. More and more bioactive components have been isolated and identified, which enables traditional Chinese medicine to be an important development direction of modern medicine and healthcare products. In addition, some scholars have isolated bioactive substances with strong antioxidant function from fungi, yeast, and algae. Natural antioxidants can be used as natural food additives with the new concept of natural healthcare concepts in food processing and preservation, which will better meet with the demands of modern society. The extraction and preservation process of natural antioxidants is the development target for the future food and medical healthcare industries. The innovation and improvement in analysis and extraction technology of natural antioxidants in foods is also an urgent matter during the development of related industries (Li et al., 2014). Saikia et al. selected 13 fruits from the region Assam, India to study their phytochemical content and antioxidant activity. Their results shown that black jamun has highest total phenolic content followed by litchi, bogi jamun, amla, hog plum, pani jamun, and carambola. The highest ferric reducing antioxidant potential was found in Amla. DPPH radical scavenging activity of amla, black jamun, hogplum, litchi, and poniol was above 90%. The highest values for metal chelation capacity were found in poniol, carambola, and leteku. The fruit extracts were studied at RP-HPLC (reversed phase high-performance

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liquid chromatography) and the results showed the presence of ascorbic acid, phenolic acids, and flavonoids with a different composition and content depending on the fruit type (Saikia et al., 2016). Below there is a list of the best ingredients for vegetable juices and the health disorders that can be treated with them (Table 11.2).

Table 11.2  Health Disorders and Vegetable Beverages Recommended Health Disorder

Fruits and Vegetables Recommended

Acidosis Acne Anemia Allergies Appendicitis Atherosclerosis Arthritis Asthma Bronchitis Colds Constipation Colitis Diabetes Dyspepsia Eczema Epilepsy Visual disturbances Fatigue Gout Headaches Heart diseases Hypertension Flu Insomnia Jaundice Obesity Hemorrhoids Sinusitis Tonsillitis

Carrot, beet, cucumber, and spinach Carrot, lettuce, and spinach Beet, celery, and carrot Carrot, lettuce, and spinach Carrot, beet, and spinach Carrot, celery, lettuce, and spinach Cucumber, beets, celery, carrot, and watercress Carrots, radishes, and celery Tomatoes, carrots, onions, and spinach Carrot, celery, onion, and spinach Carrot, beet, spinach, and watercress Carrot, beet, cucumber, and spinach Carrot, celery, lettuce, watermelon, and spinach Carrot, beet, cucumber, and spinach Carrot, spinach, cucumber, and beets Carrot, celery, and spinach Tomatoes, carrot, celery, parsley, and spinach Carrot, spinach, beets, and cucumbers Tomatoes, cucumbers, beets, carrots, celery, and spinach Carrot, lettuce, and spinach Carrot, beet, cucumber, and spinach Carrot, spinach, beets, and cucumbers Carrot, onion, and spinach Lettuce, carrot, and celery Carrot, celery, spinach, beets, and cucumbers Tomatoes, beets, cabbage, lettuce, spinach, and carrot Carrot, spinach, ham, and toast tomato, carrot, onion, and spinach carrot, spinach, beets, and cucumbers

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11.3.1  Juice with Red Beetroot, Apples, and Carrots A beverage with anticancer properties. Apples protect the stomach from harmful bacteria and lungs from the harmful effects of cigarette smoke. Red beetroot stimulates the formation of red blood cells and cleanses the liver. Lemon gives beneficial effects: it removes toxins from the liver, improves the function of the bile, favors the absorption of minerals, and purifies the blood. Ingredients: 2 apples 3 carrots ½ red beet ½ lemon Mix in a blender apples, carrots, red beets, and lemon. The composition is squeezed, served in a high glass, and seasoned with a slice of lemon.

11.3.2 Ginger and Pineapple Juice A combination that helps for detoxification. It's a real package of vitamins, minerals, fiber, and enzymes that revitalize the body help in weight loss diets and in the treatment of candida. Ingredients: 1 small pineapple juice from ½ lemon 1 teaspoon of freshly chopped ginger a handful of parsley, cilantro (coriander leaves), and fresh spinach 100 mL of water Put all the ingredients in a blender, and complete with water. Water can be replaced with a few pineapple slices.

11.3.3 Apple and Carrots Juice 8 carrots 2 apples ginger The washed carrots and apples are squeezed in the extractor. A teaspoonful of chopped ginger is added. This beverage is best to be served cold.

11.3.4 Other Combinations • 2 peaches, 1 apple, 1 per • 6 strawberries, 1 apple, half orange • 1 kiwi, half of mango, 1 orange, mineral water as desired

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• 1 apple, 4 small carrots, 1 celery stalk, half lemon, one-quarter of cucumber • 1 apple, 3 medium carrots, half pepper, 4 lettuce leaves, half lemon, 1 tomato • half a cup of fresh broccoli, 1 apple, 3 small carrots, a handful of parsley, half lemon (very rich in calcium) • 2 medium carrots, 1 celery stalk, 1 small potato, 1 apple, half lemon • maximum energy: 3 carrots with skin, 1 apple with skin, 2–3 celery stalks, 1 small orange (160 calories, 3.1 g fiber, 36 g carbohydrate, 0.9 g fat, 22.5 mg folic acid, 3451.3 mg vitamin A, and 21.8 mg vitamin C) Based on the biological compounds content, and the existing synergies between them, below are presented a few recipes for beverages that can be prepared from fruit (Table 11.3), vegetables, or mix of them (Table 11.4).

Table 11.3  Recipes for Fresh Fruit Beverages Fruits name

Recipe

Apples-apricots-peaches Apples-berries

One fruit of each goes through the juicer, then serves. 1 Cup of strawberries, raspberries, blueberries are squeezed together with 2 apples. 2 Apples, one cup of grapes, 1/4 lemon are squeezed together. 3 Apples + 1 pear + 1 slice of ½ cm fresh ginger. Squeeze ½ melon, then pour the juice into the blender and add a banana, then mix. ½ Cup berries, ½ cup strawberries, ½ cup other berries, 1 apple or 1 pear ½ Melon + watermelon by wish 1 Cup grapes + 1 grapefruit 1 Cup grapes + ¼ lemon + ½ sliced pineapple ½ Grapefruit + 2 oranges 3 Kiwi + 2 oranges 4 Apples + ¼ lemon are squeezed and served with crushed ice 1 Cup white grapes + ½ lemon + 2 oranges are squeezed and mix with 125 mL of carbonated mineral water. 1 Slice of ½ cm ginger + 1/4 lemon + 1 green apple + 125 mL carbonated mineral water. Juice is useful for intestinal disorders. 4 Apricots + 1 mango + 1 orange are squeezed in the mentioned order 2 Plums + 2 apples + 1 pear squeezed together are very useful for regulating intestinal transit in people who suffer from constipation.

Apples-grapes-lemon Apple-pear-ginger Banana-melon Berries Melon-watermelon Grapes-grapefruit Grape-lemon-pineapple Grapefruit-orange Kiwi-Orange Lemonade 1 Lemonade 2 Lemonade 3 Apricot-mango-orange Plum-apple-pear

Continued

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Table 11.3  Recipes for Fresh Fruit Beverages—cont’d Fruits name

Recipe

Grapefruit-raspberry

1 Cup of raspberries + 1/2 grapefruit. Juice is useful in weight loss diets 1 Cup cranberry + 2 apples + 1 orange Squeeze ½ cup of cranberry, then add ½ lemon, a cup of grapes and two apples. Squeeze first a slice of ginger ½ cm, ½ cup of mint, then 1 kiwi and ¼ pineapple. The juice is useful in intestinal spasms, bloating. Squeeze first a cup of mint, then 2 kiwi and then 1 green apple. ½ Mango + 2 oranges + ½ papaya + ¼ pineapple squeeze, then place in the blender with 1 banana. 1 Slice of ½ cm of ginger is squeezed, and then adds 1 apple and 4 carrots. Frequently used, the drink plays a role in lowering cholesterol levels. 1 Orange + ½ pineapple + ½ cup strawberries are squeezed then put in the blender along with 1 banana. ½ Sliced melon + 1 cup of strawberries. Juice can also be made from frozen fruits. Juice from 1 slice of 2.5 cm ginger + ¼ lemon and add it to a cup of hot water. Sweat with honey to taste. Drink has a diaphoretic effect (heats the body and facilitates sweating) Squeeze the sliced ¼ pineapple juice and insert it into the blender with a blueberry mug and a banana. 2 Apples + 1 pear + 2 kiwi + 1 ginger slice of 0.5 cm

Cranberry-apple-orange Cranberry-lemon-grape-apple Pineapple-kiwi-mint-ginger Mint-kiwi-green apple Exotic juice Apple-carrot-ginger

Orange-pineapple-strawberry-banana Melon-strawberry Lemonade with ginger for the cold

Cranberry-pineapple-banana Apple-pear-kiwi-ginger

Table 11.4  Recipes for Beverages Prepared from Vegetables of Fruit-Vegetables Mix Vegetables name

Recipe

Beet-carrot-apple Beet-carrot-parsley Carrots- spinach-beet Broccoli-carrots-celery Broccoli-carrots-parsley Cabbage-carrot-parsley

½ Red beet + 4 carrots + 2 apples ½ Beets + 4 carrots + ½ cup of parsley ½ Beets + 3 carrots + ½ spinach cup 1 Rod of broccoli + 3 carrots + 1 stick of celery 1 Rod of broccoli + 3 carrots + ½ cup of parsley ½ Cabbage + 3 carrots + ½ cup of parsley

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Table 11.4  Recipes for Beverages Prepared from Vegetables of Fruit-Vegetables Mix—cont’d Vegetables name

Recipe

Cabbage-carrot-celery

½ Cabbage + 2 carrots + 4 celery stalks are squeezed together. Juice is useful as an adjuvant in the treatment of peptic ulcer. 4 Carrots + ½ cucumbers + ½ cup of parsley 4 Carrots + 1 dandelion root + ½ cup of spinach 5 Carrots + ½ cup dandelion leaves + 2 celery stems. This juice has a diuretic effect. 1 Dandelion root + ½ beets + 2 carrots + 1 apple. This recipe improves the function of the liver. 4 Celery stalks + ½ cucumber + ½ cup parsley + ½ cup spinach ½ Cup of parsley, ½ cup of spinach, 4 tomatoes. Squeeze a cup of parsley, cup of spinach, 4 carrots. 1 Beet + ½ sweet potato + 3 carrots. A diet of this juice made before a holiday in a sunny location protects the skin from sunburn 2 Carrots + 2 apples + 1 cup of broccoli + ½ cabbage. It is a very useful juice for detoxification. 1 Apple + 4 carrots +1 celery stalk + ½ lemon + ¼ cucumber ½ Cup broccoli + 1 apple + 3 carrots + one handful of parsley + ½ lemon 2 carrots + 1 apple + 1 celery stalk + 1 small potato + half lemon. Potato juice, though unpleasant to taste, is very useful in treating many digestive disorders (gastritis, colitis, irritable bowel). 4 Berries + 1 cucumber + 2 apples + 1 spinach + ½ lemon + 2 slices of ginger. ½ Apple + 3 carrots + 2 celery stems + ½ cucumber + 1 cup spinach. 1 Apple + 1 carrot + 1 celery stalk + 1 cucumber + ½ lemon + ¼ mint cup + ¼ cup parsley + 2 cm ginger.

Carrot-cucumber-parsley Carrots-spinach-dandelion Carrot-leaves of dandelion-celery Carrots-apple-beet-dandelion Parsley-celery-cucumber-spinach Tomato-spinach-parsley Parsley-spinach-carrots Sweet potatoes-carrot-beet Apples-carrots-broccoli-cabbage Apple-carrot-celery-lemon-cucumber Apples-carrots-broccoli, parsley-lemon Carrots-apple-celery-potato-lemon

Celery-cucumber-spinach-apple-lemonginger Apples-carrots-celery-cucumber-spinach Apple-carrot-celery-cucumber-mintparsley-lemon-ginger

11.4  Concluding Remarks 11.4.1  Fruit-Based Beverages Among the healthiest fruit juices that can be prepared from fresh raw material is the one prepared from, grapes, redberry, and green apples. All these ingredients contain biologically active compounds that are excellent for the health of the blood cells and muscle function. It also gives the daily dose required for vitamin K—very important for blood and bone health.

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For a healthy skin, a beverage prepared from soothing and moisturizing ingredients, rich in vitamins A, B, C, and E, may be prepared from a mix of pear and cherry juice. Another beverage considered among the healthiest recipe, being the supreme antioxidant, is juice from blueberries, strawberries, and mangoes. It will supply the maximum energy needs especially for people who are on losing weight diet. Pomegranate juice is also one of the healthiest ingredients for fruit beverages, known worldwide as being very beneficial to the heart in treating cancer or inflammation. A glass of fresh pomegranate juice is what you need to help to maintain the health of the cells. Eventually, the fresh beverage obtained from fruits that will help to improve the health status in case of colds and help to boost immunity in the cold season, will be prepared from vitamin C-rich fruits, such as grapefruit, orange, and kiwi juice. Full in vitamin C, these combined fruits are excellent for fighting flu.

11.4.2  Vegetables-Based Beverages Fruit juices are excellent in combination with fresh vegetables. Among the healthiest fruit and vegetable juices are pineapple juice, carrots, oranges, spinach, red cabbage, and lemon juice. Good antioxidant and very effective in diets, this juice gives you the energy and daily work power. Celery juice, carrots, cucumbers, and apples are also the best choice of ingredients for a fresh and natural beverage. It provides the human body a good functioning through the detoxifying effect. Another interesting combination would be a mix of banana, kiwi, pineapple, carrot, and red beetroot. The resulting beverage protects the liver and is a rich source of natural nitrates that ensures good blood circulation to the brain, heart, and muscle. Wheat germs may be added to all these beverages. It seems that 30 mL of wheat germ juice is equivalent to eating 1 kg of fresh vegetables. It was already demonstrated that fruit juices or vegetable juices are true natural medicines, and their effect can be enhanced by combining the main ingredients. The daily consumption of fruit and vegetable juices at every meal is a recommendation to be considered by all those who want to have as few health problems as possible. Beverages prepared from fresh fruits and/or vegetables, in the form of simple juices or smoothies, have the role of protecting the body from diseases, but also of improving certain uncomfortable health disorders. It has been found that the curative effects of the various natural ingredients can be combined into a single drink, thus obtaining both a special taste and a greater range of beneficial effects.

Chapter 11  Fruit and Vegetable-Based Beverages—Nutritional Properties and Health Benefits  

Nowadays, the smoothies are frequently consumed beverages, and are usually prepared from a mix of ingredients that will boost the energetical value. Most of the consumers choose the smoothies consumption for the perceived health benefits. However, care should be taken, to avoid extreme behavior, such as excess energy intakes, and to keep a balanced intake of nutrients, including proteins originating from dairy products and animal origin products (such as meat, eggs, etc.).

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NEERA: A NONALCOHOLIC NUTRITIOUS BEVERAGE FROM UNOPENED INFLORESCENCE OF COCONUT PALM

12

Asha S*, Ratheesh M*, Svenia P. Jose*, Krishnakumar I.M†, Sandya S‡ *

Department of Biochemistry, St. Thomas College, Pala, Kottayam, India, R&D Centre, Akay Flavours & Aromatics Pvt Ltd, Cochin, India, ‡Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India †

12.1 Introduction The coconut (Cocos nucifera) is the most widely grown palm in South Asian countries with excellent nutritional and medicinal values. Coconut and its products are one of the wonder foods on the Earth that amply provides for all human needs and have multiple health benefits, so it is mentioned as “Tree of life.” These tropical palms are an environmentally valuable tree crop that develops in various, natural life steady agro-biological systems, reestablish harmed soils, and does not need much water. Coconut palms are considered to be among the most established blossoming plants on the planet. The five noteworthy financial palms of the world are African oil palm (Elaeis guineensis), coconut (Cocos nucifera), be-tel nut palm (Areca ­catechu), date palm (Phoenix dactylifera), and pejibaye (Bactris ­gasipaes). Among these, coconut fabricate inflorescences all through the year and so can be tapped. For centuries throughout the tropics, the conventional practice of “tapping” coconut trees for their highly valuable “sap” is a time-honored art form. The nutrient-rich sap, which emanate from the blossoms before they develop into coconuts, is used as natural bio-beverage and is used to make many different nutritious food products. The coconut tree produces 12–14 inflorescences (spadix) in a year, on an average one in a month. Every spadix can bolster 20–25 delicate or develop nuts. Delicate nut need 6–8 months, while developed nut takes almost an entire year for development. At a s­ ensibly Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00012-2 © 2019 Elsevier Inc. All rights reserved.

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high water substance of 500 mL for every delicate nut, the aggregate water acquired from spadix is approximately 10–12.5 L. A similar spadix, whenever tapped, could deliver 60–67.5 L of sap in a period of simply 40–45 days at a moderate yield of 1.5 L every day. Besides, it is wealthy in supplements and phytochemicals contrasted with delicate coconut water. Physiologically, tapping is more vitality effective contrasted with enabling the spadix to create nuts. The sweet, oyster white, and translucent sap obtained from unopened inflorescence of coconut trees is popularly called as Neera in India, ‘Raa’ in Sri Lanka, and ‘Tuba’ in Philippines. The freshly gathered sap is exceedingly nutrient rich, and it is delivered right out of the tree naturally sweet and abundant in minerals, 17 amino acids, broad-spectrum B vitamins, vitamin C, and has an approximately neutral pH. Coconut inflorescence sap is appropriate for natural fermentation at ambient temperature within a few hours of extraction. Once fermented, it is called toddy with 4% alcohol. By using various technologies developed by different research institutes, this unfermented coconut sap is prelucrated and conserved in its natural form to preserve the sugar, vitamins, and other nutrients beneficial for health. It is consumed as one of the natural nutritional drink in countries like Africa, Malaysia, Indonesia, Thailand, and Myanmar. The drink attained popularity on account of its high nutritive value, agreeable flavor, and delicious taste. The sap is extracted generally during the early morning hours. The tapping methods are different from country to country and within the country. The spathe is considered ready for tapping when the mature one bursts or is just about to burst. One of the most important facts about tapping a coconut tree is that once it is tapped, its sap constantly flows for the next 20  years. From a sustainability perspective, the harvestable energy (food production) from tapping coconut trees for their sap (which yields 5000 L per hectare), rather than permitting them to produce fruit, is 5–7 times higher per hectare than coconut oil production from mature coconuts. Unfermented coconut inflorescence sap (also mentioned as neera) is a sweet juice exuding from the unopened inflorescence—the spathe of coconut palms by selective cutting of it. The process is called tapping and it is a traditional practice of almost all coconut growing countries. The origin of this practice is very old and supposed to be as old as a coconut cultivation. Sap tapping should be done in a transparent manner under restrained conditions. The extraction is generally done before sunrise. This is because of its high susceptibility toward fermentation under ambient temperatures within a few hours of extraction. The spathe before opening is selected for the extraction of coconut inflorescence sap. The juice extracted is collected in an earthen vessel and fermentation processes are arrested to obtain a very sweet, nutritious, and nonalcoholic beverage.

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12.2  Selection of Inflorescence and Preparation of Sap Coconut trees are usually tapped at an early age when they achieve yield steadiness. The unopened inflorescence is used for tapping. The evolution of female blooms inside the spathe (around 60 cm long) may lead to a swelling at the base, the existence of which is taken as the appropriate stage for tapping. The inflorescence chosen for tapping is tied around with a solid coir or plastic rope to keep it from bursting. The same is prepared using a hammer, hand rubbed (utilizing the palm) twice a day, toward the beginning of the day and in the evening for 7 days. After 4–5 days of stroking, 7–10 cm of the tip is removed and in a day or two sap begins oozing from the cut surface.

12.2.1  Tapping Frequency The tapping process is done twice a day, in the morning and evening. Each time 1–2 mm spadix is cut and it is usually tapped along these lines for 40–45 days depending on the tapper's ability, nature of the palm, and seasonal conditions. A solitary spadix can be tapped until the point where it is lessened to a stump of about 10–15 cm length. Around 3  weeks before reaching this point, another spadix is set up with the final goal to guarantee the continuity of sap creation. At a time, 2–3 spadices can be tapped from a tree. Tapping is done twice a day, in the morning and evening. Each time 1–2 mm spadix is cut and it can be tapped in this way for 40–45 days depending on the tapper’s skill, seasonal conditions, and nature of the palm. A single spadix can be tapped until it is reduced to a stump of about 10–15 cm length. Around 3  weeks before reaching this point, another spadix is adapted in order to assure continuity of sap production. At a time, 2–3 spadices can be tapped from a tree (Fig. 12.1).

12.2.2  Traditional Method of Sap Collection The fundamental readiness of spadix to be tapped is the same as depicted previously. When the sap begins to overflow, tappers apply mud, some sort of sticky material, or leaf extract to the cut surface. It is presumed to invigorate sap creation, however as a general rule, it was to forestall internal leak of sap in the space accessible between the peduncles. Additionally, a coconut leaf lamina attached to the outer edge of the sliced surface enables the sap to dribble; or else it will floats along the surface as the coconut spadix is upright or vertical (shapes an edge of 20°–30° to the primary hub). The sap dribbling from the cut surface is gathered in an open earthen pot or bamboo sac, which is kept at the highest point of the palm for 8–12 h. In order to forestall

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Fig. 12.1  Coconut sap exuding from tapped inflorescence.

fermentation, lime is coated on the inner surface of the pot. The sap gathered by this technique is white in color and exudes a solid scent. It is likewise polluted with bugs, ants, dust, and residue particles. The sap gathered without applying lime is used solely for the preparation of toddy, an alcoholic beverage (Hebbar et al., 2015).

12.2.3  Advanced Method of Sap Collection Coconut sap accumulation using coco-sap chiller: The underlying planning of the spadix to be tapped is the same as that portrayed before. When the sap begins to overflow, the coco-sap chiller is buildup to be connected to the spadix13. Ice cubes (0.5–0.75 kg depending on environmental conditions and quantity of sap) or 3–4 gel ice bundles are spread inside the chiller. A compartment or plastic pocket of sustenance review quality associated with an O-ring is put in the grove made for the reason. A treated steel or plastic channel put over the O-ring keeps pollution from dust or plant material. The spadix is embedded through the spadix holder, with the end goal that the cut surface is simply over the focal point of the channel. In this position the spadix is firmly secured to the spadix holder utilizing resin or plastic cover, in this way preventing the entry of ants and other insects. The top opening of the box is closed with a lid. The box is dangled from the tree crown using the handles furnished. During an underlying couple of long periods of tapping, the spadix is upright or vertical and thus a connector is needed for the flow of sap from sliced surface to the collection container. Slowly, spathe disk becomes horizontal or flat

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and sap from cut surface trickles straight into the container without requiring the connectors. The rounded holder is taken out twice a day (toward the beginning of the day and evening) and the sap is shifted to another cooler intended for further capacity. The most critical constituent in sap tapping is the cleanliness factor. Coco-sap filter, chiller, and connectors are washed, while ice cubes and gathering holder are changed and the crate is reconnected as referenced above. Each spadix need one box and at once 2–3 boxes can be attached per tree (Hebbar et al., 2015). This new technique of sap accumulation using the coco-sap chiller overcomes the challenge of handling, that is, 'sanitizing matured sap (enhancing pH esteem, eliminating smell, and so forth.) into an attractive beverage as in the conventional technique.'

12.2.4  Processing of Collected Unfermented Sap for Industrial Purpose The sap collected is then subject to filtration, refrigeration, centrifuging, processing, and packaging. The treated product has a shelf life of up to 2 months. The DRDO (Defends Research and Development Organization, India) in collaboration with CFTRI (Central Food Technology Research Institute) developed the process for coconut sap (neera) preservation without fermentation to alcohols (Toddy). The process include collection of sap from the unopened inflorescence of spadix and immediate chilling to 4°C, followed by filtration, chilling to 2–8°C, addition of acidulant citric acid (0.04%–0.2%), and 10–15 ppm of nisin and pasteurization at 95°C for 5–10 min for long-term storage. Centrifugation at 4000 rpm for 10 min was also developed to remove the suspended particles. Heat processed neera was found to be ­stable for 72 h. Although 1-year shelf life was reported when processed by in-pack pasteurization or retort pouch processing, and storage under refrigerated conditions or 30  days under ambient conditions, it very often found to develop undesirable taste characteristics and odor making the consumption difficult. Since the unfermented coconut sap is photosensitive due to its ascorbic acid content, packaging based on polyethylene terephthalate (PET)/aluminum foil was also developed for storage. Yet another process provided a preparation of neera by retaining all its cloudiness and natural constituents. The invention relates to a process for the preservation of deodorized neera by removing the obnoxious odor. The process included the collection of sap, filtration, chilling to 2–8°C, and the addition of bentonite or activated carbon black. Stirring the contents, centrifugation, and filtration followed by pasteurization or addition of preservatives provided neera with natural cloudiness and minimized odor. Apart from this, value-added products like palm jaggery, palm syrup, and palm sugar are produced from this unfermented inflorescence sap (Fig. 12.2).

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COLLECTION OF SAP

CHILLING AT 4°C

QUALITY AND QUANTITY CHECKING

SEPARATION BASED ON QUALITY

Vaccum Evaporation

Neera honey

Centrifugation (8000–10,000 rpm)

Neera sugar

Deodorisation

Pasteurization ( 80°C , 15 min)

Addition of additives

Cooling and packaging

Neera drink

Fig. 12.2  Processing of Sap and production of its Products.

12.2.5  Yield of Sap Collection and extraction of neera are mostly done in the dry season from November to March and in wet weather period from April to October. Dry weather tapping is done mostly in the low lying lands where palms do not suffer due to moisture stress during the drought period. The spathes are viewed as prepared for tapping

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when the inflorescence opens or is going to blast. The female blossom inside the unopened spathe causes a swelling at the base and this showed the proper stage for tapping. Since coconut produces inflorescence regularly in the successive leaf axils, tapping can be produced throughout the year. High yielding young and well-cared palms have been found to yield a good quantity of sap and the yield also varies with variety. Tall palms yield more sap juice than dwarf palms. Dwarf palms are highly suitable for tapping due to its short stature and high density of palm per unit area. The yield of fresh sap will be less since the size and length of spadix is short in most of the dwarf varieties compared to tall and hybrids. However, Malaysian dwarf varieties generally healthier than other tall varieties may yield more sap and prove to be ideal for tapping in view of the advantages for tapping. A good healthy tall palm may yield up to 2 L sap per day and hybrids even more. At a sugar content of about 15%, this would give a sugar yield of 300–400 g per palm per day. In Indian conditions, it is reported that a high yielding healthy tall tree under good management have the potential to yield 50 L of sap per spadix during 1-month tapping. If six such healthy trees with long spadix is tapped for a period of 6 months, on an average 300 L of neera can be tapped in an year (Jnanadevan; 2013).

12.3  Physical Characteristics and Nutritional Aspects of Coconut Sap Unfermented sap extracted from immature coconut inflorescence has a color ranging from light yellow to cream to dark brown which is sweet in taste with pleasant nutty aroma and is free from filth or extraneous matters. Fresh sap has a basic pH, with minor variation from tree to tree. It starts to ferment within 2–3 h under ambient temperature and pH demonstrates a declining pattern. The pH of the totally matured sap is around 3.5. The sap put stored in a deep freezer (–2°C to –1°C) stays fresh and no adjustment in pH was noticed. Fresh sap has around 15% sugars. It is reduced to about 6% at pH 4. At the same time, the decreasing sugar level increments up to 5% (Table 12.1). Fresh sap, when exposed to the atmospheric environment undergoes initial lactic acid and final alcoholic fermentation due to the activity of microorganisms. They are a good source of nutrients that promote a healthy diet. About 100 mL of sap provides 75 calories of energy and 250 mg of proteins with additional supply of essential minerals, vitamins, and amino acids. It is naturally rich in magnesium, zinc, potassium, and iron. It contains around 16% carbohydrates, with sucrose as the main constituent and small amounts of glucose, fructose, inositol, and raffinose. There are about

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16 amino acids found in fresh sap with glutamic acid, threonine, and aspartic acid forming the major constituents and ascorbic acid as a major vitamin. Ascorbic acid is an important dietary antioxidant, it significantly decreases the adverse effect of reactive species such as reactive oxygen and nitrogen species that can cause oxidative damage to macromolecules such as lipids, DNA, and proteins which are implicated in chronic diseases including cardiovascular disease (CVD), stroke, cancer, neurodegenerative diseases, and cataractogenesis (Akilender, 2003). Fresh coconut sap is high in two amino acids naturally produced by the body, glutamic acid and aspartic acid. These amino acids have a number of health-­promoting benefits significant for cognitive function and metabolism. They also act as precursors to other amino acids. Unfermented sap has 84% moisture and 0.04% ether extractives (volatiles). The volatiles are composed of ethyl lactate, 3-hydroxy-2-pentanone, ethyl lactate, phenyl ethyl alcohol, 2-methyl tetrahydrofuran, farnesol, and tetradecanone. However, the astringency and harsh note of the fermented neera could be associated with the increased amounts of acids (19.0 mg/L), such as dodecanoic acid and palmitoleic acid, along with higher concentrations of ethyl alcohol and ethyl esters (Babasaheb et al., 2007). It keeps our body hydrated while the nutrients in it nourish body and make us feel energetic and refreshed (Tables 12.1–12.3).

Table 12.1  Estimated Components in Fresh Coconut Sap Total solids (g/100 mL) pH Specific gravity Total sugar (g/100 mL) Original reducing sugar (g/100 mL) Total reducing sugar (g/100 mL) Total ash (g/100 mL) Citric acid (g/100 mL) Alcohol in % Iron (g/100 mL) Phosphorus (g/100 mL) Ascorbic acid (mg/100 mL) Total Protein (g/100 mL)

15.2–19.7 – – 14.40 5.58 9.85 0.11–0.41 0.50 Nil 0.15 7.59 16–30 0.23–0.32

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Table 12.2  Amino Acid in Coconut Sap Amino Acids in Coconut Sap Trytophan Lysine Histidine Arginine Aspartic Acid Threonine Serine Glutamic Acid Proline Glycine Alanine Valine Methionine Isoleucine Leucine Tyrosine Phenylalanine

1.27 0.32 1.19 0.35 11.22 15.36 8.24 34.20 3.52 0.47 2.56 2.11 Trace 0.38 0.48 0.31 0.78

Table 12.3  Vitamin Content in Freshly Collected coconut Sap Vitamin

Value (mg/100 mL)

Thiamine Riboflavin Pyridoxal Pantothenic acid Nicotinic acid Biotin Folic acid Inositol Choline Vitamin B12 Vitamin C

77.00 12.20 38.40 5.20 40.60 0.17 0.24 127.70 9.00 Trace 17.5

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12.4  Health Benefits of Coconut Sap Coconut inflorescence, also known as palm nectar, is a delicious drink that is gaining popularity because of its high nutritional value. It is unctuous and cool in effect. Hailed as highly rejuvenative in ­traditional medicinal systems it is recommended for the cure of anemia, tuberculosis, bronchial suffocation, and piles (Hali, 2013). Even today a glass of unfermented coconut sap before going to bed is a ‘grandma’s’ prescription to pregnant women and young girls to make the skin color more charming. Coconut crystals can be produced of this pure, low glycemic natural sap. While most brown sugar is boiled at temperatures up to 221°F with the end product containing 93% sucrose, sap crystals have only 0.5% glucose, 1.5% fructose, 16% sucrose, and 82% inulin—a prebiotic that improves digestive health. It can be used as an optimal sweetener. Major health benefits of sweet fresh sap are as follows.

12.4.1  Antidiabetic Activity The youthful inflorescence of coconut palm have shown defensive and ameliorative impacts against alloxan-instigated pancreatic cytotoxicity and serious hyperglycemia by improving the fringe usage of glucose, rectifying the debilitated liver glycolysis and constraining gluconeogenic arrangement and furthermore fixing and restoring the leftover beta cell populace. These impacts might be because of the presence of phenolic acids, flavonoids, and other phytochemical constituents, which could act synergistically or autonomously in adjusting the activities of glycolytic and gluconeogenic catalysts. In this way, the discoveries of the above examination give scientific validation for the use of coconut inflorescence as a promising candidate in folk medicine in the treatment of diabetes (Raveendran and Thankappan, 2012). The GI is a measure of how fast and how high a specific carbohydrate raises blood sugar level by releasing glucose into the blood stem. Low GI is estimated at 55, less medium GI at 56—69, and high GI at least 70. Low glycemic nourishment contains unwanted, complex sugars that break down in to glucose more slowly and allow for a slower release of usable energy. In this way the glucose levels in the body are controlled. The GI ought to be considered when we choose the quality of carbohydrate in a food item. Glycemic load considers the quality and the amount of carbohydrate substance of the food. Hence, you can decrease the glycemic load of your eating regimen by restricting the food that has both high GI and high carbohydrate content. The glycemic load has been generally used to help diabetic patients control their carbohydrate consumptions as well as those managing their body weight. The GI value alone does not provide a precise picture of the food. The glycemic load takes both the quantity and the quality of carbohydrate content of the food into account. Glycemic load is the GI divided by

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100 multiplied by its available carbohydrate contents. Taking low GI food helps to keep blood sugar insulin level lower; a low-GI diet may be valuable in preventing and curing different types of health problems. The glycemic load of coconut palm sugar is 1.4, or 1 when rounded off. Research carried out by the Food and Nutrition Research Institute of India (FNRI study in 2007) have shown that coconut sugar has naturally lower GI rating of 35 compared to that of most available commercial sugar such as table sugar has GI index of 70, honey has GI of 55, and cane sugar has GI of 68. Substituting low GI sugars can enable lower blood glucose levels in individuals having diabetes. Numerous specialist have demonstrated a relationship between high insulin levels and different cancers such as pancreas, colorectal, prostate, and breast. Different examinations have likewise indicated a connection between diets with high sugar, refined carbohydrates, glycemic load and cancer. It is reccomanded that lifestyle changes like keeping a healthy body weight, exercising, and eating a healthy low-GI diet may help defend against cancer at least partially by lowering insulin levels.

12.4.2 Hypertension Hypertension is a critical public health challenge globally because of its high prevalence and a concomitant increase in the risk of disease. It is also an important risk factor for health problems like stroke, kidney damage, and CVDs. Hypertension is frequently called the “silent killer” because it is often asymptomatic until it becomes aggressive and target organ disease has occurred. Coconut inflorescence sap supplementation (100 mL/day) was found to be efficient in the management of hypertension and its associated complications without having any side effects which may be attributed to the presence of active biological constituents. The antihypertensive effect of coconut inflorescence sap is resolved through normalization of calcium channels and nitric oxide pathway which provides antiatherogenic effects and an improvement in endothelial dysfunction and increased peripheral resistance which may cause a decrease in blood pressure. Further, the presence of free amino acids and sulfur-­containing amino acids (cysteine, L-Arginine, and tyrosine) and antioxidant vitamins A and C leads to the activation of the antioxidant system, thereby decreasing oxidative stress (Bhagya and Soumya, 2016). These studies concluded that coconut inflorescence is effective in managing hypertension and associated complications without causing any side effects.

12.4.3  Antioxidant Activity The antioxidant properties of coconut sap were analyzed for which studies were conducted on the reducing power, levels of ascorbic acid, polyphenol content, and alpha-amylase inhibitory activity.

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Polyphenols and ascorbic acid are very good antioxidants and possess free radical scavenging activity, thereby exhibiting good reducing power. Alpha amylase inhibitors cause a delay in the digestion of carbohydrates, thus causing a reduction in the rate of glucose absorption. A number of antioxidants have been shown to inhibit the induction of cancer by a wide variety of chemical carcinogens and/or radiation at many target sites in mice, rats, and hamsters. Epidemiological studies suggest that a diet rich in plant products containing natural antioxidants may be a deterrent to carcinogenicity. Vitamin C or L-ascorbic acid has been shown to scavenge superoxide, hydrogen, peroxide, hydroxyl radical, peroxyl radicals, and ‘O2’ (Valko et al.; 2006) efficiently. Ascorbic acid can also defend membranes against peroxidation by increasing the activity of tocopherol, the chief lipid-soluble vitamin. It is considered to be the most valuable antioxidant in extracellular fluids (Proteggente et al., 2002) and has numerous cellular activities of an antioxidant nature as well. Coconut inflorescence sap being rich in ascorbic acid protrudes its antioxidant capacity that may favor its action against oxidative stress produced during cancer therapy.

12.4.4  Effect on CVD Atherosclerosis is a life-long illness that begins with risk factors, which in turn contribute to the development of subclinical disease, followed by the establishment of overt CVD. Oxidized low-density lipoprotein (OxLDL) plays an important role in atherogenesis by promoting an inflammatory environment and lipid deposition in the arterial wall. Recent studies have investigated the anti-­inflammatory effect of an improved formulation of coconut inflorescence sap (CSP—coconut sap powder) against ox-LDL-induced inflammatory responses in human peripheral blood mononuclear cells (hPBMCs). Coconut inflorescence was found to downregulate and reverse the ox-LDL-induced alterations showing its potential anti-inflammatory effect on hPBMCs via TLR-NF-jB signaling pathway (Ratheesh et al.; 2017). As with type 2 diabetes, researchers have identified that a diet rich in refined and high GI carbohydrates may considerably increase the risk of heart disease. These foods raise blood insulin levels which in turn contribute to higher levels of blood fats (triglycerides), lower levels of high-density lipoprotein (HDL) (good) cholesterol, high blood pressure, and an expanded tendency for dangerous clots to develop and linger in the blood. Ascorbic acid a major component in coconut inflorescence is known to prevent the oxidation of low-­ density lipoprotein (LDL) primarily by scavenging the free radicals and other reactive oxygen species in the aqueous milieu. In addition, in vitro studies have shown that physiological concentrations of ascorbic acid strongly inhibit LDL oxidation by vascular endothelial cells

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(Melissa and Ock, 2016). Adhesion of leukocytes to the endothelium is a valuable step in initiating atherosclerosis. In vivo studies have demonstrated that ascorbic acid inhibits leukocyte-endothelial cell interactions induced by cigarette smoke (Lehr et al., 1994) or oxidized LDL Thus unfermented coconut sap may reverse the risk associated with CVDs.

12.4.5  Nephroprotective Action Kidneys are essential for maintaining many aspects of metabolic homeostasis. They perform major functions of the human body such as the removal of metabolic waste products, regulation of water, electrolyte, and acid-base balance, synthesis and regulation of hormones, etc. Gentamicin is known to enhance the generation of superoxide anion and hydrogen peroxide by renal cortical mitochondria resulting in severe renal damage. Coconut inflorescence being a good anti-inflammatory and antioxidant showed a nephroprotective effect against gentamicin-induced kidney toxicity by inhibiting oxidative stress, lipid peroxidation, inflammation, thereby suppressing the pro-inflammatory cytokines such as TNF-a, IL-6 and preventing nephritis and necrosis of kidney tissues (Svenia et al., 2017). It offers new possibilities for drug development in the management of acute renal disease, especially drug-induced kidney damage with the etiology of oxidative stress and lipid peroxidation. Phosphourous present in neera plays a significant role in renal health. Phosphorus plays a vital role in keeping the kidneys healthy. It does this by allowing the proper release of waste from kidneys through the process of urination and excretion (Uribarri, 2007). By raising the quantity and frequency of urination, the body is able to balance its levels of excess salts, uric acid, water, and even fat, since urine is normally about 4% fat. Phosphorous encourages the healthy balance of all fluids and materials that are eliminated from the body, thereby helping the entire body remain healthy and toxin free.

12.4.6 Hypoglycemia Individuals who have meal-related reactive hypoglycemia secrete excessive insulin after eating. This may lead to the elimination of so much sugar from the blood by the cell that they feel irritable, hungry, weak, and giddy. Coconut sap has high nutrient content, such as essential minerals (iron, potassium, magnesium, and zinc) and vitamins. It has a very low GI and glycemic load as well. So coconut organic nectar will generate a moderate release of energy, without regular blood glucose levels becoming too low or too high. By keeping blood glucose as well as insulin level in a normal range, coconut organic nectar can help prevent and treat different health issues.

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12.4.7  Hepatoprotective Effect According to a study conducted in Indian Institute of Science, unfermented coconut inflorescence is effective in curing liver diseases, especially the liver problems caused as a result of excessive alcohol consumption. Acetaldehyde, a poisonous substance, gets accumulated in the liver predominantly due to liquor consumption. Coconut sap has the ability to eliminate this poisonous product from the liver. The enzymes in the liver transform alcohol into acetaldehyde. When this harmful chemical is assimilated in considerable amounts, liver cells get destroyed due to oxidative stress. Fresh coconut sap inhibited the alcoholic hepatic damage by modulating inflammatory markers, extracellular matrix metalloproteinase, and oxidative stress (For more detail refer to http://english.mathrubhumi.com/health/ neera-can-cure-liver-disease-says-study-1.510228.)

12.4.8  Improves Digestion Natural fresh coconut inflorescence sap is good for improving the overall health of a person. Since it is rich in vitamins and minerals, it can be used as a supplement. It contains high amounts of glutamic acid, which is an amino acid used by your body to build proteins. This amino acid is one of the most common neurotransmitters in the nervous system. It is one of the good source of phosphorous. Phosphorus plays a crucial role in promoting effective digestion in the human body. It does this by stimulating the digestion of riboflavin and niacinin in an efficient way. These two vitamins are likewise fundamental for human health, so in any case that their take-up can be expanded is something worth being thankful for. These two assortments of vitamin B are in charge of everything from vitality metabolism to neurological and emotional reaction systems. Beyond the uptake of other vitamins and minerals, phosphorous directly clears up indigestion, constipation, diarrhea, and generally tones up the digestive system for regular, healthy bowel movements. This improves the health of the digestive system, as well as that of the kidneys since the toxins are being removed from the body, rather than recycling through the kidneys and stressing that system. The drink contains high amounts of vitamins and minerals that increase the immune system and helps your body fight against various diseases.

12.4.9  Reduces Body Weight Obesity has become one of the critical health threats worldwide. Additionally, an excessive body fat gathering, which describes this disease, could contribute to various associated clinical manifestations such as inflammation, type 2 diabetes, cardiovascular events, and

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some types of cancer. Therefore, antioxidant-based treatments could be considered as fascinating approaches to possibly fight obesity and fat accumulation complications. Among the possible beneficial effects of ascorbic acid on obesity-related mechanisms, it has been suggested that this vitamin may: (a) regulate the glucocorticoid release from adrenal glands; (b) modulate adipocyte lipolysis; (c) lead to an improvement in hyperglycemia and decrease glycosylation in obese-­ diabetic models; (d) inhibit glucose metabolism and leptin secretion on isolated adipocytes; and (e) decrease the inflammatory response (Garcia-Diaz et al., 2014). Coconut sap being a rich source of ascorbic acid may aid a greater impact on obesity.

12.4.10  Strengthens Bones The proper balance of phosphorus and calcium is needed for strong, healthy bones. Phosphorus helps our body to absorb calcium. As the amount of phosphorus you consume rises, so does your calcium requirement. The main function of phosphorus is to make bones and teeth strong, according to Medline Plus, a service of the US National Library of Medicine and the National Institutes of Health. All adults require about 700 mg of phosphorous a day. Coconut sap contains a sufficient amount of phosphorous that meets its daily requirement.

12.4.11  Keeps Body Cool It regulates the body’s fluid balance and controls body temperature. The high amount of electrolytes in neera makes it a good postoperative care drink. It is considered a natural detoxifying drink that does not involve any side effects. Fresh coconut sap has less glyemic index, keeps the body cool, and reduces the cause of dehydration. It is a natural electrolyte which boosts your immunity system.

12.4.12  Enhances Neurological function Thiamin plays an important role in the regeneration of brain function. Thiamin diphosphate is a cofactor for various enzymes implicated in glucose metabolism whereas thiamin triphosphate has specific properties at the neuronal membrane. Thiamin metabolism in the brain is divided between neurons and neighboring glial cells. Highest levels of inositol concentrations can be identified in the heart and brain; inositol is associated with neurotransmitters in message circulation. Inositol is added to energy drinks because it is effective in converting nutrients into energy. Unfermented coconut sap contains both thiamin and inositol that may enhance the neurological function of the body.

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In addition to the above-mentioned benefits, coconut sap also possess other health benefits. According to various studies, it has applications for various health conditions including asthma, anemia, bronchial suffocation, tuberculosis, and piles. It is high in inositol, a naturally occurring nutrient, which is favorable for the treatment of eczema, eye abnormalities, etc. It is also associated with the regulation of enzyme activity, nerve transmission, and transportation of fats within the body. Inositol is essential for hair growth and also help prevent hair fall and baldness to a great extent. It is a natural remedy for kidney stones as well as urinary problems. It helps reduce high cholesterol levels in the blood. Coconut sap is a good source of antioxidants and therefore exhibits antiaging properties.

12.5  Value-Added Products from Coconut Sap Unfermented coconut sap and its value-added products are fabricated by all the major coconut producing countries. The principal players in the field are Indonesia, Philippines, Thailand, Malaysia, Sri Lanka, and Vietnam. The major destinations are Canada, France, United States, Norway, South Korea, Middle East, Australia Japan, and New Zealand. Export of neera and its products, particularly palm sugar, has proved an increasing trend in production and market demand as a natural and healthy product. Industries based on the coconut with extensive economic prospects have been established to provide to the local and domestic demands. Indonesia produces over 6 lakh MT of palm sugar in a year, that is, around 50,000 MT of palm sugar is produced per month. They moved through farmer groups since 90% of the coconut growers are small and marginal. Big tree farms are the forerunner in coconut palm sugar production in Indonesia. Indofood and Unilever purchased around 30,000 MT of coconut palm sugar each in 2011. The production of palm sugar in Indonesia was estimated to reach 10 lakh MT in 2012. Even countries like Sri Lanka and Malaysia which are very much behind India in the fabrication of coconut have ventured into production of neera and palm sugar. Codex Alimentarius Commission and Asia Pacific Coconut Community (APCC) have designed quality standards for neera and its products. In countries like Philippines various products can be fabricated from coconut sap. The processing of which does not need the application of advanced technologies.

12.5.1  Coconut/Palm Sugar It is a crystalline form of sugar prepared from coconut sap concentrate. Boiling the sap and preparation of granular palm sugar is the value-added product of the future with great potential from neera.

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Ordinary Palm sugar has a polarization value of 96°–98°. Coconut sap sugar is very tasty and has more nutrients. Since it has a low GI and low glycemic load, it is especially beneficial for diabetes. Toffees, chocolates, and confectionery items are created from palm sugar. The application of this palm sugar is largely owing to the low GI and high nutrient content. Low GI food finds applications in suitable control of diabetes mellitus and in bringing down cholesterol levels. The GI of table sugar is nearly 60 while that of palm sugar is only 35. Generally, GI below 55 is considered low. It is also beneficial for weight maintenance preventing obesity and overweight. These products have enhanced demand in the international and domestic markets. It is a valuable alternative for commercial sweeteners that can be found in the market (Table 12.4). The production of coconut sugar from unfermented sap is a profitable on-farm activity and is encouraged in many coconut growing countries for local consumption as well as for export marketing. The experience in countries like Philippines, Thailand, Indonesia, etc., is that assigning palms for sugar production is much more profitable to the farmers than allowing to yield nuts. In the Philippines the

Table 12.4  Comparison of Mineral Nutrients Composition of Coconut Sugar With Unrefined and Refined Cane Sugar Minerals

Coconut Sugar

Unrefined Cane Sugar (Brown)

Refined Cane Sugar (White)

10 3 24 65 7 2 13

0 0.07 6.0 2.5 1.0 1.0 2.0

0 200 200 1260

0 120 0 120

Macro-minerals (mg/100 g dry wt) Nitrogen Phosphorus Calcium Potassium Magnesium Sodium Sulphur

202 79 6 1030 29 45 26

Micro-minerals (μg/100 g dry wt) Boron Zinc Manganese Iron

30 2100 130 2190

Source: Philippine Coconut Authority.

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a­ verage income from palms set aside for tapping and sugar production is 7–10 times that from palms maintained only for nut production. In Thailand producing sugar has been found to be eight times more profitable than producing coconut or copra. In Indonesia the farmers are encouraged to leave up to 30% of the palms in plantations for sugar production. The Bureau of Agriculture and Fisheries Products Standards in Philippines has developed specific standards in quality for coconut palm sugar. For instance, premium class is classified as a superior quality which has a color ranging from light yellow to cream. Class I which is of good quality has a color ranging from light brown to brown. Class II includes those which do not fall in the above two.

12.5.2  Palm Syrup Apart from solid palm sugar, another useful product that could be made out of unfermented sap is treacle or sugar syrup. The syrup is a golden colored product and the recovery is 16% of the sap used. It is a delicacy and its use is preferred as a bread spread in place of fruit jam and a sweetening agent for special breakfast dishes. Palm syrup is manufactured when fresh sap is heated and concentrated into asyrup. It is formulated at 78 Brix level. It is dense liquid syrup like honey. It is used as table syrup or as a sweetener in confectionery. It is an abundant source of iron; it is beneficial for anemic patients. So it is mostly used in pharmaceuticals formulation. In various countries, palm syrup is used as a wellness and health drink and is basically used in Ayurveda and other segments of medicine. Boiling the sap under moderate to low heat yields a golden brown sticky liquid with a big mineral capacity which is used as palm syrup. It is free from cholesterol and total fats with a sucrose content of 50% and a GI of 35 GI. It can be used for healthy food manufacturing, as topping on a large variety of desserts, appetizers, or beverages.

12.5.3  Palm Jaggery Further boiling and crystallization of the sap in molds yields palm jaggery. Sap transformed into a semisolid or a solid crystalline mass ready to use is called palm jaggery. It is used as a sweetening agent for the preparation of dishes, desserts, and is superior to cane jaggery. Preparation of this granular palm sugar is the quality added product of the future with great potential from coconut inflorescence sap. It has got wide use as a sweetening agent in Indian villages. The palm jaggery is produced by boiling raw palm sap in shallow, large, round-bottom vessels. The raw juice is heated at 40°C in a dish and this juice is then limed to neutrality, that is, pH balanced by adding either triple super phosphate solution or phosphoric acid slowly and mixing all the while. Boiling of the filtered juice is realized over

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open-fired enhanced furnaces using metal pans of 20–24 gauge thickness. As boiling continues, the froth and foam coming up to the surface are removed by means of a perforated ladle. The juice is mixed at intervals to promote blending and fast evaporation. At the point when the juice thickens, the fire is wisely controlled with the end goal to keep it from caramelizing. Precise strike temperature is judged by patting a small quantity of the thickened mass in water and rotating it into a ball shape. If ball assembles into a hard one, the strike is over and the mass is molded into molds. The strike temperature can also be manipulated through the use of thermometers. In order to moderate the removing of the blocks from the molds, the molds are either besmeared with fresh sweet oil or moistened with water before including the thick mass into them. After permitting setting for some time, it is eliminated from the molds and packed. It will be hard, crystalline, and golden in color (Table 12.5).

12.5.4  Palm Cookies These types of cookies are fabricated with grated coconut, flour, grated coconut, and jaggery powder. These are the best choice for patients with diabetes. It is well known that eating healthy snacks between main meals will help keep glucose levels in diabetic patients. Cookies manufactured with coconut sap jaggery are fit for this objective since its GI is very low (GI 35). Different types of cookies can be made with different main contents like corn, oats, arrowroot, whole wheat, multigrain, and Fige.

12.5.5  Palm Chocolate The consumer may never again need to stress over calories while eating chocolate. There is an encouraging news for kids and furthermore for the grown-ups who love chocolate. Mangalore based Central Arecanut and Cocoa Marketing & Processing Cooperative (CAMPCO)

Table 12.5  Nutrient Contents in Palm Jaggery Component

Quantity (mg)

Thiamine Riboflavin Nicotonic acid Ascorbic acid

21.00 432.00 5.24 11.00

358  Chapter 12  NEERA: A NONALCOHOLIC BEVERAGE FROM COCONUT PALM

Ltd. on July 2016 launched a chocolate that will have sugar made from “Neera” or sap of coconut palm which will be safe for consumption even for diabetic.

12.5.6  Neera Sweet This is an extremely fruitful dessert for diabetic patient who are lovers of sweets. It is fabricated and marketed by popular sweet producer and seller of West Bengal—Felu Modak. The sweet is made with kheer as a principal ingredient and coconut sap or neera as sweetener. The color of the sweet is yellowish and named as Kesar Peda or sometimes neera. The price of this peda is Rs. 15/pc. This sweet is a gift for diabetic patients and they like it so much these days.

12.5.7  Palm Candy Palm candy is also one of the important products of coconut sap. It is being fabricated and used since procuring sweet sap from palmyra has been known. It plays an important role in Ayurvedic medicinal preparations.

12.5.8 Molasses Palm molasses is a sweet syrupy material got as a result of palm sugar. Cattle feed and golden syrup and are alternate items produced using molasses. Biochemical products like acetic acid, citric acid, ethyl alcohol, etc., can be made of molasses by fermentation methods.

12.5.9  Palm Vinegar Coconut vinegar can also be manufactured from the inflorescence sap other than from matured coconut water. Fresh sap is poured in a large plastic container with a clean netted cover to allow aeration and to avoid entry of dirt and foreign objects. After fermentation in well-ventilated room, the sap can be collected as vinegar. Vinegar has wide use as a flavoring agent in pickle industry and preservative in the food processing sector. The palm vinegar has favorable export potential in comparison to the synthetic vinegar. We are living in an era where consumers become more responsive to quality and health. If cost was the key factor for purchase in the 20th century; health, aspirations, and quality determine the purchasing decisions today. With healthy nutrient-rich products like unfermented coconut sap and palm sugar, establishing and designing and a market space, both in the export and domestic market provides great potential. The production of coconut sugar from unfermented sap is a profitable on-farm activity and is encouraged in many coconut

Chapter 12  NEERA: A NONALCOHOLIC BEVERAGE FROM COCONUT PALM   359

growing countries for local consumption as well as for export marketing. Besides a natural drink, different types of value-added products and confectionaries like ice cream, cake, and sweets can be fabricated from this sap which has low GI index, and this is an excellent news for diabetic patients who are afraid of taking such sweet foods. Now they can easily buy their favorite confectioneries without any harmful effect on blood sugar level.

12.6 Conclusions Coconut has provided us with food, beverages, oil, timber, sugar, and other valuable products since time immemorial. Coconut inflorescence sap is another boon from the coconut tree. It is considered to be as pure as mothers’ milk and traditionally believed that it has many medicinal properties and used as a refreshing health drink. Coconut sap is a sweet and highly nutritious extract collected by slicing the spathes, scraping the tender most part below the crown area of coconut and palm trees. It is a nonalcoholic nutritious bio-beverage with amazing health benefits and with no alcohol content in it. This beverage is promoted globally due to its nutritional value as well as due to its potential for value addition. They make human body cool and are good for digestion. It has a very low GI, so it does not increase the blood sugar levels like normal fruit juices and even diabetic patients can drink it safely. Repeated consumption of sap restricts diseases like jaundice and keeps one healthy. It is a natural detoxifying drink that does not shown any side effects. It is best consumed during summer time. Its nectar is widely consumed in Thailand, Sri Lanka, India, Malaysia, Africa, Indonesia, and Myanmar. It is an improved substitute for other commercially available artificial soft/cool drinks which are available in the market since it contains all most all nutrients that are need for a healthy living. Adopting a healthy lifestyle by exercising and eating a healthy diet not only improves your bodily function but also helps you lead a disease-free life. In spite of its amazing health benefits, coconut inflorescence sap has not received the popularity and acceptance. This may be due to the fact that it has a short shelf life and is cost effective. It can be promoted as an instant energy provider, health drink, functional food, and nutraceuticals.

References Akilender, K.N., 2003. Vitamin C in human health and disease is still a mystery? An overview. Nutr. J. 2, 7. Babasaheb, B.B., Lingamallu, J.M.R., Ramalakshmi, K., Bashyam, R., 2007. Chemical composition of volatiles from coconut sap (neera) and effect of processing. Food Chem. 101, 877–880.

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Bhagya, D., Soumya, G., 2016. Effects of coconut neera (Cocos nucifera L.) on blood pressure among hypertensive adult women. IJAPSA 2, 1–7. Garcia-Diaz, D.F., Lopez-Legarrea, P., Quintero, P., Martinez, J.A., 2014. Vitamin C in the treatment and/or prevention of obesity. J. Nutr. Sci. Vitaminol. 60, 367–379. Hali, R., 2013. Bio beverage – Coco Neera. Indian Coconut J. LVI 17–19. Hebbar, K.B., Arivalagan, M., Manikantan, M.R., Mathew, A.C., Thamban, C., Thomas, G.V., Chowdappa, 2015. Coconut inflorescence sap and its value addition as sugar—­collection techniques, yield, properties and market perspective. Curr. Sci. 109, 1411–1417. Jnanadevan, R., 2013. Coconut palms suitable for Neera tapping. Int Coconut J., 15–16. Lehr, H.A., Frei, B., Arfors, K.E., 1994. Vitamin C prevents cigarette smoke-induced leukocyte aggregation and adhesion to endothelium in vivo. Proc. Natl. Acad. Sci. USA 91, 7688–7692. Melissa, A.M., Ock, K.C., 2016. Vitamin C and heart health: a review based on findings from epidemiologic studies. Int. J. Mol. Sci. 17 (8), 1328. Proteggente, A.R., Pannala, A.S., Paganga, G., Burner, L.V., Wagner, E., Sheila Wiseman Van de Put, F., et al., 2002. The antioxidant activity of regular consumed fruit and vegetables reflects their phenolic and vitamin C composition. Free Radic. Res. 36, 217–233. Ratheesh, M., Svenia, J.P., Asha, S., Sandya, S., Girishkumar, B., Krishnakumar, I.M., 2017. Anti-inflammatory effect of a novel formulation of coconut inflorescence sap against ox-LDL induced inflammatory responses in human peripheral blood mononuclear cells by modulating TLR-NF-κB signaling pathway. Toxicol. Mech. Methods 27, 615–621. Raveendran, S.R., Thankappan, R., 2012. Protective and curative effects of Cocos nucifera inflorescence on alloxan-induced pancreatic cytotoxicity in rats. Indian J. Pharm. 44, 555–559. Svenia, J.P., Asha, S., Krishnakumar, I.M., Ratheesh, M., Savitha, S., Sandya, S., Girish, K.B., Pramod, C., 2017. Nephro-protective effect of a novel formulation of unopened coconut inflorescence sap powder on gentamicin induced renal damage by modulating oxidative stress and inflammatory markers. Biomed. Pharmacother. 85, 128–135. Uribarri, J., 2007. Phosphorus homeostasis in normal health and in chronic kidney disease patients with special emphasis on dietary phosphorus intake. Semin. Dial. 4, 295–301. Valko, M., Rhodes, C.J., Monocol, J., Izakovic, M., Mazur, M., 2006. Free radicals, metals and antioxidants in oxidative stress-induced cancer. Chem. Biol. Interact. 160, 1–40.

Further Reading Bhagya, D., Prema, L., Rajamohan, T., 2010. Tender coconut water maintains the level of electrolytes and renin in fructose-fed hypertensive rats. Int. J. Biol. Med. Res 1, 44–48. Bipasa, M., 2016. Neera: The coconut sap: a review. Int. J. Food Sci. Nutr. 1, 35–38. 2016. http://english.mathrubhumi.com/health/neera-can-cure-liver-disease-says-study-1.510228. Jayaprakash, B.N., Suresh, P.R., Manjusha, M., Balachandran, P.V., Subramanium, M., Balakrishnan, P.C., 2013. Keratheertham—a health drink from coconut inflorescence sap. Int Coconut J., 9–10. Muraleedharan, K., Deepthi, N.S., 2013. Coconut Neera –the hidden unexplored treasure. Int Coconut J. 2 (3). Philippine Coconut Authority—Plant and Tissue Analysis Laboratory. Coconuts Today, November 2004, vol. XIX. Siddarameswara, S.G.M., 2013. Coconut production and processing in Karnataka. Int Coconut J. 31–33. Sunil, A.N., Mejosh, J.R., Reji, J.T., Nair, R.V., 2013. Production of neera. Int. Coconut J., 25–26. SyamalaDevi, N., HariPrasad, T., Ramesh, K., Ramchander, M., 2015. Antioxidant properties of coconut sap and its sugars. Int J Pharm Tech Res. 8, 160–162. Thampan, P.K., 2013. Production of Neera and coconut sugar deserves encouragement. Int Coconut J., 11–14.

TRENDS AND POSSIBILITIES OF THE USAGE OF MEDICINAL HERBAL EXTRACTS IN BEVERAGE PRODUCTION

13

Senem Suna, Canan Ece Tamer, Gülşah Özcan-Sinir Department of Food Engineering, Uludag University, Bursa, Turkey

13.1 Introduction Over the past decades, researchers have gained increasing insight in understanding the presence, formation, health benefits, and potential risks to public health posed by several compounds. In this shed of light, natural components like polyphenols, carotenoids, vitamin E, and ascorbic acid stand out as well as miscellaneous nutritional compounds. Polyphenols, which are formed of approximately four thousand identified molecules, are commonly found in many fruit and vegetables, herbs, cereals, and nuts. Anti-inflammatory, antimicrobial, antidiabetic, and antitumor activities can be revealed as the major health beneficial effects. Furthermore, due to the growing awareness, there has been in an increase in the published material on the formation and presence of polyphenols in different foods, the total amounts consumed in the diets, and their potential. For instance, daily intake of polyphenols may be 800 mg (Pietta, 2000). According to a research conducted by 610 healthy human subjects, total polyphenol intake was determined as 1492 mg/day, while the highest ratio of which was specified by beverages (79.1%). Additionally, it was revealed that, the daily consumption of polyphenol contrasted to a great extent among people (183–4854 mg/day), while espresso and green tea were recorded as the highest sources of polyphenols together with 43.2% and 26.6% ratios (Taguchi et al., 2015). During the last decade, consumption of foods with health beneficial effects and phytomedicine has gained great importance. Several components like fiber, protein, and vitamin are being used for the enrichment of foods, while nutraceuticals found mainly in plants, fruit Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00013-4 © 2019 Elsevier Inc. All rights reserved.

361

362  Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE

and vegetables, and root extracts took place in modern markets. In this concept, nutraceuticals, functional foods, and dietary supplements come as the major terms which are confused with each other. Nutraceuticals could be described as “the whole food or a part of it that supports medical or health beneficial effects such as the suppression and/or cure of an illness.” It could be fortified food, dietary supplement, or herbal product (Trottier et al., 2010; Pandey et al., 2011). Functional foods are regular foods in diets having the components with a particular medicinal or health benefit beyond nutritional effect (Chauhan et al., 2013; Kalra, 2003). They are involved in a class of nutraceutical that improves health through the daily diet. Additionally, dietary supplements could be defined as the products that are labeled and involved in diets as a constituent like a mineral, vitamin, amino acid, an herb, and an extract or a concentrate for the supplementation of daily intake (Zeisel, 1999).

13.2  Trends in the Worldwide Consumption of Drinks 13.2.1 Tea Tea is one of the extremely popular, nonalcoholic drinks consumed worldwide (Alasalvar et al., 2012). Main tea producer countries can be listed as China, India, Kenya, Sri Lanka, Turkey, and Vietnam, respectively, with the ratios of 36%, 21.2%, 7.8%, 7.0%, 4.8% and 4.6%. Turkey, which is at the top of tea consumption per person, has annual production of 226,800 tons, in an 76,049 ha area, in 2014 (FAO, 2014; Azapagic et al., 2016). According to the report of Food and Agriculture Organization (FAO) of the United Nations, black tea production was estimated to be moderately higher than the previous decade and reach 4.17 million tons with a 2.9% annual growth. Additionally, green tea production has been expected to be more rapid than black tea (8.2%), with a reflection of the expansion in China, where tea production is relied on to reach 2.97 million tons by 2023. Moreover, consumption of black tea worldwide is estimated to be evolved 3% per year and reached 4.14 million tons in 2023 (FAO, 2015). The Camellia sinensis (L.) O. Kuntze plant was first developed more than three thousand years ago and has customarily been utilized as a part of Chinese medicine. Tea, derived from this plant is one of the most popular low-cost drinks that have been consumed as a beverage and a herbal medicine due to its taste, aroma, and health effects for many years (Jain et al., 2013). Today, it is still popular in several Asian, South American, and European countries. This popularity has risen as a result of its antioxidant property. In addition, health-beneficial

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   363

i­ mpacts were explored by various in vitro and in vivo techniques (Yang et al., 2016). Different types of tea are obtained from fresh tea leaves, as a consequence of the diverse kind of production methods. Based on the level of fermentation in the course of processing, tea can be classified into the fundamental groups like; green tea (unfermented), oolong tea (semi-fermented), and black tea (fully fermented) contrasting in the quality and amount of mixes in charge of the remarkable smell, flavor, and bioactive capacities (The United Kingdom Tea Council Ltd, 2017; Wang et al., 2016). Additionally, white tea is one of the less considered sorts of tea, in spite of the fact that it contains considerably higher amounts of antioxidants than green, oolong, and black tea (Martins et al., 2014). As a result of the fact that green tea does not undergo fermentation, enzymatic oxidation of catechins is prevented/inhibited. In the production process of black tea, fermentation is applied to the leaves in which catechins were subjected to oxidation and oligomerization by endogenous polyphenol oxidases and peroxidases, the following theaflavins (F) and thearubigins (R) have occurred. Oolong tea is stated between green and black tea with its semi-fermented property (Liu et al., 2016). Green tea contains the highest content of unoxidized catechins, while black tea and oolong tea includes the oxidized derivatives of the catechins, “F” and “R” related with the oxidative production (Stodt and Engelhardt, 2013). In overall evaluation, composition of tea could change with the assortment, season, period of leaves, humidity, and agricultural practices (Kim et al., 2011a). Furthermore, infusions of all tea types include glycosides of flavonols like quercetin, rutin, and other derivatives, phenolic and organic acids (Lin et al., 2008). Green tea and black tea are two main types of tea and their antioxidative impacts are believed to be provided by polyphenols (Vinson and Dabbagh, 1998). The polyphenolic components of tea are flavonols (quercetin, kaempferol, and myricetin), flavan-3-ols (catechins and theaflavins), and a small amount of purine alkaloids (caffeine and theobromine), gallic acid derivatives (gallic acid, and 5-galloylquinic acid), and hydroxycinammate quinic esters (caffeoylquinic acids) (Del Rio et al., 2004). Between these compounds, catechins and theaflavins are the indicators that play an important role for the determination of antioxidant activity (Zhang et al., 2018). Green tea leaves and its infusions include miscellaneous bioactive ­components of the unoxidized catechins such as (+)-catechin, (−)-gallocatechin, (−)-epicatechin, (−)-epigallocatechin, (−)-epicatechin gallate, (−)-epigallocatechin gallate (Naldi et  al., 2014; Theppakorn, 2016). As major compounds of green tea, catechins constitute up to 30% of the dry weight.

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(−)-Epigallocatechin gallate (ECGC) known as green tea catechin (GTC), is the most plentiful catechin in green tea with the ratio of 50%–75% of the catechins (Chen et al., 2011). In a research, amount of GTC in one cup of green tea (250 mL) was reported as 100 and 200 mg (Zaveri, 2006). The GTC has been appeared to have various anticancerous properties together with antioxidant, antibacterial, antidiabetic, antiobesity, and anti-inflammatory effects. According to the results of a research, EGCG might be used as a cell proliferation inhibitor and epigenetic modifier for the treatment of acute promyelocytic leukemia (Borutinskaitė et al., 2018). Aroma of tea is affected by different manufacturing steps involved in tea production. Oolong tea is a semi-fermented product of Camelia sinensis leaves. The unique method for the manufacture of oolong tea subscribes to the creation of sweet, fruit, and floral aroma (Gui et al., 2015; Zeng et al., 2017). Additionally, oolong tea includes incomparable theasinensins, a group of tea phenolics, differing from GTCs and black tea theflavins (Hou et  al., 2010). According to several studies, regular oolong tea intake is conclusively accompanied with the decreased risk of cardiovascular diseases (Arab et al., 2009) and body weight control (Uchiyama et al., 2011; Liu et al., 2016). Black tea is of great importance for phytochemicals and antioxidant activity apart from the particular quantities of nutritional components (Serpen et al., 2012). Black tea leaves and infusions contain flavanols (catechins) and flavonoids as oligomeric theaflavins and thearubigins shaped in the oxidation procedure (changed over from monomeric catechins or flavan-3-ols) (Jeszka-Skowron et al., 2015). The formation system of these components all along the tea processing and fermentation and additionally their individual bioactivities are of incredible significance for scientific and business interest. As a result of the increased interest in market demand, white tea production in China was increased by 300 times in 2014 (Ministry of Agriculture of China, 2014). It is produced from immature C. sinensis leaves or buds, which are steamed or dried right after harvesting. Heat treatment was applied to prohibit the fermentation process, to inactivate degradation enzymes such as polyphenol oxidase, and to prevent the oxidation of catechins. It is viewed as an unfermented type and no precise description has been agreed so far except from the report prepared by ISO working group (ISO, 2013). When compared to diverse kinds of teas, white tea directly goes to withering and drying, differing from the fermentation step as in oolong or black tea or enzyme deactivation in green tea (Tan et  al., 2017). The most obvious contrast between green tea and white tea could be considered as harvest time, as the youngest buds are used in the production process of white tea (FAOSTAT, 2008).

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13.2.2  Herbal Teas Teas (black, green, oolong, and white) are the most favored drinks worldwide and are known as nonherbal teas. Teas prepared from the other species of the plants are recognized as herbal teas (Bliss, 2003). In other words, herbal teas, particularly herbal infusion or tisane, are defined as regularly consumed beverages prepared from the leaves, blossoms, seeds, fruits, stems or roots of plant other than C. sinensis L. Herbal teas have been utilized for well-being advancement and illness counteractive action since ancient times in several countries like China, India, Japan, Thailand, Greece, and Turkey (Tulukcu, 2011; Kaliora et al., 2014). In China, particularly, the historical background of herbal teas may be as old as the utilization of Chinese medicine, and most of the Chinese medicine was applied in tea form (Zhao et al., 2013). Over the past decades, consumers as well as researchers have gained an increasing awareness in understanding the potential health beneficial effects posed by the compounds, which are found mainly in herbal teas. Therefore, for living a healthy life, herbal teas have turned out to be popular as alternative to caffeinated drinks. Caffeinefree status and health-promoting features, prominently antioxidant properties, improved their acceptance. Besides, these features are accompanied with the existence of various polyphenols with known antioxidant, diuretic, and anti-inflammatory characteristics. In a universal manner, advancing impacts on well being revealed for herbal tea are related with phytochemicals and phenolics which exist in plants. These impacts and biological and antioxidant activities of commonly consumed herbal teas worldwide are briefly discussed by Li et al. (2016). In this study, they focused on the main topics and listed them respectively as, antioxidant efficacies; anti-inflammatory, antiproliferate, and antimicrobial activities; immunological efficacies, antiglycation, and antimalarial activities together with the effects on metabolic enzymes and other benefits.

13.3  Medicinal and Aromatic Herbs 13.3.1  Overview of Medicinal and Aromatic Herbs Plants are among the main food sources of people. Through t­ rial-and-error method, people have learned from the early ages which plant can be consumed, and which are toxic or curative (Baydar and Baydar, 2005). Medicinal and aromatic plants come at the forefront of product groups that are increasingly important and updated in the world today, as the trend of return to nature is experienced. These plants are widely used in many industrial fields, including medicine, food,

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c­ osmetics, and perfumes. The emphasis on bioactive components of medicinal and aromatic plants, especially in recent years, has increased the consumption and value of these plants (Jokara et al., 2017). Nearly 80% of the world, consume traditional medicine and medicinal plants for their healing effects (Toksoy et al., 2010). There are 422,000 different kinds of plants in the world, of which 52,885 are in the medical plant category. The World Health Organization (WHO) reported that medicinal and aromatic plants used worldwide is counted as 20,000. While 4000 drugs are widely used, there are currently more than 2000 medicinal plants are traded in the world and 500 in western Europe (Anonymous, 2012a).

13.3.2  Consumer Trends of Medicinal and Aromatic Herbs Comtrade (commodity trade statistics) database by the United Nations Statistics Division, New York, has been used nearly by 180 different countries since 1962 (Lange, 2006). It is an important source to be aware of the data obtained from the industrialized world. Besides, these results give an outline on the fundamental highlights of the worldwide trade. Moreover, these data also put forth the significance of the commidities and the fundamental countries as well as the principal trade streams. In the recent years, the volume of world trade of medicinal and herbal plants has increased in great ratios and it is estimated that this growth will continue further in the coming years. According to the results of the statistics, “medicinal and pharmaceutical products” resulted with the highest scores between the exported commodities worldwide by the end of 2016. The amount of exports was announced as 198.3 billion US$ while imports were stated as 197.6 billion US$. Exports of this merchandise elucidated the 11.1% of the world total. Switzerland, Germany, and the United States were stated as the top three countries that meet medicinal and pharmaceutical products exports with the ratios of 15.9%, 14.0%, and 13.8% respectively, while Belgium, Netherlands, United Kingdom, China, France, and Italy were recorded as the following countries. Furthermore, USA, Germany, and Belgium were specified as the top destinations with 14.0%, 11.7%, and 7.7% respectively, of world imports (Comtrade, 2016a). In a special category of “tea and mate,” the amounts of exports and imports were given in the following as 8.4 billion US$ and 7.7 billion US$. In the year of 2016, China, Sri Lanka, and Kenya were listed as the top exporters with 19.0%, 15.1%, and 14.9% internationally. At the same time, the United States, Russian Federation, and United Arab Emirates were recorded as the countries which had purchased these products with the percentages of 8.7, 7.3, and 6.4, respectively (Comtrade, 2016b).

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   367

In another category, spices which are defined as the dried vegetable products used for giving the aroma and flavor to foods, gained importance related to their phenolic profile as well as plants and herbs. When the export and import amount of spices are evaluated internationally, it was seen that the export value of spices were reduced by 0.4%, while imports were decreased in a higher ratio with 1.0%. These values were given respectively as 10.3 billion US$ and 9.5 billion US$ worldwide. Likewise, Vietnam and India had the ultimate amount of exports respectively reported as 1.3 billion US$ and 1.2 billion US$. In 2016, Turkey was stated in the top exporting countries or areas list together with a 14.8% growth and 1.5% world share (Comtrade, 2016c). Turkey is a country with biological diversity in terms of plants due to its geological position. In Turkey, there are three plant geographical regions, Mediterranean, Europe-Siberia, and Iran, as a sign of climate and topography. Each of these regions has its own endemic species and natural ecosystems (Tan, 2010). Turkey also contains many herbal products which constitute the raw material of herbal medicines, plant chemicals, food and additives, cosmetics and perfumery industries of developped countries. Of these plant products, 8988 plant species are natural and 2991 plant species are endemic species (Bayram et al., 2010). In addition, Turkey has 75% of European-based plant species, of which about one-third are endemic. Harvesting of wild and aromatic plants from nature is seen as an economic raw material supply route for now. However, the inconveniences such as the lack of a standard production and the mixing of different plant groups into the main crop during the establishment of plants affect the continuity of production and product safety. Thus, cultivating medicinal and aromatic plants, which have a lot of demand has become a necessity to ensure continuity in quality and not to destroy genetic diversity. The proper cultivation of the correct plant species, processing of the raw materials with the help of advanced technologies, packaging, storage, and marketing of this plants, can be listed as the most important factors in this area (Baydar and Baydar, 2005).

13.3.3  Commonly Used Medicinal Herbs Commonly used parts of herbs in drinks/beverage production, their bioactive compounds, and health benefits are given in Table 13.1.

13.4  Fortification of Beverages With Herbal Extracts In the process of the fortification of beverages, diverse kinds of ingredients can be added to the formulations for the improvement of

368  Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE

Table 13.1  Properties of Some Herbs Commonly Used in Drinks Name of the Herb

Used Parts of the Herb

Artichoke (Cynara scolymus)

Bioactive Compound

Health Beneficial Effects

Fresh or dried basal leaves

Chlorogenic acid, flavonoids, sesquiterpene lactones (cynaropicrin)

Burdock (Arctium lappa)

Dried aerial parts and roots

Flavonoids, polyacetylenes, inulin

Clover (Red) (Trifolium pretense)

Flowering tops

Damiana (Turnera diffusa)

Dried leaves

Volatile oil (benzyl alcohol), isoflavonoids, coumarin derivatives, cyanogenic glycosides, genistein Volatile oil, tannins, resins, glycosides

• Regenerate liver tissues, • Treat dyspeptic problems • Reduce blood lipids, serum cholesterol, and blood sugar • Blood purifier • Remove toxins from blood • Orexigenic properties • Relaxant (sedative) • Expectorant • Wound healing properties

Dandelion (Taraxacum officinale) Echinacea (Echinacea purpurea)

Fresh and dried root and leaves

Elderflower (Sambucus nigra) German chamomile (Matricaria recutita) Ginkgo (Ginkgo biloba)

Fresh or dried rhizomes and roots, aerial parts and juice Dried or fresh flowers berries, leaves and bark Flowers and flowering tops

Dried leaves

Sesquiterpene lactones, triterpenes, steroids, flavonoids, mucilages, inulin Water soluble polysaccharides, glycoproteins, volatile oil, caffeic acid derivatives, alkamides, polyynes, pyrrolizidine alkaloids Flavonoids, chlorogenic acids, volatile and fixed oils Volatile oil, flavonoids, coumarin compounds, mucilages

Proanthocyanidins, flavonoids, bioflavonoids, diterpenes, sesquiterpenes

• Nerve stimulant • Treat nervous exhaustion and anxiety of a sexual nature • Mild irritant of the genitourinary tract • Promote the flow of digestive juices in the upper intestinal tract • Antibacterial • Virostatic effects • Anti-inflammatory effect • Immune stimulant • Antiviral activities • Usage for colds and fevers • Induce sweating • Reducing temperature • Sedative and calming properties • Calm the digestive system

• Improve blood flow • Retarding the degenerative effect of Alzheimer’s disease • Improve memory and learning capabilities • Countering altitude effects

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   369

Table 13.1  Properties of Some Herbs Commonly Used in Drinks—cont’d Name of the Herb

Used Parts of the Herb

Ginseng (Panax ginseng)

Bioactive Compound

Health Beneficial Effects

Main root, side roots and rootlets

Triterpene saponins, ginsenosides, water soluble polysaccharides and polyynes

Guarana (Paullinia cupana)

Seeds

Caffeine, theophylline, theobromine, purine alkaloids, tannins and saponins

Hops (Humulus lupulus)

Dried strobile

α and β bitter acids (humulone and lupulone), volatile oil

Horehound (white) (Marrubium vulgare) Kola (Cola nitida and C.acuminata)

Fresh or dried aerial parts

Diterpenes, caffeic acid derivatives, flavonoids, volatile oil

• Help the body fight off physical, chemical and biological attacks • Raise the body’s own defense mechanisms • Benefit in terms of physical and mental performance • Reducing blood sugar levels in Type II diabetics • Central nervous system stimulant • Short-term diuretic effects • Astringent effect • Treating diarrhea • Sedative • Soporific • Antibacterial • Antifungal • Stimulate the secretion of gastric juice • Anaphrodisiac • Stimulate digestive juices • Traditional expectorant

Seed after removal of the testa

Lemon balm (Melissa officinalis)

Dried aerial parts

Limeflower (Tilia cordata and T.platyphyllos)

Dried flowers

Purine alkaloids (caffeine), theophylline, theobromine, tannins, proanthocyanidins, starch Volatile oils, glycosides of the alcoholic and phenolic volatile compounds, caffeic acid derivatives, flavonoids, triterpene acids Mucilages, flavonoids, tannins, chlorogenic acid, volatile oils

• Nervous stimulant • Stimulate the digestive system • Lipolytic • Diuretic • Antibacterial • Antiviral • Sedative for nervous indigestion • Given to children for stomach upsets • Diuretic • Expectorant • Calm the nerves • Lower blood pressure • Improve digestion Continued

370  Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE

Table 13.1  Properties of Some Herbs Commonly Used in Drinks—cont’d Name of the Herb

Used Parts of the Herb

Maté (Ilex paraguariensis) Meadowsweet (Filipendula ulmaria) Nettle (Urtica dioica)

Dried leaf and leaf stems

Passion flower (Passiflora incarnata) Rooibos (Aspalathus linearis) Rosehip (Rosa canina)

Aerial tops of the stems, comprising leaves flowers fruit Leaves and stems of new grown shoots Fruit

Sarsaparilla (Smilax regelii, S. aristolochiaefolia, S. febrifuga) Schisandra (Schisandra chinensis) Siberian ginseng (Eleutherococcus senticosus)

Dried rhizomes and roots

Valerian (Valeriana officinalis)

Flowering tops and leaves Fresh or dried aerial parts, roots

Bioactive Compound

Health Beneficial Effects

Caffeine, theobromine, caffeic acid derivatives, flavonoids, saponins, volatile oil Salicin

• Stimulant effects • Diuretic • Lipolytic (fat-burning) • Astringent • Antacid properties • Sooth and relieve pain • Anti-rheumatic • Anti-arthritic • Diuretic

Vitamins A and C, iron, histamine, serotonin, acetylcholine, formic acid, flavonoids, silicic acid, volatile oil, potassium and nitrate ions Flavonoids

Polyphenols

• Antioxidant • Anti-aging

Vitamin C, fruit acids, pectins, sugars, carotenoids, flavonoids Steroidal saponins

• Usage in cold and influenza preparations

Fruit

Essential oil, fruit acids, sugars, resin

Dried root and root bark

Triterpene saponins, steroid glycosides, hydroxycoumarins, caffeic acid derivatives, lignans, steroids, polysaccharides Valepotriates, volatile oils, valeric acid

Fresh or dried rhizomes and roots

• Sedative

• Used for skin complaints • Diuretic • Diaphoretic • Blood purifier • Used for kidney complaints • Control the secretion of body fluids • Act as a tonic for nervous system and circulatory system • Usage as tonic for strength and revitalization • Immunostimulatory effect

• Daytime sedative to reduce anxiety and stress

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   371

Table 13.1  Properties of Some Herbs Commonly Used in Drinks—cont’d Name of the Herb

Used Parts of the Herb

Bioactive Compound

Health Beneficial Effects

Vervain (Verbena officinalis)

Aerial parts of the herb

Iridoids, flavonoids, caffeic acid derivatives

Wolfberry (Goji Berry) (Lycium barbarum)

Fruits

Carotenes, Vitamins B1, B2, B3, and C, β-sitosterol, linoleic acid

Wormwood (Artemisia absinthium)

The upper shoots and leaves

Volatile oil, bitter sesquiterpene compounds

• Astringent, cough, suppressant and lactation promoting properties • Diuretic • Sedative • Improve the liver and gall bladder functions • Nourishing effect for convalescence • Lower blood pressure and blood cholesterol levels • Inhibit the deposition of fat in liver cells • Promote regeneration of liver cells • Stimulate the appetite • Stimulate an increase in secretion of digestive juices • Increase liver function

Modified from Shaw, E.F., Charters, S., 2016. Functional drinks containing herbal extracts. In: Ashurst, P.R. (Ed.), Chemistry and Technology of Soft Drinks and Fruit Juices. John Wiley & Sons Ltd., West Sussex, pp. 310–354.

nutritional properties and health benefits while providing sensorial and palatable balance. For this aim, mostly added ingredients can be listed categorized as polyphenols, carotenoids (Xanthophylls, i.e., astaxanthin, cryptoxanthin, lutein, and zeaxanthin), oils (Omega-3, i.e., alpha-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid), sterols, stimulants, and botanicals (Superfruits, i.e., acai, mangosteen, pomegranate, teas, and herbal extracts) (Gruenwald, 2009). Some of the fruits are called as “superfruits” because of their high antioxidant contents. They are generally used in beverage formulations and juices made from them have advantages both in terms of palatable balance and functional properties (Shaw and Charters, 2016). Used parts in the beverage formulations, bioactive compounds, and health benefits of common superfruits are given in Table 13.2. When the subtitle “stimulants” is taken into consideration, it is seen that, in several parts of the functional beverages sector, an inclination for more advantageous vitality alternatives with expanded demand for herbal and natural items can be seen. Hence, energy/wellness drinks have started to gain more popularity compared to caffeinated drinks.

Table 13.2  Bioactive Compounds and Health Benefits of Superfruits Name of the Superfruit

Used Parts of the Superfruit

Acai berry (Euterpe oleraceae)

Bioactive Compound

Health Beneficial Effects

References

Fruits

Anthocyanins, proanthocyanidins, flavonoids, resveratrol

Shaw and Charters, 2016; Schauss et al., 2006

Chia (Salvia hispanica)

The seeds

Guava (Psidium guajava L.)

Fruits and dried leaves

Mangosteen (Garcinia mangostana)

Fruit

Omega-3 fatty acids, flavonol glycosides, chlorogenic acid, caffeic acid Vitamins A, C, B1, B2, and B6, iron, calcium, fiber, tannins, flavonoids, essential oils, sesquiterpene alcohols and triterpenoid acids Flavonoids, tannins, xanthones

Noni (Morinda citrifolia L.)

Fruit, leaves

Scopoletin, nitric oxide, alkaloids, anthraquinones, capric and caprylic acids, sterols

Papaya

Fruit, seeds, leaves, roots

Polysaccharides, vitamins C and E, alkaloids, glycosides, lectins, saponins, flavonoids, sterols

• Increase mental alertness • Increase energy • Restore memory • Help to prevent cancer • Reduce inflammation • Improve hearth health • Stabilize blood sugar levels • Prevent of cardiovascular damage • Positive effects on dyslipidemia • Anticancer properties • Lower cholesterol, gycemia • Hypoglycemic effects • Anti-mutgen • Anti-carcinogen • Anti-inflammatory • Antifungal • Antibacterial • Antioxidant • Antimicrobial effects • Anticancer activity • Antioxidant properties • Anti-inflammatory activity • Analgesic activity • Cardiovascular activity • Diuretic • Expectorant • Sedative • Relieve obesity • Skin diseases psoriasis • Antibacterial activity • Hepatoprotective

Shaw and Charters, 2016; Taga et al., 1984 Barbalho et al., 2012; Thuaytong and Anprung, 2011

Pedraza-Chaverri et al., 2008; Pothitirat et al., 2009

Chan-Blanco et al., 2006

Krishna et al., 2008

Passion fruit (Passiflora edulis Sim.)

Fruits

Anthocyanins (pelargonidin), carotenoids, potassium, vitamins A, B6, C, and E, polyphenols

Pomegranate (Punica granatum L.)

Fruit and seeds

Polysaccharides, polyphenols, triacylglycerols, flavonoids, tannins

Star fruit (Averrhoa carambola L.)

Fruit

Flavonoids, vitamin C and E, carotenoids, polyphenols

• Treat anxiety, insomnia, asthma, bronchitis, urinary tract infection • Sedative • Treat gastrointestinal disorders • Antioxidant • Anti-inflammatory activity • Antifungal • Inhibiting growth of breast cancer • Antimicrobial activity • Antioxidant activity • Anti-carcinogen • Anti-inflammatory activity • Antioxidant activity • Relieve pain from indigestion and bleeding hemorrhoids • Reduce fever

Schotsmans and Fischer, 2011

Miguel et al., 2010

Bhat et al., 2011; Zainudin et al., 2014

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Herbs are added to functional beverages to raise cognitive performance, as well as the aim of preventing tiredness. One of the added extracts is caffeine, which is a xanthine alkaloid sourced from the beans, leaves, and fruit of the plants especially from coffee plant, tea, kola nut, or cacao. Yerba maté, guarana berries, and the Yaupon holly can be listed as the others. The amount of caffeine in common energy drinks is adjusted to 80 mg as the same in a cup of coffee but in several brands this amount can change as 160 and 260 mg per serving (FDA, 2012).

13.4.1  Energy Drinks 13.4.1.1  Herbal Content of Energy Drinks Energy drinks mainly include caffeine, sugar, amino acids (taurine), electrolytes, vitamins, and herbal ingredients. They are consumed cold just like soft drinks. Herbal ingredients play an important role in the sensory evaluation of energy drinks as well as improving their health beneficial effects. The most common herbs used in energy drinks can be listed as ginseng and ginkgo biloba. Other botanical ingredients can be summarized as bee pollen and guarana. Royal jelly is also used in the energy drinks formulations as an animal product. Many of the botanicals are used in beverage formulations in the form of standardized liquid extracts solved in water/alcohol or glycerine. Fully water-soluble spray-dried premixes are additionally accessible (Ragsdale, 2016).

13.4.1.2 Ginseng Herbal drinks, commonly known since a very long time, are believed to be originated from China with defined recipes approximately by the third century BC. Ginseng is archived as one of the oldest herbal drinks together with wolfberries and linghzi mushroom and was considered as a general remedial agent (Bown, 2003). One of the traditional methods for the utilization of ginseng was the preparation of tea with the dried roots. The other treatments applied for the consumption of ginseng can be listed as immersing the root in water, preparing an infusion of the root or drinking the boiled root (Pokladrik, 2008). Till date, 80 diverse kinds of ginsenosides, obtained from different parts of the Panax ginseng plant were isolated. Furthermore, antioxidant, anti-inflammatory, anticarcinogenic, antidiabetic, cardiovascular system dysfunction-improving, and anti-stress activities of ginsenosides were reported (Lim et al., 2010; Nag et al., 2012). Ginseng content of energy drinks ranges between 2 and 200 mg in approximately 227 g/1 cup/237 mL (Kim et al., 2010; Loeb, 2010). Ginseng, a plant-based herb, is commonly extracted from the Panax ginseng plant which has been traditionally utilized as a customary medicine by people. Panax ginseng Meyer, the Korean red ginseng is the most popular processed ginseng item in the Orient (Vinh et al., 2017).

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   375

Before marketing, plant extract is usually processed. Its pharmaceutical properties revealed that the consumption of this plant intended to help resistant activities, enhance state of mind, and increase vitality (Kennedy et  al., 2002). Ginsenosides (dammarane-type triterpene glycosides) form the main active compounds of Panax ginseng. Ginsenoides are divided into two main groups like the protopanaxadiol (X) and the protopanaxatriol (Y). X include Rb1, Rb2, Rc, and Rd ginsenosides with C-3 stated sugar moieties while Y contains them (Re, Rf, Rg1, and Rg2) placed in the C-6 position (Vinh et  al., 2017). According to the results of a study (Kim et al., 2011b) extracts of red ginseng included total flavonoids with an amount of 13.20 μg/mg, while this quantity raised by 39% in the fermented form in which the red ginseng was fermented with Lactobacillus fermentum (0.1%) at 40°C for 12 h. Additionally, unfermented red ginseng was not reported to contain Rb1 and Rh2 ginsenosides that possess antioxidant properties, while they were detected in fermented red ginseng. Moreover, the amount of antidiabetic ginsenosides such as Rg3 was found to be increased almost threefold when compared to the unfermented herb. In this shed of light, fermentation can be revealed as a supportive process for the improvement of bioactive components of red ginseng. In general applications, it may be concluded that fermentation with probiotics can also serve as a key factor for both the preservation of foods and the manufacturing of functional foods with enhanced antioxidant activities.

13.4.1.3 Ginkgo Ginkgo biloba is indicated to give mental vitality by expanding blood flow to the cerebrum. Ginkgo is thought to have nootropic impacts and cerebral and cardiovascular benefits identified with antiplatelet initiation and enhance blood dissemination, a considerable lot of which are identified with antioxidant potential (Ramassamy, 2006). The incidence of bleeding related with ginkgo is related to doses that overrun 240 mg/day, a sum that incredibly surpasses that in energy drinks (15–20 mg/ 237 mL). This degree of ginkgo removal is quite below that of any cardiovascular or neurological benefit or hazard (Anonymous, 2012b).

13.4.1.4 Guarana Guarana is an additive obtained from Paullinia cupana berries. These berries include caffeine as twice as the practically identical measure of coffee beans. Its extract includes theobromine and theophylline. Guarana is put in to energy drinks between 1.4–300 mg/355 mL. L—carnitine, L—theanine and acai berry extracts can be revealed as the other herbal ingredients of energy drinks which existed in trace amounts (Loeb, 2010).

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13.5  Production Methods and Applications of Herbal Extracts Production of herbal extracts is of great importance in terms of preventing the mistakes applied in traditional techniques that may cause diverse deteriorative effects. The most common misstep can be mentioned as mixing a wide variety of herbs in random proportions and preparing them at promiscuous parameters such as long infusion time or high temperatures. By controlling and standardizing the production processes, achieving a microbiologically safe product while benefiting from the nutritional and functional properties should be aimed.

13.5.1  Common Techniques Herbal extracts are mainly produced with several methods such as; infusion, decoction, percolation, liquid extract production, soft extraction, tincture, powdered extracts production, and novel techniques such as supercritical carbon dioxide extraction, microwave-assisted extraction, and ultrasound-assisted extraction.

13.5.2 Infusion Infusion is the production of aqueous extracts via the method of steeping a herbal raw material. Traditionally, infusions are prepared by the addition of boiled water on to the dried herb, abandoning it to soak and afterward straining out the resultant. Infusions used in beverage formulations are frequently completed at ambient temperature yet utilizing some alcohol in the liquor. Since infusion is an extremely broad term, there is not any defined value for the plant/extract proportion. However, 1 part of herb can give yield of 4 to 10 parts of mixture. The quality of the extraction relies upon the bulk density of the dried herb and provided with 1 part of herb yielding around 2.5 parts of extract in most cases. Customarily, dried herbs are used in the production of the extracts, due to storage convenience. In the event that it is important to utilize fresh herbs for extraction, the expanded water content, which can be up to 90% with leafy herbs, must be taken into consideration. Along these lines, a significantly weaker concentrate is acquired if fresh herbs with just around 10% dry weight are utilized as a part of an indistinguishable extent from dried herbs (Shaw and Charters, 2016).

13.5.3 Decoction Decoction can be defined as the strategy utilized for the extraction of harsh materials like roots and barks. There is a minor difference from the common infusion process, which is the constant supplement of heat, to keep the finely partitioned herb saturated in boiling water.

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   377

The mixture is left simmering slowly, as opposed to strong boiling. For the compensation of losses that may come from the evaporation, water is added to the mixture. On cooling, decoction is filtered then the herb is removed. Basically, steps of making a decoction is very similar to brew a cup of tea. Plant cells are swelled as a result of the effects of heat and moisture, the cell wall is extented and then plant constituents are hydrodispersed from the swollen membranes (Wren et al., 1988).

13.5.4 Percolation One of the alternatives to infusion is percolation which can be described as the solvent extraction process. Differing incidence of liquor and water solvents are trapped on to the highest point of the crude material, which is implicated in a glass or metal section recognized as a percolator. The steady expansion of the solvent to the highest point of the segment causes a gradual down flow direct to the crushed crude material. Soluble plant compounds which are contained in the liquid are collected from the underside of the vessel. This process can be reused for the achievement of higher yields and quicker extraction rates, when compared to the static soaking treatments. Osmosis and diffusion all through the cells composes of the mechanical part of the process. This delicate technique can be utilized as a part of the creation of natural flavours (Shaw and Charters, 2016).

13.5.5  Liquid Extract Production Liquid extracts give more perpetual and advantageous types of s­ aving the constituents of botanicals in higher condensations while they customarily create 1:1 yield (Wren et  al., 1988). It is produced by the filtration process after drenching the crude material in the water or potentially ethanol twice or thrice. Extraction continues with a progression of fresh groups of extracting fluid. These bulks are consolidated and concentrated back to the first weight of the herb by the evaporation under decreased pressure. The replacement of liquid extracts with the dried herbs can be possible as they can be evaluated in a weight-for-weight base. This type of concentrate commonly contains 20% liquor, which goes about as a compelling additive. A few concentrates are determined at higher liquor qualities to deliver the ideal extraction of the actives contained in the crude material. As a consequence of the heating in the concentration step, the liquid extract may ­regularly result with caramelized color and scent (Shaw and Charters, 2016).

13.5.6  Soft Extraction Stepping of the crude material in the solvent includes the initial phase of soft extraction arrangement. A few splashes might be

378  Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE

r­ equired, which are filtered and evaporated down in a steady progression. The underlying arrangement is the same as the liquid extract; in any case, the concentration obtained is then proceeded until the point that the resultant concentrate includes a moisture of 30% or less. The last product is typically exceptionally thick, like a syrup or delicate thick glue and is normally dull dark colored with a caramelized flavor. The principle application for a soft extract in a beverage is the point at which the item name guarantees a moderately high level of plant dynamic in its recipe. The concentrate may need to contain a predefined convergence of tested dynamic inside it to guarantee that the broad coasted assertion is met. The specialized test is frequently conducted to create a detailing that can disguise the color, smell, and taste of the extract. A soft extract might be utilized as the ingredients of a system for spray-drying or freeze-drying when the system is needed to include natural parts. For this procedure, infusions may be inadmissible related to their high liquid substance. Soft extracts can serve as new alternatives as they normally contain a considerably bigger amount of the dynamic segment from the plant from which they are obtained, and in higher ratios than the liquid extracts (Shaw and Charters, 2016).

13.5.7 Tincture A tincture can be revealed as an ambient temperature extract. It included extraction liquid with the ratios of commonly being 60%–70% or more. Without the expansion of heat the solvent acts specifically. Similar to liquid extracts, tinctures are perpetual arrangements. They are particularly appropriate for separating drugs containing resinous and volatile standards, since the liquor accelerates undesirable gums and albuminous issue. This empowers tinctures to be filtered to yield clear, rich arrangements which are all around protected from corruption. A wide assortment of crude parts (e.g., dried plant, leaves, roots, bark, and blossoms), which are able to be generally splashed at least twice in a blend of water and ethanol, can serve as a material for the utilization of tinctures. Diverse qualities of the splashes are assembled like: 1–10 compares to 10 kg of extract acquired from 1 kg of crude material, and a grouping of 1–5 implies 5 kg are recuperated from 1 kg of crude material. The quantity of douses can fluctuate in terms of the different extracts (Wren et al., 1988).

13.5.8  Powdered Extracts Production A powdered extract is made by replacing the moisture in a delicate concentrate with an equivalent measure of a substrate, for example, calcium phosphate, starch, or maltodextrin. The moisture is regularly

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   379

expelled utilizing a vacuum oven to prevent the extract from thermal degradation (Shaw and Charters, 2016).

13.5.9  Novel Extraction Methods Customary pharmaceutical extraction forms are renewed with huge improvements due to the positive effects of the current flavor and phytopharmaceutical businesses. Though ethanol was extremely the major solvent differing from water utilized by the conventional pharmaceutical extractors, solvents like hexane and acetone have been utilized by the factories which make soft extract oleoresins for regular flavor components. In recent years, sub- and supercritical carbon dioxide and furthermore some fluorohydrocarbons are presently used to deliver some top notch extracts. According to the present day focus, drying procedures like reverse-osmosis, spray-drying, and freeze-drying can yield extracts with less color loss and caramelization issues. However, this advantage comes with high installation costs. When all of the methods used for the chemical separation and the improvement of the productivity of herbs are taken into consideration, supercritical fluid (SCF) extraction, membrane separation, ultrasound-assisted extraction, molecular distillation, and polymeric adsorbent technique are coming forward as new trends (Zhu, 2000; Li, 2002). At temperatures and pressures more noteworthy than the critical point esteems a one-part liquid can have densities and solvent features drawing closer those of the suitable fluid. Fluids in this administration are characterized as SCFs. Other interesting highlights of SCFs are that the solvent nature of a SCF is pressure dependent, temperature dependent, or both, while the dispersion coefficient is nearer to that of a gas. Because of the difference in external parameters of temperature and pressure, solute-solvent associations like those between a dissolved polymeric compound in an SCF can be controlled (McHugh and Krukonis, 1994). The properties like the moderate critical features (Tc=31.3°C, Pc=7.38 MPa), nontoxicity, chemical inertness and presence in superior purity together with low cost of supercritical CO2, brings it to the fore as the widespread material used in the applications. For this reason, carbon dioxide is preferred in the extraction of natural foods especially like coffee, tea, and hops (King, 1989; Bruno and Ely, 1991; Koga et al., 2001).

13.5.9.1  Supercritical Fluid Extraction Finding new extraction methods alternative to traditional techniques has become increasingly necessary for producers. Sub- and supercritical types of carbon dioxide come as the response to this ­demand as they bring out fine quality extracts together with the

380  Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE

­ robability of utilizing the distinction in extremity between the subp and supercritical status to aid specific extraction. Extraction of caffeine is one of the most important examples of supercritical carbon dioxide applications. During the process caffeine is selectively extracted while organic solvents are not used. However, there can be difficulties with the implementation of the system commercially (Kim et al., 2007; Cardozo-Junior et al., 2007). The most conventional technique for handling herbs includes boiling them in water for a considerable length of time so that a large portion of the ingredients are dissolved. The other strategy includes the utilization of customary organic solvents such as ethanol, methanol, chloroform, and ether for the extraction as opposed to boiling water. At the point when the conventional extraction techniques for handling of herbs are utilized, the extract comprises of different mixes, like the unwanted matters in the final product. In this manner advance refinement steps, which can last for a week, are important to expel the coextracted impurities. Besides, boiling/extraction at high temperatures regularly prompt debasement of heat-sensitive components. Additionally, toxic solvent trails, which straightforwardly impacts the nature of the products, may not be really expelled from the extracts. In volatile oil production, hydrodistillation is the most operated technique for the obtainment of volatiles from the plants, whereas it also leads to heat-sensitive components degradation. On account of this situation, alternative extraction systems with preferable particularity and performance are exceedingly attractive. Applications of SFE in the processing of herbal materials can be classified as, supercritical carbon dioxide extraction, SFE with carbon dioxide in the presence of surfactant, its combination with ultrasound assisted extraction, its combination with separation techniques, and the combination with other techniques to yield maximum from herbal products.

13.5.9.2  Microwave-Assisted Extraction The extraction techniques, in which solvents are used at low pressures, come as an alternative for product specific systems. According to the type of the system, extraction might be applied with microwave-­ assisted or ultrasound-assisted differing from the simple solid-liquid extraction. In this point, a change in the cell structure is occurred by the reason of electromagnetic or sound waves respectively for microwave and ultrasound processes (Takeuchi et al., 2009). The frequency of the microwaves ranged from 0.3 to 300 GHz while they are defined as non-ionized electromagnetic energy. Waves are used for the transmission of energy and they have an ability to penetrate in biological materials. Microwave-assisted extraction has advantages like shorter extraction time and solvent usage, volumetric

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   381

heating, and manageable heating operation (Wang and Weller, 2006). Microwave-assisted extraction is mainly used in the extraction of bioactive compounds and essentially from the medicinal and aromatic plants. There are several studies focused on microwave-assisted extraction from the plants like ginger (Zingiber officinale), paprika (Capsicum annum L.), cardamom (Elletaria cardamomum L.), and essential oil from bay laurel (Laurus nobilis L.) (Csiktusnádi Kiss et al., 2000; Alfaro et al., 2003; Lucchesi et al., 2007).

13.5.9.3  Ultrasound-Assisted Extraction For the extraction of medicinal and aromatic herbs, commonly used solvents can be considered as water and organic solvents. Ultrasound is used as a new method in the extraction of bioactives like flavonoids, essential oils, polysaccharides, and esters in food and pharmaceutical sector. Elastic sound waves with a frequency about 20 kHz can be defined as ultrasonic waves. In food, waves radiate through solid-liquid, moving in longitudinal and perpendicular, while longitudinal waves can be seen in gases and liquids. The effect caused from the sound waves in matter can form a negative pressure at 50 MPa and this effect can make bubbles in a liquid while the collapse of the bubbles cause cavitation. This collapse near cell walls results with cell corruption and solvent penetration in to the cells. Benefits of this method are the capability of carrying out several samples at the same time and short extraction periods. This extraction method is applied to several herbs like fennel, hops, lime, mint, and the extraction of oleuropein from olive leaves and carvone and limonene extraction from caraway seeds (Toma et al., 2001; Chemat et al., 2004; Japón-Luján et al., 2006).

13.6  Instant Tea Production 13.6.1  Overview of Tea Marketing Tea is marketed in several forms like black tea, green tea, herbal tea, instant tea, and ice tea (Sinija et  al., 2007). In Turkey, black tea has been the most consumed type for years. During the last decade, green tea, and herbal teas are started to be preferred by consumers (Tontul et al., 2013). Furthermore, ice tea can be produced in a different way than the other products as it is the form of diluted tea extract and is marketed in ready to drink cans or bottles. In the year of 2016, ice tea had 45.7% of market share and reached more than 1.7 billion gallons category volume while other products with the inclusion of loose and bagged tea, mixes, and pods accounted the rest of this ratio with 54%. Additionally, specialty tea/ice tea is of increased attention in beverage sector related with the consumer’s demand for natural foods and health and wellness products. As this demand grows, innovative

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t­ echniques and new products are becoming the key factors which will focus on lifestyle and diets specific to consumers (Goggi, 2016).

13.6.2  Production Methods and Microencapulation of Herbal Extracts Along with the importance of developing new techniques for the production of standard food and herbal extracts, dried products have attracted increased interest. When compared to liquid forms, advantages of drying treatments are getting to the foreground. These advantages could be itemized as prolonged shelf life, improved nutritional properties, ease in storage and transportation, production of more concentrated products, and steady form of the active components (Suna et al., 2014; Tontul et al., 2013). Miscellaneous types of tea products are available on the market like; tea bags, packets, blended tea, ready to drink tea, and instant tea (Alasalvar et  al., 2013). Within these varieties, instant tea is distinguished from the others with its totally soluble form. Instant tea is generated from tea by the extraction of the brewed, processed, or undried fermented leaves and tea residuals (Mason and Zhao, 1994). Vacuum with low temperature was applied for the concentration of the extract for the minimization of the flavor and aroma losses and then the extracts was dried. The most common methods for instant tea powder production could be listed as spray, freeze, and vacuum drying (Someswararao and Srivastav, 2012). Spray drying is generally utilized in food and chemical industry, especially in pharmaceuticals and aroma (Rojas Salas et  al., 2017; Donhowe et  al., 2014). While milk and whey powders compose the majority of the spray-dried products, this technique is well suited to the production of instant coffee and tea as well as several products. The most common spray dried products are depicted in Fig. 13.1. Spray drying falls inside the gathering of microencapsulation techniques that contain spray-chilling, fluidized-bed coating, extruding, lyophilization, coacervation, besides others (Nedovic et  al., 2011). Encapsulation is defined as the process in which particles (bioactive components) are entrapped inside a wall material (carrier). It is a significant issue in the delivery of bioactive components and living cells into food. Moreover, carriers should be food-grade, biodegradable, and capable of forming a barrier between the internal phase and its surroundings. The results of such a technique are microcapsules, including active components with diameters involved in the scope of μm-mm (Avelleno et al., 2018). Particularly, spray drying is an innovative procedure where a fluid is atomized through a hot gas (air or nitrogen) current, ending up with a powder (Aundhia et al., 2011). It is the common method, which immediately dries liquid droplets under

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   383

Fig. 13.1  Examples of spraydried products. Adapted from Suna, S., Özcan Sinir, G., Çopur, Ö.U., 2014. Nano-spray drying applications in food industry, Bulg. Chem. Commun. 46, 137–141.

hot inlet air for the production of powder from liquid and semiliquid foods. Furthermore, spray drying is also a brief and manageable treatment for the retention of quality parameters like color, flavor, and nutrients (Kraujalyte et al., 2016). For a successfully completed spray-drying process, selection of carrier material as an encapsulating agent specific to the process comes as the most important factor. In this point, carriers must be able to be steady over time, protect the content of the capsule, and to refrain interaction with external conditions. Several drying aids or carriers which ensure stability and advance product recovery can be listed as maltodextrin, modified starches, and arabic gum (AG). Furthermore, spray drying and other encapsulation techniques are applicable to the other products like dried detergents. Herein, diversified synthetic polymers could be used as wall materials, differing from those designed for food consumption (Barbosa-Cánovas and Vega-Mercado, 1996). For the use in food and products, mostly carbohydrates (starches, syrup solids, maltodextrins, and pectins), gums (gum arabic and mesquite gum), and milk proteins are employed as carriers (Gharsalloui et al., 2007).

13.6.3  Spray Dried Instant Tea and Other Products During the production of instant foods, valuable constituents of tea like volatile compounds and polyphenols comes as the priority of the process. Polyphenols are effectively disrupted when presented to the improper conditions such as heat, moisture, and light, as a result of

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the existence of active phenolic hydroxyl in their structure (Jayasekera et  al., 2011). Their thermally unstable and degradable structures affect thoroughly the properties of the powder such as the color and flavor. Additionally, adverse effects on polyphenols and their antioxidant activity during storage is a challenging subject together with the protection of bioactive content from damage throughout the process. Microencapsulation comes as an effective technology for the preservation of the stability and efficiencies of polyphenols (Çam et al., 2014). The increase in the stability of polyphenols from cactus pear (Opuntia ficus-indica) pulp and bayberry when subjected to spray dried were stated, respectively, by Saénz et al. (2009) and Zheng et al. (2011). When the instant tea production is evaluated, like in the majority of the food products, polyphenols could be damaged. For example, the epistructured catechins have a tendency to be changed over to their nonepistructured equivalents or be debased because of oxidation at extreme temperatures (Vuong et al., 2010). Besides, microcapsules of tea polyphenols had not been reported so far and it is still an important topic provided that the stability and the efficiencies of microencapsulated polyphenols could be developed. Wang et  al. (2016) investigated the effects of microencapsulation on the stability of “tea polyphenols” by using spray drying. For this aim, stabilities of free and microencapsulated tea polyphenols under in vitro digestion, encapsulation efficiency according to total phenolic content and antioxidant activity were analyzed. Extracted green coarse tea phenolics were coated with “hydroxypropyl methylcellulose phthalate” water solution (4%). Microcapsules particle size was analyzed between 10 and 200 μm by scanning electron microscopy. Microencapsulated tea polyphenols resulted with a 70.98% encapsulation efficiency. They were released from the microcapsules in simulated intestinal fluid more than the gastric fluid. Additionally, it was revealed that microencapsulation improved the storage stability of tea polyphenols besides protecting the antioxidant potential. Consequently, its use for the storage and applications of tea polyphenols may be proposed as an alternative way in industrial scale. Nadeem et al. (2011) studied the possibilities of instant mountain extract (Sideritis stricta) by spray drying. For the determination of the most suitable drying conditions and carrier applications, they used different inlet temperatures like 145°C, 155°C, and 165°C and agents like β-cyclodextrin, AG, and maltodextrins (MD19 and MD12) in the concentrations of 0, 3, and 5 g/100 g. They calculated product yield, bulk density, and solubility as the main parameters of spray-dried tea powders whereas they analyzed color, turbidity, total phenolic content, antioxidant activity, and β-pinene content of reconstituted instant mountain tea. They reported 155°C as the important point that directs the temperature changes. Consequently, β-cyclodextrin and

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   385

maltodextrins were resulted with higher product yield together with solubility, color, and NTU turbidity whereas AG and maltodextrins were found to be more effective in maintaining aroma.

13.7  Usage of Herbal Extracts in Heverage Production Herbal extracts could be added to different formulations with the aim of improving health-beneficial effects. Several studies were focused in this topic and provided positive outcomes. Acrylamide, a molecule formed in food as a consequence of heat treatment, is mainly found in baked and fried products, coffee, and chocolate (Anese et al., 2014). In beverage category, coffee has a significant place and acrylamide amount in coffee is affected by the species and roasting time (Şenyuva and Gökmen, 2005; Gökmen, 2016). Therefore, reduction of acrylamide could be achieved by blending coffee with different vegetable matrices. In a patent, it is revealed that herbal blend inclusion to roasted coffee (e.g., Sambucus and Hibiscus) before or after the brewing process could decrease acrilamide quantity in the brewed coffee product by at least 10% (Fasullo-Nachtrieb, 2013). This result expressed an alternative method to lessen a level of toxic molecule. N-ethyl-L-glutamine, commonly referred to as L-Theanine (L-THE) is an amino acid placed in tea leaves which enhances taste sensation. It is mostly found in green tea leaves (Sakato, 1949). L-THE is added to functional foods in a tea form or imbedded in another matrix, related with beneficial properties such as developing cognitive function and relaxation (Williams et al., 2016; Lardner, 2014). In a recent study, 200 mgL-THE was conducted to healthy participants in a beverage, for the determination of useful stress-related effects (White et al., 2016). As a result, a decrement in stress and cortisol responses with a support in anti-stress actions was recorded. In another research, antiglyco-­ oxidative effects of L-THE obtained from the decaffeination process of tea powder was studied in maillard reaction products in breads. As a by-product, L-THE was found applicable as a dietary ingredient and it was concluded that the product had the same quantity of polyphenolics and L-THE as the decaffeinated tea (Culetu et al., 2016). Chemical structure of L-THE is depicted in Fig. 13.2. Mangiferin(1,3,6,7-tetrahydroxy-2-[(2S,3R,4R,5S,6R)-3,4, 5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]xanthen-9-one), in shorter definition “2-C-β-glucoside of 1,3,6,7-tetrahydroxyxanthone,” is a ­xanthone placed in the higher plants and in the different parts such as the peel, stalks, leaves, barks, kernel, and stone of the mango fruit (Imran et al., 2017). Mangiferin is stated as a natural ­promising ­bioactive

386  Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE

O H N

H

H

O

H N

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Fig. 13.2  Chemical structure of L-Theanine (Pubchem, 2017a).

c­ omponent with health beneficial properties like antioxidant, antiviral, antidiabetic, immunomodulatory and anti-­inflammatory activities (Dar et al., 2005; Imran et al., 2017). In a research, “tea” is legally defined as a traditional herbal beverage prepared by infusion, decoction, or maceration with water and is used for medicinal effects and the potential in the treatment of chronic noncommunicable illnesses (Medina Ramírez et al., 2016; Saleh et al,. 2013). It was also revealed that tea can be prepared from the edible parts of the plants for several health benefits such as sedative and detoxifying actions together with the treatment of depression and antihypertensivity (Unno et al., 2016). In this research, Mangifera indica L. leaf tea (M) was used for the development of mangiferin and total phenolic source. M. indica L. leaves contain phenolics such as mangiferin, quercetin, gallic acid, α-tocopherol, propyl benzoate, (+) catechin, (−) epicatechin, benzoic acid, and D-glucose. Two types of leaves were used in three different preparation process and plant:solvent ratios. For this aim, decoction (utilization of direct flame), infusion (5 min duration in boiling water), and ultrasound (sonication at 26°C for 15 min, with 135 W ultrasonic power and 40 kHz excitation frequency in the water bath) were utilized as the processes, while portions of tea was equal to 2.5 g/100 mL. Additionally, 0.0125, 0.0250, and 0.0500 (g/mL) were chosen as the plant:solvent ratios of the used young and mature leaves. As a result, the highest mangiferin content was obtained from the teas prepared with young leaves by decoction. Besides, the utilization of mature leaves stepped up the extraction of mangiferin by

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   387

infusion and as it is known, when the plant ratio in tea is increased, mangiferin resulted in higher concentrations. Consequently, “M” was proposed as a source of bioactive components specially mangiferin for the evaluation of functional beverages. Chemical structure of mangiferin is shown in Fig. 13.3. Habtemariam and Varghese (2015) investigated the rutin content and antioxidant activity of Moringa stenopetala (Ethiopian moringa) and Moringa oleifera (Indian moringa). Moringa is referred as a miracle tree due to the usage as food, medicine, edible oil, biofuel, and the utilization for water sanitation (Melesse et al., 2012). M. stenopetala is commonly recognized as “cabbage-tree” and aleko or shiferaw locally. It is an easy to grow in poor soil plant together with a short harvesting period. Additionally, its importance lies in the usage as an industrial source of rutin in nutritional and medical areas. With the aim of extracting rutin from the leaves (1 g), water, methanol, and methanol:water (50:50) were selected as solvents. It was concluded that rutin was not detected from M oleifera and it resulted with a lower antioxidant capacity (approximately fivefold) than ethiopian moringa. However, rutin (analyzed as 2.34% on dry weight) was determined as an easily extractible compound from the leaves of M. stenopetala with a 1% (leaves/boiled water) infusion ratio. In the past decades, alternative medicines have gained increasing interest among modern consumers who have a natural perspective. Supporting this situation, herbal extracts have been used in miscellaneous studies. In a research, chamomile (Matricaria chamomilla L.), meadowsweet (Filipendula ulmaria L.), and willow bark (Salix alba L.) herbal extracts were blended to produce an organic beverage and the beverage’s anti-inflammatory effects were studied in vivo. For this aim, anti-inflammatory effect in a cohort of 20 healthy adults was tested in a duration of 4 weeks. Subjects were randomized both to a treatment and placebo. Moreover, the impact of herbal beverage in lowering inflammatory cytokines and improving markers of joint

O

H

O

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H

O

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O

O

O H

O H

H

H

O

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Fig. 13.3  Chemical structure of mangiferin (Pubchem, 2017b).

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function were investigated. Consequently, anti-inflammatory effects were not found significantly different. It was revealed that further studies focusing on greater cohort with a degree of raised inflammatory properties are needed (Drummond et al., 2013). Tamer et al. (2017) explored the alternative consumption of herbal extracts in the form of cold beverages by adding them into different lemonade formulations. They aimed to design beneficial drinks having nutritional properties and a good commercialization potential. For this aim, herbal extracts of linden (Tilia argentea), heather (Erica arborea), green tea (C. sinensis), lemon verbena (Lippia citriodora), clove (Eugenia caryophyllata), peppermint (Mentha piperita), ginger (Z. officinale), and mate (Ilex paraguarensis), were used for the beverage production. Every herb extract (1%) was brewed at 98°C for 5 min and cooled down to room temperature. Besides the extract, sucrose, citric, and ascorbic acids, natural lemon flavor and lemon-­flavored emulsion were added to lemon juice concentrate. The shelf life of the products was maintained by adding sodium benzoate and potassium sorbate. As a result of the sensory analyses, lemonade with heather and ginger were the best preferred, whereas mate was found to be the least favorite. For the terms of antioxidant capacity, linden resulted with the highest amounts in FRAP (The Ferric Reducing Ability of Plasma) [26.79 μmol TE (trolox equivalent)/ mL], and DPPH ((1,1-­diphenyl2-picrylhydrazyl) radical scavenging activity) (17.72 μmol TE/mL) methods, whereas total phenolic content was determined the highest in ginger with 396.57 mg GAE (gallic acid equivalent) /100 mL. Consequently, a cloudy appearance was seen in beverages at the end of 1 year storage. In another research, formulation of a novel carbonated herbal tea beverage was investigated. For this aim, dried linden (T. argentea) flowers and leaves (1%) were infused in water and the obtained extract created the main ingredient of the beverage. Besides, sucrose, citric acid, ascorbic acid, natural lemon flavor, Na-benzoate, and K-sorbate were added to the recipe. After the plate filtration process, mixture was filled into glass bottles, carbonated, and then sealed. Antioxidant capacity was determined as the highest with 45.37 μmol TE/mL, 30.13 μmol TE/mL, and 24.44 μmol TE/mL in CUPRAC (cupric reducing antioxidant capacity), FRAP, and DPPH assays. Consequently, it was revealed that 3% of polyphenols of linden were transmissioned to the beverage and the bioaccessibility of antioxidants were ranged from 1.4 to 36.08 % in the extracts obtained by an in vitro digestion method (İncedayı, 2017). Suna (2017) investigated the production of novel ready to drink rooibos beverage. Sucrose (A), agave (B), aspartame, and acesulfame-K (C) were respectively added to the formulations. Added amounts of sweeteners instead of sugar were calculated in accordance with the

Chapter 13  TRENDS AND POSSIBILITIES OF THE USAGE   389

sweetness degree of the sweeteners. Besides, bioaccessibility of phenolics and antioxidant capacity were analyzed to put forth the ratio of available bioactive ingredients. Phenolics were calculated more accessible from “A” (405.02 ± 4.57 mg GAE/100 mL), while “B” had the highest bioaccessibility of antioxidant capacity with CUPRAC (7.19%) and FRAP (1.82%) assays. In conclusion, it was reported that all drinks were accepted as the result of sensory analysis. Kim and Baik (2015) studied the production of a probiotic functional beverage by utilizing dandelion (Taraxacum officinale) which is rich in nutritional components. Dried dandelion leaves were extracted with hot water (8%), after the addition of ingredients like jujube extract (1.5 g/100 g), honey (3 g/100 g), citric acid (0.1 g/100 g), taurine (0.03  g/100  g) and carboxymethyl cellulose sodium (0.15  g/100  g) mixture was sterilized at 121°C for 15 min. This was coded as non-­ fermented beverage (a). Afterward, sterilized extract was inoculated with L. plantarum KACC 3108, L. helveticus KCCM 11223, and L. acidophilus F46 and incubated for 8 days at 37°C then coded as fermented beverage (b). As a result of this research, fermentation significantly raised the antioxidant capacity and caffeic acid content (up to 9.91 mg/100 mL). Consequently, dandelion was proposed as a potential source for functional beverage production. In another research, Kim et al. (2016) studied the possibility of a functional beverage production with radish (Rapharus sativus L.), barley (Hordeum vulgare), and cassia (Cassia tora L.) seeds. Cassia extract (infusion and/or decoction) is preferred in beverages related with antioxidant properties together with pleasant aroma. Besides, it has diuretic effect and it comes as a significant issue in the reduction of hypercholesterolemia and hypertension (Yen et  al., 1998). In this point, hot water extracts of dried radish, barley, and cassia seeds were obtained by boiling them (1/20 w/v) separately at 100°C for 1 h. Then sugar syrup, stevia, citric acid, ascorbic acid, and short-chain fructooligosaccharides (scFOS) were, respectively, added in the ratios of 54.4 g/L, 0.73 g/L, 0.01%, 0.05%, 17 g/L. As a result, cassia extracts showed higher antioxidant capacity values with DPPH assay than other roasted grains used for the improvement of radish tea beverage. Additionally cassia seed was used for hiding the unwanted flavor of radish. Sreelakshmi and Abraham (2017) studied with edible Cassia tora leaves on the reduction of cataract pathology. In this research, Cassia tora leaves extract prepared with methanol, possessed positive activity on the interception of cataract on Sprague-Dawley rats. This activity was actualized by reducing protein and lipid modifications and by decreasing the fiery reaction, smothering protein denaturation, and cross connecting. Consequently, this result supported its traditional utilization in the treatment of eye diseases as well as being an ­alternative in

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the preventive therapy. Besides, the protective effect revealed to be related with the phytochemicals placed in the leaves. Quercetin, which has shown repressive effect on diabetic cataract could be given as an example (Vijayalakshmi and Geetha, 2014; Ramana et al., 2007).

13.8 Conclusion The widespread use of herbal teas is in the form of ready to brew bags or plant leaves, stems, roots, seeds, etc. in dried form which are able to be prepared with different traditional methods according to taste and consumer’s preference. However, the differences between the brewing methods and parameters of each plant and the promiscuous practices made, may lead to lessen the expected benefits and even result with major health risks. Therefore, in order to prevent mistakes in traditional methods, to maintain a microbiologically safe product while allowing them to be consumed in every season, to find out a value added material for the usage in beverage sector, herbal extracts are produced by standardized methods. Furthermore, miscellaneous studies have been performed in the topic of medicinal herbal extracts and their addition to the beverages for the development of the taste and sensorial characteristics, nutritional values, and functional properties. This chapter has reviewed the utilization of globally used herbs in the production of herbal extracts, explained the health beneficial effects while giving special emphasis to their properties, focused on novel applications in the food industry, and revealed up-to-date data in terms of exports and imports worldwide. Consequently, the usage of the medicinal herbal extracts in different beverage formulations as well as their manufacturing limitations were mentioned in details through current studies.

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Toma, M., Vinatoru, M., Paniwnyk, L., 2001. Investigation of effects of ultrasound on vegetal tissues during solvent extraction. Ultrason. Sonochem. 8, 137–142. Tontul, I., Torun, M., Dincer, C., Sahin-Nadeem, H., Topuz, A., Turna, T., Ozdemir, F., 2013. Comparative study on volatile compounds in Turkish green tea powder: impact of tea clone, shading level and shooting period. Food Res. Int. 53, 744–750. Trottier, G., Boström, P.J., Lawrentschuk, N., Fleshner, N.E., 2010. Nutraceuticals and prostate cancer prevention: a current review. Nat. Rev. Urol. 7, 21–30. Tulukcu, E., 2011. Herbal tea fatty acid contents of some medicinal plants grown in Konya. Turkey. Asian J. Chem. 23, 1369–1372. Uchiyama, S., Taniguchi, Y., Saka, A., Yoshida, A., Yajima, H., 2011. Prevention of diet-­induced obesity by dietary black tea polyphenols extract in vitro and in vivo. Nutrition 27, 287–292. Unno, K., Hara, A., Nakagawa, A., Iguchi, K., Ohshio, M., Morita, A., Nakamura, Y., 2016. Anti-stress effects of drinking green tea with lowered caffeine and enriched theanine, epigallocatechin and arginine on psychosocial stress induced adrenal hypertrophy in mice. Phytomedicine 23, 1365–1374. Vijayalakshmi, A., Geetha, M., 2014. Anti-psoriatic activity of flavonoids from Cassia tora leaves using the rat ultraviolet B ray photodermatitis model. Rev. Bras. Farma. 24, 322–329. Vinh, L.B., Lee, Y., Han, Y., Kang, J.S., Park, J.U., Kim, Y.R., Yang, S.Y., Kim, Y.H., 2017. Two new dammarane-type triterpene saponins from Korean red ginseng and their anti-inflammatory effects. Bioorg. Med. Chem. Lett. 27, 5149–5153. Vinson, J.A., Dabbagh, Y.A., 1998. Tea phenols: antioxidant effectiveness of teas, tea components, tea fractions and their binding with lipoproteins. Nutr. Res. 18 (6), 1067–1075. Vuong, Q.V., Golding, J.B., Nguyen, M., Roach, P.D., 2010. Extraction and isolation of catechins from tea. J. Sep. Sci. 33, 3415–3428. Wang, J., Li, H., Chen, Z., Liu, W., Chen, H., 2016. Characterization and storage properties of a new microencapsulation of tea polyphenols. Ind. Crop. Prod. 89, 152–156. Wang, L., Weller, C.L., 2006. Recent advances in extraction of nutraceuticals from plants. Trends Food Sci. Technol. 17, 300–312. White, D.J., de Klerk, S., Woods, W., Gondalia, S., Noonan, C., Scholey, A.B., 2016. Anti-stress, behavioural and magnetoencephalography effects of an L-theanine-based nutrient drink: a randomised, double-blind, placebo-controlled, crossover trial. Nutrients 8, 53. Williams, J., Kellett, J., Roach, P.D., McKune, A., Mellor, D., Thomas, J., Naumovski, N., 2016. L-Theanine as a functional food additive: Its role in disease prevention and health Promotion. Beverages 2, 13. Wren, R.C., Williamson, E.M., Evans, F.J., 1988. Forms of medicinal preparations. In: Walden, S. (Ed.), Potter’s New Cyclopedia of Botanical Dugs and Preparations. The C.W. Daniel Company Ltd., Essex, pp. 296–298. Yang, C., Du, W., Yang, D., 2016. Inhibition of green tea polyphenol EGCG ((−)-epigallocatechin-­ 3-gallate) on the proliferation of gastric cancer cells by sup-pressing canonical wnt/ß-catenin signalling pathway. Int. J. Food Sci. Nutr. 67 (7), 818–827. Yen, G.C., Chen, H.W., Duh, P.D., 1998. Extraction and identification of an antioxidative component from Jue Ming Zi (Cassia tora L.). J. Agric. Food Chem. 46, 820–824. Zainudin, M.A.M., Hamid, A.A., Anwar, F., Osman, A., Saari, N., 2014. Variation of bioactive compounds and antioxidant activity of carambola (Averrhoa carambola L.) fruit at different ripening stages. Sci. Hortic. 172, 325–331. Zaveri, N.T., 2006. Green tea and its polyphenolic catechins: medicinal uses in cancer and noncancer applications. Life Sci. 78, 2073–2080. Zeisel, S.H., 1999. Regulation of “Nutraceuticals”. Science 285, 1853–1855. Zeng, L., Zhou, Y., Fu, X., Mei, X., Cheng, S., Gui, J., Dong, F., Tang, J., Mae, S., Yang, Z., 2017. Does oolong tea (Camellia sinensis) made from a combination of leaf and stem smell more aromatic than leaf-onlytea? Contribution of the stem to oolong tea aroma. Food Chem. 237, 488–498.

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Zhang, C., Li-Chieh, S.C., Yang, C., Young Quek, S., 2018. Antioxidant capacity and major polyphenol composition of teas as affected by geographical location, plantation elevation and leaf grade. Food Chem. 244, 109–119. Zhao, J., Deng, J.W., Chen, Y.W., Li, S.P., 2013. Advanced phytochemical analysis of herbal tea in China. J. Chromatogr. A 1313, 02–23. Zheng, L., Ding, Z., Zhang, M., Sun, J., 2011. Microencapsulation of bayberry polyphenols by ethyl cellulose: preparation and characterization. J. Food Eng. 104, 89–95. Zhu, Z.Q., 2000. Supercritical Fluids Technology. Chemical Industry Press, Beijing.

Further Reading Ayala-Zavala, J.F., González-Aguilar, G.A., 2011. Use of additives to preserve the quality of fresh-cut fruits. In: Martín-Belloso, O., Soliva-Fortuny, R. (Eds.), Advances in Fresh-Cut Fruits and Vegetables Processing. CRC Press, Boca Raton, pp. 231–254. Saleh, I.G., Ali, Z., Abe, N., Wilson, F.D., Hamada, F.M., Abd-Ellah, M.F., Walker, L., Khan, I.A., Ashfaq, M.K., 2013. Effect of green tea and its polyphenols on mouse liver. Fitoterapia 90, 151–159.

NATURAL FERMENTED BEVERAGES

14

Reyhan Irkin Health Science Faculty, Nutrition and Dietetics Department, Izmir Democracy University, Izmir, Turkey

14.1 Introduction In recent years, consumers are demanding natural and fresh products with nutritional properties and attractive sensorial characteristics. The industry looks for market possibilities and tends to transfer their products by the preparation of novel foods with improved sensorial, nutritional, and functional criteria. In this view, the beverage sector is rapidly developed with the new ready-to-drink beverages which are based on fruits, vegetables, and milk (Andres et al., 2015). Healthconscious consumers indicate an increasing desire for functional beverages and foods that can improve well-being and reduce the potential of disease (Marsh et al., 2014). Consumption of sugar- and artificially sweetened beverages and fruit juices has increased among children, adolescents, and adults in the last few years. Increasing intake of sweetened beverages is also observed in consumers of the Mediterranean regions, although it stays lower than in other industrialized regions. Intake of >5 servings/wk of all the types of beverages is analyzed and the result showed an increased risk of metabolic syndrome (MetS) and middle-aged and elderly individuals are at a high risk of cardiovascular diseases (CVD). However, these associations [especially sugar sweetened beverages (SSBs) and bottled fruit juices] should be explained with caution because of their large consumption. Furthermore, it was reported that consumption of 1–5 servings of natural and bottled fruit juices/wk can reduce the risk of MetS (Ferreira-Pego et al., 2016). A functional food/beverage can be defined as an unmodified natural food/beverage; a food/beverage which is improved through special growing conditions or biotechnological means; a food/beverage to which a compound is added to provide benefits; a food/beverage from which a compound is removed by technological or biotechnological means so that the food/beverage provides benefits not otherwise available; Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00014-6 © 2019 Elsevier Inc. All rights reserved.

399

400  Chapter 14  Natural Fermented Beverages

a food/beverage in which a component is replaced by an alternative compound with desirable properties; a food in which a component has been modified by enzymatic, chemical, or technological means to provide a benefit; a food in which the bioavailability of a component has been modified; or a combination of any of the above (Corbo et al., 2014). Fermentation is a natural process bringing unique flavors and other benefits to consumer products in a 100% natural way. Natural approach is done using to turn a traditional production into a largescale process (Huhenholtz, 2013). Today we can give some examples to fermented natural beverages; Rela (Biogaia, Sweden), a fruit juice with L. reuteri MM53; Gefilus (Valio Ltd., Finland), a fruit drink with a 5-week shelf life under cold storage; Bioprofit (Valio Ltd.), with L. rhamnosus GG and Propionibacterium freudenreichii ssp. shermanii JS; and Biola (Tine BA, Norway), a juice drink with more than 95% fruit without sugar (Prado et al., 2008). In the study of Lodi et al. (2015), fermented milk (Batavito) (contains a combination of 3 probiotic bacteria; Lactobacillus acidophilus, Bifidobacterium sp., and Lactobacillus paracasei) can inhibit the amount of microorganisms in the oral cavity, which can cause mineral loss.

14.2  Fermented Dairy-Based Beverages Fermented milk products are processed and consumed since a long time in human history. Different starters including lactic acid bacteria (LAB) and other bacteria, yeasts, and molds can be used in fermentation (Alatossava et al., 2013). Various kinds of the bacteria, yeasts, and molds that are present in fermented foods and beverages are known probiotics and probably provide health benefits. The significance of the microorganisms are present in fermented food in maintaining human health is first noticed by Elie Metchnikoff (Nair et al., 2016).The production of fermented dairy products is increasing in all the developing countries of the world. The fermented milk products like ayran, kefir, koumiss, acidophilus milk, etc. are being manufactured in many countries. Fermented milks are consumed throughout the world for their aroma, nutritive values, and therapeutic properties (Ramod et al., 2017). Fermented beverages are basic products in the human diet and they have been consumed since many years. Fermented foods are defined as foods or beverages conducted with controlled microbial growth and enzymatic reactions of food compounds. Fermentation processes can be classified by the basic metabolites and microorganisms required: alcohol and carbon dioxide (yeast), acetic acid (Acetobacter), lactic acid (LAB associated to genera such as Lactobacillus, Leuconostoc, and Streptococcus), propionic acid (P. freudenreichii), and ammonia and fatty acids (Bacillus, molds). Raw materials that contain high levels of monosaccharides and disaccharides, or starch, are fermented by yeasts or LAB (Marco et al., 2017).

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Cow’s milk is generally used in the manufacture of fermented dairy products but goat’s milk may also has certain therapeutic and nutritional value, if compared to cows’ milk it has better digestibility and good immunological properties (Ranadheeraa et  al., 2016). The physicochemical property of fermented milk beverages obtained from goat’s milk, cow’s milk and a mixture of the two milks is affected by the kind of milk used and storage time. Increasing in acidity and a decrease in viscosity of the fermented dairy beverages during storage can change. Addition of fruit jelly, particularly guava jelly offers an opportunity to produce a dairy product with nutritional quality. Guava jelly can provide supportive changes in the rheological and sensory behaviors of the fermented dairy beverages, suggesting its potential use of total solids and/or stabilizers in the production of these products (Gomes et al., 2013). A variety of vitamins including vitamins D, E, and C and minerals calcium and magnesium can be used for fortification of fermented products to improve the growth of preschool children. Microorganisms can also perform functional metabolites, which are supported by the screening of ecological niches, such as marine environments, in addition to the previously mentioned gut derived probiotics, for novel nutraceuticals they can be incorporated into functional beverages (Marsh et al., 2014).

14.2.1 Kefir Kefir is from the Caucasus Mountains and contains white or yellow irregular granules of protein and a polysaccharide matrix, which is kefiran, produced by LAB. The symbiotic microflora in kefir depends on the source and geographic area. Kefir grains contain LAB such as Lactobacillus, Leuconostoc Lactococcus, Streptococcus, and yeasts (Kluyveromyces, Candida, and Saccharomyces). The bacteria and yeasts are found in kefiran matrix, which is a water-soluble branched glucogalactan (Puerari et  al., 2012). Some beneficial effects of kefir on health have reported in vivo studies. A study results show that the bacteria obtained from kefir is considered to have probiotic properties (Dogan and Ozpınar, 2017). The beneficial health properties of kefir are related with protein, vitamins, antioxidants, minerals, and many biogenic compounds. The health benefits of kefir are associated with antibacterial spectrum, anticarcinogenic effect, hypocholesterolemic effect, inhibition of gastrointestinal proliferation, β-galactosidase activity, antidiabetic properties, antimutagenic activity, scavenging activity, lactic acid content, balance effects on lipid and blood pressure level, protection against apoptosis, antiallergic properties, antiinflammatory action, bacterial colonization, and immune system booster (Ahmed et al., 2013a,b,c).

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Goat’s milk in the production of dairy products has important nutritional properties, such as the presence of organic and nitrogen matter (casein and albumin), minerals, and vitamins, as well as lactic ferments, which improve the digestion process and defense against intestinal pathogenic bacteria. Goat’s milk has some particular properties that confer technological advantages in comparison to cow’s milk, such as a smaller size of fat globules, which provides a smoother texture in derived products, lower amounts of as1-casein, resulting in softer gel products, a higher water holding capacity, and a lower viscosity. In the study of Songun (2015) some microbiological, chemical, and physical properties of 1% (w/v) and 2% (w/v) inulin added cow-goat milk’s kefir are determined (Fig. 14.1). The analyses are done at the storage days of 1, 4, 7, 14, 21, and 40. On the 40th day total logarithmic numbers of total mesophilic aerobic bacteria are 10.50–10.55, Lactobacillus sp. are 10.24–10.58, Lactococcus sp. are 10.25–10.58 and yeasts are 7.60–7.93 cfu/mL reported. Songun (2015) is found significantly (p˂0.05) different results for 1%, 2% (w/v) inulin added and control groups on the various storage days (Table 14.1). Kefir grains vary in size, from 0.3 to 3.0 cm in diameter, are characterized by an irregular, elastic, and a viscous firm texture. During fermentation, the grains increase in size and number of microorganism increase as well. Grains are recovered from the fermented milk and again utilized. If grains are carefully preserved, they can remain active for years (Leite et al., 2013). Cow:goat milks (1:1 v/v)

Pasteurized (85°C/ 10 min)

Cooled to 25°C and Kefir granules are added (2% w/v) + Inulin (Orafti HPX, Artisan) (1% and 2% w/v)

Fermentation at 25°C/18 h until (pH 4.6)

Kefir grains are separated

Kefir samples are stored 4°C/ 40 days

Fig. 14.1  Production of Cow-Goat Milks’ Kefir with inulin addition (Songun, 2015).

Chapter 14  Natural Fermented Beverages   403

Table 14.1  Lactobacillus sp. Numbers (log cfu/mL) of Goat-Cows Milk Kefir Produced with Different Ratios of İnulin Additions [1% (A) and 2% (B) w/v inulin] (Songun, 2015) Storage Period (days)  1.  4.  7. 14. 21. 40. ⁎

A (1 % w/v) ⁎

8.08 ± 0.36a  9.11 ± 0.34a,b 10.36 ± 0.26b 10.06 ± 0.33b,c 10.78 ± 0.16c 10.58 ± 0.25c

B (2 % w/v)

C (control)

8.99 ± 0.53a 9.10 ± 0.25a,b 10.46 ± 0.30b 10.20 ± 0.05b,c 11.17 ± 0.32c 10.24 ± 0.13b,c

8.55 ± 0.29a 9.12 ± 0.32a,b 10.30 ± 0.24b,c 10.21 ± 0.19b 10.36 ± 0.11b,c 10.57 ± 0.42c

Means ± SD within each row not sharing the same lowercase letter are statistically different (p 8 log cfu/mL) during 4 weeks of storage (Shori, 2016).

Chapter 14  Natural Fermented Beverages   413

Tursu juice is produced from a traditional fermented Turkish pickle made of vegetables such as cabbage, beet, pepper, cucumber, carrot, turnip, eggplant, and beans. It was reported that L. plantarum as a starter culture into the tursu developed taste and the healthy properties of the product. It is also stated that although P. pentosaceus, Lc. mesenteroides can be used for fermenting vegetables but L. plantarum is more adaptive microorganism, in addition to this property L. plantarum NCULI005 has conjugated linoleic acid-producing capacity, too (Irkin and Songun, 2012). In some researches, it is reported that in 95% of active individuals exercise-associated muscle cramps (EAMCs)have occurred during or after exercise. Although EAMCs are common, their reasons remain unknown. Consuming 1 mL/kg body mass of pickle juice (PJ) while in hypohydrated condition causes exercise-stimulated hypertonicity or hyperkalemia (Miller, 2014). Shalgam, a traditional red, sour, cloudy, and soft fermented beverage is produced by lactic acid fermentation of sourdough, bulgur flour, black carrot, salt, turnip, and water (Tanguler and Erten, 2013; Tanguler et al., 2017). In the study of Tanguler et al. (2015), the volatile compounds of shalgam obtained from different processes are defined. The aroma compounds of shalgams manufactured by traditional and direct processes with the addition of LAB cultures are studied. It is showed that volatile content of the shalgam samples increased with the addition of Lb. plantarum., Lb. plantarum, and Lb. buchneri are the most isolated bacteria in shalgam samples. Sensory tests of shalgam samples produced by using traditional method and the applying of starters have the highest scores (Swain et al., 2014). The main component of shalgam is black carrot, which is rich in anthocyanins. Commercially obtained shalgam juice is characterized by determining its chemical properties and antioxidant capacity by identifying its microflora. Researchers suggest that addition of (poly) phenolic compounds results in antioxidant, probiotic, and antiproliferative properties of shalgam juice (Ekinci et al., 2016; Altay et al., 2013). In Irkin (2018) research, during the fermentation stage 2% (v/v) dried artichoke leaves (DAL) filtrate and Bf. bifidum NRRL B41410 are added in one group of shalgam (BSDAL). Control shalgams marked as CS were also prepared and they do not contain Bf. bifidum NRRL B41410 and DAL filtrate. And one group of shalgams contained Bf. bifidum NRRL B41410 without DAL filtrate (BS). °Brix (%), pH values are reported for shalgams and their mean ranges are shown in Table 14.2. °Brix is a measure of all soluble solids coming from the natural vegetable components and acid. In the beginning of the fermentation shalgam samples have higher brix values but after the 7, 14, and 25 days of storage brix values decreased to about 1.4% and because of the

Table 14.2  Changes in Brix (%) and pH Values of Shalgams During 40 Storage Days (Irkin, 2018) Storage Period (days)  0.  1.  2.  7. 14. 25. 40.

CS

BS

BSDAL

pH

Brix

pH

Brix

pH

Brix

⁎

1.80 ± 0.6A 1.90 ± 0.5A 1.80 ± 0.3A 1.40 ± 0.4B 1.40 ± 0.3B 1.40 ± 0.4B 2.20 ± 0.5C

4.11 ± 1.0A 4.07 ± 1.1A 3.95 ± 0.5A 3.82 ± 0.9B 3.79 ± 0.5B 3.68 ± 0.7B 3.55 ± 1.0C

2.00 ± 0.3A 1.80 ± 0.5A 1.70 ± 0.5B 1.60 ± 0.6B 1.40 ± 0.3B 1.40 ± 0.4B 2.10 ± 0.7A

3.98 ± 0.7A 3.81 ± 1.1A 3.88 ± 0.5A 3.79 ± 0.9B 3.67 ± 0.8B 3.59 ± 0.2B 3.37 ± 1.0B

1.90 ± 0.5A 1.60 ± 0.4A 1.50 ± 0.5B 1.50 ± 0.3B 1.40 ± 0.8B 1.40 ± 0.5B 2.20 ± 0.3C

4.30 ± 1.2A 4.20 ± 1.1A 4.15 ± 1.3A 4.13 ± 1.7B 4.13 ± 0.5B 4.10 ± 0.8B 3.65 ± 0.3C

A–B Means in the same column with different letter differ significantly at (p