Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products 3030913805, 9783030913809

Citation preview

Reference Series in Phytochemistry Series Editors: J.-M. Mérillon · K. G. Ramawat

Mohamed Fawzy Ramadan Hassanien Editor

Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products

Reference Series in Phytochemistry Series Editors Jean-Michel Mérillon, Faculty of Pharmaceutical Sciences, Institute of Vine and Wine Sciences, University of Bordeaux, Villenave d’Ornon, France Kishan Gopal Ramawat, Department of Botany, University College of Science, M. L. Sukhadia University, Udaipur, Rajasthan, India

This series provides a platform for essential information on plant metabolites and phytochemicals, their chemistry, properties, applications, and methods. By the strictest definition, phytochemicals are chemicals derived from plants. However, the term is often also used to describe the large number of secondary metabolic compounds found in and derived from plants. These metabolites exhibit a number of nutritional and protective functions for human wellbeing and are used e.g. as colorants, fragrances and flavorings, amino acids, pharmaceuticals, hormones, vitamins and agrochemicals. The series offers extensive information on various topics and aspects of phytochemicals, including their potential use in natural medicine, their ecological role, role as chemo-preventers and, in the context of plant defense, their importance for pathogen adaptation and disease resistance. The respective volumes also provide information on methods, e.g. for metabolomics, genetic engineering of pathways, molecular farming, and obtaining metabolites from lower organisms and marine organisms besides higher plants. Accordingly, they will be of great interest to readers in various fields, from chemistry, biology and biotechnology, to pharmacognosy, pharmacology, botany and medicine. The Reference Series in Phytochemistry is indexed in Scopus.

Mohamed Fawzy Ramadan Hassanien Editor

Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products With 104 Figures and 130 Tables

Editor Mohamed Fawzy Ramadan Hassanien Department of Clinical Nutrition Faculty of Applied Medical Sciences Umm Al-Qura University Makkah, Saudi Arabia

ISSN 2511-834X ISSN 2511-8358 (electronic) Reference Series in Phytochemistry ISBN 978-3-030-91380-9 ISBN 978-3-030-91381-6 (eBook) https://doi.org/10.1007/978-3-030-91381-6 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG. The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Dedicated to the soul of my father, Fawzy Ramadan Hassanien, Professor of Food Science and former Vice Dean of the Faculty of Agriculture, Zagazig Univeristy, Egypt

Preface

Improving waste management is one of the cornerstones to ensuring the industry’s economic, social, and environmental sustainability. For their oils and fats, many oilseeds, vegetables, and fruits are cultivated, wherein the waste (meal or cake) produced by the oil extraction business is about 350 million tons of oil meal produced per year. In the European Union, there are around 35 million tons of by-products from oilseeds processing. Additionally, the waste produced during the manufacture of olive oil amounts to around 30 million m3 annually. By-products from manufacturing vegetable oil and oilseeds are rich in lipophilic and hydrophilic phytochemicals. Additionally, the by-products of the manufacturing of vegetable oil and oilseeds contain 1–2% residual oil. From an economic and environmental standpoint, it would be advantageous to valorize this waste appropriately. The idea of a Zero Waste Economy, in which waste is transformed into valuable products and finds practical applications by providing potential energy savings, may be used to inform the valuation of vegetable oil and oilseed processing by-products. A variety of phytochemicals, such as phenolics, carotenoids, pigments, tocols, and vitamins, might be utilized to enhance the quality of food rich in lipids. A functional food designation might also be given to the bioactive-enriched goods due to their excellent nutritional value and quality. In addition to potentially prolonging the shelf life of various goods (including food, cosmetics, and pharmaceuticals), phytochemicals generated from edible oil industry by-products may also offer additional benefits due to their antioxidant and antibacterial capabilities. Studies demonstrated bioactive phytoconstituents’ recovery and composition from oil processing by-products. Soybean (Glycine max) cake contains glycosides, isoflavone aglycones, and phenolic acids, contributing to its antioxidant potential. Sunflower (Helianthus annuus) seeds and leaf extracts are also rich in phenolics. The major phenolics in the rapeseed (Brassica napus) cakes are sinapine and sinapic acid. Sesame (Sesamum indicum) meal is valorized to compensate for synthetic antioxidants. Palm (Elaeis guineensis) kernel is rich in biophenols with healthpromoting traits. Flax (Linum usitatissimum) cake extract showed antioxidant and antibacterial effects in food and cosmetic products. Olive (Olea europaea) leaves are rich in oleuropein, having a health-promoting impact. Olive pomace is rich in tyrosol, verbascoside, hydroxytyrosol, rutin, catechol, and phenolic acids. Besides,

vii

viii

Preface

olive mill wastewater is a source of polar phytochemicals with several biological traits. Conditions for processing and extraction impact the by-products produced during oil manufacturing. Heat is needed for physical oil extraction, whereas solvent extraction might be hazardous. Pre-treatment technologies are crucial to replace conventional methods and more effective procedures. Some oils are refined after crude oil extraction to remove unwanted components (e.g., mono-acylglycerols, phospholipids, di-acylglycerols, free fatty acids, and pigments). Because active phytoconstituents, like vitamins and antioxidants, may also be removed during this procedure, the resulting oils are of poor quality. Oil production bio-wastes are a rich source of phenolics, sterols, carotenoids, tocols, fatty acids, and proteins that are valuable for their technological functions (such as coloring and texturing), nutritional qualities, or benefits to human or animal health. In order to employ these chemicals as ingredients, it is necessary to remove them using methods that do not impair their effectiveness. Due to variations in the crop, the timing of the harvest, and the oil extraction techniques, the chemical composition of by-products of oil processing varies. Green solvent extraction under high pressure has been the subject of recent research. On the other hand, the by-products of the oil production process are often roasted, crushed, and utilized as fertilizers or animal feed. There have also been reports of cooking oil being contaminated with used cooking oil reprocessed. Waste cooking oils have been converted into biodiesel by chemical processes. This book aims to establish a multidisciplinary discussion forum on the phytochemistry, functional properties, and health-promoting effects of bioactive compounds in oil processing by-products, as well as the applications of oil processing by-products in both food and non-food contexts. The scientific underpinnings of the uses and health-promoting advantages of oil refinery by-products revealed. In addition, the book goes through pertinent recovery-related concerns and various methods for creating new applications. The work is a valuable contribution to the scientists and researchers researching the recycling of agro-industrial wastes resulting from by-products of the production of vegetable oil and oilseeds. Furthermore, food scientists, technicians, chemists, nutritionists, and pharmacists will find this book helpful in creating novel medications and food products. With a focus on the connection between age-associated diseases and the health-improving effects of the active phytochemicals in the aforementioned bio-wastes, the authors of this book contribute the functional characteristics of active phytoconstituents from edible oil and oilseed industrial bio-wastes that may be responsible for health-enhancing effects. The book contains several chapters that cover the following topics: 1. Economic values of bio-waste from oil processing 2. Chemical profile and bioactive compounds of extracts from oil processing by-products 3. Biological and functional traits of extracts and bioactive compounds from oil processing by-products

Preface

ix

4. Food and non-food applications of extracts and bioactive compounds from oil processing by-products 5. Valorization of oil processing by-products for non-health purposes, i.e., source of bioenergy The editor would like to thank all contributors for their valuable work and collaboration during the book’s production. In addition, the Springer staff’s help and support, especially Sylvia Blago, Sofia Costa, and Veronika Mang, was essential for completing the task and is appreciated. Makkah, Saudi Arabia March 2023

Prof. Mohamed Fawzy Ramadan Hassanien

Contents

Part I 1

General Aspects

....................................

1

Introduction to Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . Mohamed Fawzy Ramadan Hassanien

3

Part II Phytochemicals from Common Vegetable Oil and Oilseed Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3

4

5

6

11

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Onur Ketenoglu, Sündüz Sezer Kiralan, and Mustafa Kiralan

13

Bioactive Phytochemicals from Rapeseed (Brassica napus) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Parisa Jafarian Asl and Razieh Niazmand

27

Bioactive Phytochemicals from Sunflower (Helianthus annuus L.) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mariana Buranelo Egea, Josemar Gonçalves de Oliveira Filho, Mirella Romanelli Vicente Bertolo, Jamile Castelo de Araújo, Gabrielle Victoria Gautério, and Ailton Cesar Lemes

49

Bioactive Phytochemicals from Rice Bran Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sook Chin Chew and Suk Kuan Teng

65

Bioactive Phytochemicals from Peanut Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Seok Shin Tan, Chin Xuan Tan, and Seok Tyug Tan

105

xi

xii

7

8

9

Contents

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tainara Leal de Sousa, Josemar Gonçalves de Oliveira Filho, Mirella Romanelli Vicente Bertolo, Gabrielle Victoria Gautério, Giovana Maria Navarro de Mendonça, Ailton Cesar Lemes, and Mariana Buranelo Egea Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . Josemar Gonçalves de Oliveira Filho, Mirella Romanelli Vicente Bertolo, Gabrielle Victoria Gautério, Giovana Maria Navarro de Mendonça, Ailton Cesar Lemes, and Mariana Buranelo Egea Bioactive Phytochemicals from Sesame Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Reham Hassan Mekky, Mostafa M. Hegazy, María de la Luz Cádiz-Gurrea, Álvaro Fernández-Ochoa, and Antonio Segura Carretero

Part III Phytochemicals from Fruit Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

11

12

13

14

15

117

139

155

195

Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Amélia Delgado, Nadia Chammem, Manel Issaoui, and Emna Ammar

197

Bioactive Phytochemicals from Palm Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hamide Filiz Ayyildiz, Hadia Shoaib, and Hüseyin Kara

235

Bioactive Phytochemicals from Citrus Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Şelale Öncü Glaue and Tolga Akcan

269

Bioactive Phytochemicals from Grape Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Massimo Lucarini, Alessandra Durazzo, Vita Di Stefano, Gabriella Di Lena, Ginevra Lombardi-Boccia, and Antonello Santini

289

Bioactive Phytochemicals from Coconut (Cocos nucifera) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Veysel Umut Celenk, Zinar Pinar Gumus, and Zeliha Ustun Argon

309

Bioactive Phytochemicals from Pumpkin Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Leila Rezig, Karima Gharsallah, and Moncef Chouaibi

323

Contents

16

17

18

19

20

Bioactive Phytochemicals from Cactus (Opuntia) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . M. N. Zourgui, S. Ben Lataief, M. Ben Dhifi, A. Agil, and L. Zourgui

377

Bioactive Phytochemicals from Papaya Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chin Xuan Tan, Seok Tyug Tan, and Seok Shin Tan

391

Bioactive Phytochemicals from Avocado Oil Processing By-Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Alicia P. Cárdenas-Castro, Álvaro Fernández-Ochoa, María de la Luz Cádiz-Gurrea, Antonio Segura Carretero, and Sonia G. Sáyago-Ayerdi Bioactive Phytochemicals from Berries Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ivanka Ćirić, Milica Sredojević, Dragana Dabić Zagorac, Milica Fotirić-Akšić, Mekjell Meland, and Maja Natić Bioactive Phytochemicals from Date Palm (Phoenix dactylifera L.) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . Sudheer Narasimha Wudali, Akshatha Banadka, Praveen Nagella, and Jameel M. Al-Khayri

Part IV Phytochemicals from Non-traditional Vegetable Oil and Oilseed Processing By-products . . . . . . . . . . . . . . . . . . . . . . 21

22

23

24

25

xiii

403

431

455

483

Bioactive Phytochemicals from Jatropha (Jatropha curcas L.) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mohamed Fawzy Ramadan Hassanien

485

Bioactive Phytochemicals from Cumin (C. cyminum) and Caraway (C. carvi) Oil Processing By-products . . . . . . . . . . . . . . . Matin Soleimanifar and Razieh Niazmand

505

Bioactive Phytochemicals from Tiger Nut Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mustafa Kiralan, Onur Ketenoglu, and Sündüz Sezer Kiralan

527

Bioactive Phytochemicals from Walnut (Juglans spp.) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Biljana Rabrenović, Maja Natić, Dragana Dabić Zagorac, Mekjell Meland, and Milica Fotirić Akšić Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Asad Nawaz and Ibrahim Khalifa

537

559

xiv

26

27

28

29

30

31

32

33

34

Contents

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Onur Özdikicierler and Burcu Öztürk-Kerimoğlu Bioactive Phytochemicals from Almond (Prunus dulcis) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hüseyin Kara, Hamide Filiz Ayyildiz, İsmail Tarhan, Fatih Erci, and M. Raşit Bakır Bioactive Phytochemicals from Nigella sativa Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Zeliha Ustun Argon, Zinar Pinar Gumus, Veysel Umut Celenk, and Mohamed Fawzy Ramadan Hassanien Bioactive Phytochemicals from Chia (Salvia hispanica) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . Oscar Abel Sánchez-Velázquez, Martin Mondor, Maira Rubí Segura-Campos, Nidia del Carmen Quintal-Bojórquez, and Alan Javier Hernández-Álvarez Bioactive Phytochemicals from Hemp (Cannabis sativa) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Zinar Pinar Gumus, Zeliha Ustun Argon, Veysel Umut Celenk, and Hasan Ertas

577

595

621

643

669

Bioactive Phytochemicals from Moringa (M. oleifera) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . Mohanish N. Bokhad and Umesh B. Jagtap

685

Bioactive Phytochemicals from Castor (Ricinus communis Linneo) Seed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . Natascha Cheikhyoussef and Ahmad Cheikhyoussef

703

Bioactive Phytochemicals from Evening Primrose (Oenothera biennis) Oil Processing By-products . . . . . . . . . . . . . . . Alessandra Durazzo, Massimo Lucarini, Gabriella Di Lena, Ginevra Lombardi-Boccia, and Antonello Santini

723

Bioactive Phytochemicals from Acorn (Quercus spp.) Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Onur Özdikicierler and Tolga Akcan

739

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

753

About the Editor

Mohamed Fawzy Ramadan Hassanien is a Food Chemistry Professor at the Department of Clinical Nutrition, Faculty of Applied Medical Sciences at Umm Al-Qura University, Makkah, Saudi Arabia. Prof. Ramadan obtained his Ph.D. (Dr. rer. nat.) in Food Chemistry from Berlin University of Technology (Germany, 2004). Prof. Ramadan continued his post-doctoral research in ranked universities such as University of Helsinki (Finland), Max-Rubner Institute (Germany), Berlin University of Technology, and University of Maryland (USA). In 2012, he was appointed to be visiting Professor (100% teaching) in the School of Biomedicine, Far Eastern Federal University in Vladivostok, Russian Federation. Prof. Ramadan published more than 300 research papers and reviews in international peer-reviewed journals. In addition, he edited and published several books and book chapters (Scopus h-index is 45 and more than 7000 citations in Scopus). In addition, he was an invited speaker at several international conferences. Since 2003, Prof. Ramadan is a reviewer and editor in several highly cited international journals, such as the Journal of Umm Al-Qura University for Medical Sciences, Journal of Medicinal Food, and Journal of Advanced Research. Prof. Ramadan received several prizes, including Abdul Hamid Shoman Prize for Arab Researcher in Agricultural Sciences (2006), the Egyptian State Prize for Encouragement in Agricultural Sciences (2009), European Young Lipid Scientist Award (2009), AU-TWAS Young Scientist National Awards (Egypt) in Basic Sciences, Technology and Innovation (2012), TWAS-ARO Young Arab Scientist (YAS) Prize in Scientific and Technological Achievement (2013), and Atta-ur-Rahman Prize in Chemistry (2014). xv

Editorial Board

Bharat B. Aggarwal Inflammation Research Center, San Diego, CA, USA Halina Maria Ekiert Department of Pharmaceutical Botany, Jagiellonian University, Medical College, Kraków, Poland Sumita Jha Department of Botany, University of Calcutta, Kolkata, West Bengal, India Atanas I. Pavlov University of Food Technologies, Plovdiv, Bulgaria Céline Riviere Joint Res. Unit BioEcoAgro (UMRt 1158), University of Lille, Lille Cedex, France Pierre Waffo-Téguo UFR des Sciences Pharmaceutiques, University of Bordeaux, Villenave d’Ornon, Gironde, France Michael Wink Institute for Pharmacy & Molecular Biotechnology (IPMB), Heidelberg University, Heidelberg, Germany

xvii

Contributors

A. Agil Department of Pharmacology and Biohealth and Neurosciences Institutes, Faculty of Medicine, University of Granada, Granada, Spain Tolga Akcan Dokuz Eylül University, Efes Vocational School, İzmir, Turkey Jameel M. Al-Khayri Department of Agricultural Biotechnology, College of Agriculture and Food Sciences, King Faisal University, Al-Ahsa, Saudi Arabia Emna Ammar Laboratory of Environmental Sciences and Sustainable Development (LASED), University of Sfax, National Engineering School of Sfax, Sfax, Tunisia Hamide Filiz Ayyildiz Faculty of Pharmacy, Department of Basic Pharmacy Sciences, Selçuk University, Konya, Turkey M. Raşit Bakır Faculty of Pharmacy, Department of Basic Pharmacy Sciences, Selçuk University, Konya, Turkey Akshatha Banadka Department of Life Sciences, CHRIST (Deemed to be University), Bangalore, Karnataka, India M. Ben Dhifi Research Lab BMA “Biodiversity, Molecules, Application”, Higher Institute of Applied Biology of Medenine, University of Gabes, Medenine, Tunisia S. Ben Lataief Research Lab BMA “Biodiversity, Molecules, Application”, Higher Institute of Applied Biology of Medenine, University of Gabes, Medenine, Tunisia Mirella Romanelli Vicente Bertolo São Carlos Institute of Chemistry (IQSC), University of São Paulo (USP), São Carlos, SP, Brazil Mohanish N. Bokhad Department of Botany, Government Vidarbha Institute of Science and Humanities, Amravati, Amravati, India Jamile Castelo de Araújo Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, GO, Brazil

xix

xx

Contributors

María de la Luz Cádiz-Gurrea Research and Development Functional Food Centre (CIDAF), Bioregión Building, Health Science Technological Park, Granada, Spain Analytical Chemistry Department, Faculty of Sciences, University of Granada, Granada, Spain Alicia P. Cárdenas-Castro Tecnológico Nacional de México/Instituto Tecnológico de Tepic, Laboratorio Integral de Investigación en Alimentos, División de Estudios de Posgrado, Tepic, Nayarit, Mexico Veysel Umut Celenk Eurofins Izmir Food and Feed Testing Laboratory, Bornova/ Izmir, Turkey Nadia Chammem Laboratoire d’Ecologie et de Technologie Microbienne, University of Carthage, Institut National des Sciences Appliquées et de Technologie (INSAT), Tunis, Tunisia Ahmad Cheikhyoussef Science and Technology Division, Multidisciplinary Research Centre, University of Namibia, Windhoek, Namibia Natascha Cheikhyoussef Ministry of Higher Education, Technology and Innovation, Windhoek, Namibia Sook Chin Chew Xiamen University Malaysia Campus, Selangor, Malaysia Moncef Chouaibi Research unit ‘Bio-preservation and valorization of agricultural products UR13-AGR 02’, High Institute of Food Industries, University of Carthage, Tunis, Tunisia High Institute of Food Industries, University of Carthage, Tunis, Tunisia Ivanka Ćirić Innovative Centre Faculty of Chemistry Belgrade, University of Belgrade, Belgrade, Serbia Dragana Dabić Zagorac Innovative Centre Faculty of Chemistry Belgrade, University of Belgrade, Belgrade, Serbia Giovana Maria Navarro de Mendonça School of Pharmaceutical Sciences, São Paulo State University (UNESP), Araraquara, Brazil Josemar Gonçalves de Oliveira Filho School of Pharmaceutical Sciences, São Paulo State University (UNESP), Araraquara, SP, Brazil Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, Brazil Tainara Leal de Sousa Institute of Tropical Pathology and Public Health, IPTSP – UFG, Goiás Federal University (UFG), Goiânia, Brazil Amélia Delgado Mediterranean Institute for Agriculture, Environment and Development (MED), University of Algarve Edf 8, Faro, Portugal Nidia del Carmen Quintal-Bojórquez Facultad de Ingeniería Química, Universidad Autónoma de Yucatán, Mérida, Mexico

Contributors

xxi

Gabriella Di Lena CREA-Research Centre for Food and Nutrition, Rome, Italy Vita Di Stefano Dipartimento Scienze e Tecnologie Biologiche Chimiche e Farmaceutiche, Università degli Studi di Palermo, Palermo, Italy Alessandra Durazzo CREA-Research Centre for Food and Nutrition, Rome, Italy Mariana Buranelo Egea Institute of Tropical Pathology and Public Health, IPTSP – UFG, Goiás Federal University (UFG), Goiânia, Brazil Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, GO, Brazil Fatih Erci Faculty of Science, Department of Biotechnology, Necmettin Erbakan University, Konya, Turkey Hasan Ertas Department of Chemistry, Faculty of Science, Ege University, Bornova/Izmir, Turkey Álvaro Fernández-Ochoa Analytical Chemistry Department, Faculty of Sciences, University of Granada, Granada, Spain Max Delbrück Center for Molecular Medicine in the Helmholtz Association, Berlin, Germany Berlin Institute of Health Metabolomics Platform, Berlin, Germany Milica Fotirić-Akšić Faculty of Agriculture, University of Belgrade, Belgrade, Serbia Gabrielle Victoria Gautério School of Chemistry, Department of Biochemical Engineering, Federal University of Rio de Janeiro (UFRJ), Rio de Janeiro, RJ, Brazil Karima Gharsallah Physics laboratory of Soft Matter and Electromagnetic Modeling, LR99ES16, Faculty of Science of Tunis, Tunis El Manar University, Tunis, Tunisia Process engineering department, Higher Institute of Technological Studies of Zaghouan, General Direction of Technological Studies, Tunis, Tunisia Zinar Pinar Gumus Central Research Testing and Analysis Laboratory Research and Application Center, EGE-MATAL, Ege University, Izmir, Turkey Mostafa M. Hegazy Department of Pharmacognosy, Faculty of Pharmacy, AlAzhar University, Nasr City, Cairo, Egypt Alan Javier Hernández-Álvarez School of Food Science and Nutrition, University of Leeds, Leeds, UK Manel Issaoui Lab-NAFS ‘Nutrition – Functional Food & Vascular Health’, Faculty of Medicine, University of Monastir, Monastir, Tunisia Parisa Jafarian Asl Department of Food Chemistry, Research Institute of Food Science and Technology (RIFST), Mashhad, Iran

xxii

Contributors

Umesh B. Jagtap Department of Botany, Rajaram College, Kolhapur, Kolhapur, India Hüseyin Kara Faculty of Science, Department of Chemistry, Selçuk University, Konya, Turkey Onur Ketenoglu Department of Food Engineering, Faculty of Agriculture, Eskisehir Osmangazi University, Eskisehir, Turkey Ibrahim Khalifa Food Technology Department, Faculty of Agriculture, Benha University, Moshtohor, Egypt Sündüz Sezer Kiralan Department of Food Engineering, Faculty of Engineering, Balikesir University, Balikesir, Turkey Mustafa Kiralan Department of Food Engineering, Faculty of Engineering, Balikesir University, Balikesir, Turkey Ailton Cesar Lemes School of Chemistry, Department of Biochemical Engineering, Federal University of Rio de Janeiro (UFRJ), Rio de Janeiro, RJ, Brazil Ginevra Lombardi-Boccia CREA-Research Centre for Food and Nutrition, Rome, Italy Massimo Lucarini CREA-Research Centre for Food and Nutrition, Rome, Italy Reham Hassan Mekky Department of Pharmacognosy, Faculty of Pharmacy, Egyptian Russian University, Badr City, Cairo, Egypt Research and Development Functional Food Centre (CIDAF), Bioregión Building, Health Science Technological Park, Granada, Spain Mekjell Meland Norwegian Ullensvang, Lofthus, Norway

Institute

of

Bioeconomy

Research-NIBIO

Martin Mondor Agriculture and Agri-Food Canada, Saint-Hyacinthe, QC, Canada Institute of Nutrition and Functional Foods (INAF), Université Laval, Quebec City, QC, Canada Praveen Nagella Department of Life Sciences, CHRIST (Deemed to be University), Bangalore, Karnataka, India Maja Natić Faculty of Chemistry, University of Belgrade, Belgrade, Serbia Asad Nawaz Jiangsu Key Laboratory of Crop Genetics and Physiology, Key Laboratory of Plant Functional Genomics of the Ministry of Education, College of Agriculture, Yangzhou University, Yangzhou, People’s Republic of China Razieh Niazmand Department of Food Chemistry, Research Institute of Food Science and Technology (RIFST), Mashhad, Iran Şelale Öncü Glaue Department of Food Processing, Efes Vocational School, Dokuz Eylül University, Izmir, Turkey

Contributors

xxiii

Onur Özdikicierler Faculty of Engineering, Food Engineering Department, Ege University, Bornova/Izmir, Turkey Burcu Öztürk-Kerimoğlu Faculty of Engineering, Food Engineering Department, Ege University, Bornova/Izmir, Turkey Biljana Rabrenović University of Belgrade – Faculty of Agriculture, BelgradeZemun, Serbia Mohamed Fawzy Ramadan Hassanien Department of Clinical Nutrition, Faculty of Applied Medical Sciences, Umm Al-Qura University, Makkah, Saudi Arabia Leila Rezig National Institute of Applied Sciences and Technology, LR11ES26, ‘Laboratory of Protein Engineering and Bioactive Molecules’, University of Carthage, Tunis, Tunisia High Institute of Food Industries, University of Carthage, Tunis, Tunisia Oscar Abel Sánchez-Velázquez Facultad de Ciencias Químico-Biológicas, Universidad Autónoma de Sinaloa, Culiacán, Mexico Sonia G. Sáyago-Ayerdi Tecnológico Nacional de México/Instituto Tecnológico de Tepic, Laboratorio Integral de Investigación en Alimentos, División de Estudios de Posgrado, Tepic, Nayarit, Mexico Antonello Santini Department of Pharmacy, University of Napoli Federico II, Naples, Italy Antonio Segura Carretero Research and Development Functional Food Centre (CIDAF), Health Science Technological Park, Granada, Spain Analytical Chemistry Department, Faculty of Sciences, University of Granada, Granada, Spain Maira Rubí Segura-Campos Facultad de Ingeniería Química, Universidad Autónoma de Yucatán, Mérida, Mexico Hadia Shoaib National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, Pakistan Matin Soleimanifar Department of Food Science and Technology, Damghan Branch, Islamic Azad University, Damghan, Iran Milica Sredojević Innovative Centre Faculty of Chemistry Belgrade, University of Belgrade, Belgrade, Serbia Chin Xuan Tan Department of Allied Health Sciences, Faculty of Science, Universiti Tunku Abdul Rahman, Kampar, Perak, Malaysia Seok Shin Tan Jeffrey Cheah School of Medicine and Health Sciences, Monash University Malaysia, Bandar Sunway, Selangor, Malaysia Department of Nutrition and Dietetics, School of Health Sciences, International Medical University, Kuala Lumpur, Malaysia

xxiv

Contributors

Seok Tyug Tan Department of Healthcare Professional, Faculty of Health and Life Sciences, Management and Science University, Shah Alam, Selangor, Malaysia İsmail Tarhan Faculty of Science, Department of Biochemistry, Selçuk University, Konya, Turkey Suk Kuan Teng Xiamen University Malaysia Campus, Selangor, Malaysia Zeliha Ustun Argon Department of Biosystems Engineering, Eregli Faculty Agriculture, Necmettin Erbakan University, Konya, Turkey Medical and Cosmetic Plants Application and Research Center, Necmettin Erbakan University, Konya, Turkey Sudheer Narasimha Wudali Department of Life Sciences, CHRIST (Deemed to be University), Bangalore, Karnataka, India L. Zourgui Research Lab BMA “Biodiversity, Molecules, Application”, Higher Institute of Applied Biology of Medenine, University of Gabes, Medenine, Tunisia M. N. Zourgui Research Lab BMA “Biodiversity, Molecules, Application”, Higher Institute of Applied Biology of Medenine, University of Gabes, Medenine, Tunisia

Part I General Aspects

1

Introduction to Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products Mohamed Fawzy Ramadan Hassanien

Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 By-products from Vegetable Oil and Oilseed Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 UNSDGs and Sustainable Food Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Bioactive Markers in Vegetable Oil and Oilseed Processing By-products . . . . . . . . . . . . . . . . . . . 5 Expected Outputs and Potential Impacts on the Environment and Economy . . . . . . . . . . . . . . . . 6 Features and Goals of the Book . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4 6 6 7 8 8 9

Abstract

Traditional edible oil mills are complicated plants processing fruits or seeds to high-quality vegetable oils and fats with functional traits. Almost all biowastes and by-products from edible oil and oilseed processing are utilized. However, most of the ingredients and active phytochemicals in the biowaste from edible oil and oilseed processing are used only in low-price applications (i.e., animal feeding). Recently, there has been a global consumer’s interest in the healthenhancing impacts of agricultural by-products. Focusing on the relation between age-associated diseases and the health-enhancing impacts of the active phytochemicals in the biowaste from edible oil and oilseed processing, the authors of this book contribute the functional traits of active phytoconstituents from edible oil and oilseed industrial biowastes that might be responsible for healthenhancing impacts. This handbook describes the state-of-the-art healthenhancing benefits of phytoconstituents from vegetable oil and oilseed processing by-products, the characterization of active chemicals in edible oil, and oilseed industrial biowastes with a particular interest in antioxidants to develop novel M. F. Ramadan Hassanien (*) Department of Clinical Nutrition, Faculty of Applied Medical Sciences, Umm Al-Qura University, Makkah, Saudi Arabia e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_1

3

4

M. F. Ramadan Hassanien

food and nonfood kinds of stuff. As a consequence of the outcomes of this scientific book: (1) the health-enhancing impacts and applications of phytoconstituents from edible oil and oilseed production biowastes will be discussed, (2) the consumer will understand the health-enhancing impacts of phytoconstituents from edible oil and oilseed production biowastes supported by scientific evidence, (3) the chapters review the recovery methods and unique techniques to develop novel applications from phytoconstituents from edible oil and oilseed production biowastes, and (4) the economy will be enriched by the integration of active chemicals from edible oil and oilseed processing biowastes to industrial applications (novel food items, pharmaceuticals, livestock, and cosmetics). Keywords

Biowaste · Circular economy · Environment · Food technology · Novel food · Phytochemistry · Recycling · Sustainable Development Goals · Waste valorization

1

Introduction

The circular economy tries to turn items into reusable materials for additional useful applications at the end of their lifecycle, with two essential outcomes: resource maximization and by-product minimization. The management of agro-industrial by-products addresses agricultural challenges such as bio-economy and industrialization sustainability [1–4]. Meanwhile, the European Commission (EC) aspired to move toward a circular economy. In response to the announcement of the Green Deal, a goal to make Europe carbon neutral by 2050, companies predicted that biowaste and its negative environmental impacts would be minimized in the future. In addition, the “Farm to Fork” strategy tries to apply circular economy models to make food processing effectively sustainable [5]. Edible oils and fats could be divided into fruit and seed oils and fats. Fruit oils are palm oil, olive oil, and avocado oil [6]. The world’s most essential seed oils are sunflower, peanut, soybean, rapeseed, cottonseed, and palm kernel oils. Besides, flax, hemp, safflower, grape seed, and other oils are produced at more minor levels [4, 7]. Figure 1 presents the world’s fruit and seed oils and fats production. The total food biowaste at the production stages was ca. 30.5 million tons annually, as estimated by Caldeira et al. [8] using the mass flow analyses. At the processing stages, Fig. 2 presents the estimated contribution of food’s top five subsectors. Because different food items are wasted in significant quantities at the processing stages, it is critical to figure out which biowaste should be prioritized for valorization [5]. Traditional edible oil and oilseed processing plants process oilseeds and fruits into high-quality oils and fats with unique traits. Almost all processing biowastes are

Introduction to Bioactive Phytochemicals from Vegetable Oil and. . .

1

5

World production (million tons/year) 60

56

50 43

40 30 20

25 14

10

6

5

4

3

2.93

2.85

0.87

0.68

0.6

0

Fig. 1 World production of fruit and seed oils and fats [7]

Dairy

4%

Cereal grains

8%

Meat, fish & poultry

20%

Oil crops

33%

Fruits, vegetables & tubers 0%

35%

5%

10% 15% 20% 25% 30% 35% 40%

Fig. 2 Food biowaste estimated per subsector at the processing stages [8]

utilized: phospholipids as a food additive, free fatty acids (FFA) in chemistry, cake or meal as protein-rich animal feed, deodorizer distillates in the biodiesel industry, or to recover active phytoconstituents such as sterols and carotenoids [4, 7].

6

2

M. F. Ramadan Hassanien

By-products from Vegetable Oil and Oilseed Processing

Ensuring the industry’s economic, environmental, and social sustainability is essential to improving waste management. Different vegetables, oilseeds, and fruits are cultivated for their fats and oils, whereas oil processing produces considerable biowastes (cake or meal). The amounts of oil cake or meal reached approximately 351 million tons annually [9]. In the European Union (EU), oilseed biowastes comprise about 35 million tons. Besides, biowastes recovered during olive oil processing are approximately 30 million m3 annually [10–13]. Fats and oils obtained from the germs, fruits, and seeds of soybean, sesame, olive, camellia, rapeseed, palm, and coconut generate high amounts of by-products. At the EU level in 2019, sunflower, rapeseed, and soybean represented the highly cultivated oilseeds. The EU-27 reported a yield of 28,433 thousand tons of oilseeds, wherein Romania was the greatest producer of sunflower, comprising about 35% of total EU production of sunflower [14–18]. Edible oil and oilseed processing biowastes are rich in lipophilic and hydrophilic nutrients and phytochemicals. Besides, the vegetable oil and oilseed processing by-products contain ca. 1–2% residual oils. If those biowastes are adequately valorized, they might be useful for environmental and economic issues. The notion of a “Zero Trash Economy” in which waste is turned into valuable goods and finds new applications can be applied to edible oil and oilseed manufacturing by-products. Phytochemicals including phenolics, sterols, carotenoids, pigments, tocols, vitamins, and phyto-extracts could improve the quality of lipid-containing foodstuffs. Besides, the bioactive-enriched products might be accepted as functional food since their nutritional value and quality are unique. Furthermore, phytochemicals derived from the edible oil and oilseed processing by-products could play a key role in extending the shelf life of different products (i.e., foodstuffs, cosmetics, and pharmaceuticals) and providing value-added effects with their functional and antioxidative traits [10–13].

3

UNSDGs and Sustainable Food Production

Biowaste disposal is complicated by legal constraints imposed by by-products’ adverse environmental effects. However, because the recovery of these bioactive substances could be economically valuable, employing those biowastes to make edible additives or supplements with nutritional value has piqued attention. The 2030 Agenda for Sustainable Development Goals (SDGs) reflects global attention on the issue of food biowaste (https://sustainabledevelopment.un.org). The SDG target 12.3 aims to halve global food biowaste per capita and reduce food biowaste along the processing and supply chains [15–17]. A significant link between people and a sustainable circular economy in the food sector is the value-added

1

Introduction to Bioactive Phytochemicals from Vegetable Oil and. . .

7

chain, which includes how plants are farmed, transported, marketed, processed, and consumed [19]. Therefore, biowastes from edible oil and oilseed processing could be inexpensive, efficient, and environmentally benign, reducing environmental consequences. This strategy aligns with the SDGs for “Good Health and Well-Being” which aims to improve human well-being through health-promoting plants and environmentally friendly food processing (https://sdgs.un.org/goals/goal3).

4

Bioactive Markers in Vegetable Oil and Oilseed Processing By-products

Studies reported the recovery and the composition of active phytochemicals from oil processing wastes. Soybean (Glycine max) cake contains isoflavone aglycones, glycosides, and phenolic acids, associated with its antioxidant potential. Sunflower (Helianthus annuus) seeds and leaf extracts are also rich in phenolics [5]. Sinapic acid and sinapine are the major phenolics in the rapeseed (Brassica napus) cake [20]. Sesame (Sesamum indicum) meal is valorized for compensating for synthetic antioxidants. Palm (Elaeis guineensis) kernel is rich in phenolics with healthpromoting potential [4]. Flax (Linum usitatissimum) cake extract showed antioxidant and antibacterial effects in food and cosmetic products. Olive (Olea europaea) leaves are rich in oleuropein and have health-promoting properties. Olive pomace is rich in bioactive ingredients such as tyrosol, verbascoside, hydroxytyrosol, rutin, catechol, and phenolic acids. Besides, wastewater from the olive mill is a source of bioactive phytochemicals with biological activities [5, 10–12]. Processing and extraction conditions affect the by-products generated during edible oil production. For example, physical oil extraction requires heat, while solvent extraction might be toxic. Thus, pretreatment technologies replacing traditional methods and achieving the processes more efficiently are essential. After crude oil extraction, some fats and oils are refined to remove unwanted materials (e.g., monoacylglycerols, phospholipids, diacylglycerols, FFA, pigments). However, this process might also remove valuable phytochemicals, including antioxidants and vitamins, so the obtained oils are generally of low quality. Biowastes from the oil production are rich in phenolics, sterols, carotenoids, tocols, fatty acids, and proteins, which are interested in their techno-function (e.g., coloring and texturing) nutritional traits or having a positive impact on human or animal health. Recovery of these compounds involves their removal by processing systems that do not affect their functionality, to be used as ingredients. The chemical composition of oil processing by-products varies due to crop differences, oil extraction techniques, and harvest time. Recent studies focused on green extraction under high pressure. On the other side, the oil processing by-products are generally roasted and ground and used as fertilizer or animal feed. The adulteration of cooking oil with recycled waste oils was also reported, causing food safety issues. Through chemical reactions, waste cooking oils have been transformed into biodiesel [10–13].

8

5

M. F. Ramadan Hassanien

Expected Outputs and Potential Impacts on the Environment and Economy

Edible oil and oilseed manufacturing biowaste recycling promise to increase resource efficiency in food production and improve future food security. Furthermore, efficient edible oil and oilseed manufacturing biowaste valorization should increase farmers’ income, decrease animal feeding costs, reduce environmental pollution, and retrieve value-added products [21, 22]. It is possible to valorize vegetable oil and oilseed processing biowastes while ensuring nutritional quality, food safety, and sustainability. This concern agrees with SDGs, especially goal 12, which focuses on responsible production and consumption. Therefore, policy-makers, regulatory authorities, and legislators need to react to new developments and consider new ideas. The valorization of vegetable oil and oilseed processing by-products could enhance food security, new sustainable protein sources, and health-promoting active constituents [5].

6

Features and Goals of the Book

This book intends to provide a multidisciplinary discussion on phytochemistry, functional characteristics, health-enhancing impacts of bioactive chemicals in oil processing biowastes, and food and nonfood applications from oil processing biowastes. The scientific foundations of oil processing by-products’ health-promoting advantages and applications will be revealed. The book focuses on the characteristics of vegetable oil and oilseed processing by-products, mainly from a phytochemistry standpoint. The chapters review the processing techniques used to develop novel applications. In addition, by incorporating vegetable oil and oilseed processing by-products into applied operations, the economy will be boosted (food production, livestock production, pharmaceuticals, and cosmetics). Furthermore, researchers exploring the recycling of agro-industrial waste originating from vegetable oil and oilseed industry products will benefit from this work. The tentative book chapters cover a wide range of phytochemistry and environmental chemical discoveries. Each chapter covers the following topics: 1. An overview of each discussed biowaste from the oil processing industry and its economic value. 2. Bioactive substances and chemical makeup of extracts from oil processing by-products. 3. Biological and functional properties of oil processing by-product extracts and bioactive substances. 4. Extracts and bioactive substances from oil production by-products in food and nonfood applications. 5. Valorization of by-products of oil manufacturing for non-health uses.

1

Introduction to Bioactive Phytochemicals from Vegetable Oil and. . .

9

References 1. Stahel WR (2016) The circular economy. Nature 531:435–438 2. Clark JH, Farmer TJ, Herrero-Davila L, Sherwood J (2016) Circular economy design considerations for research and process development in the chemical sciences. Green Chem 18:3914– 3934 3. Sherwood J (2020) The significance of biomass in a circular economy. Bioresour Technol 300: 122755 4. Mora-Villalobos JA, Aguilar F, Carballo-Arce AF, et al (2021) Tropical agroindustrial biowaste revalorization through integrative biorefineries-review part I: coffee and palm oil by-products. Biomass Conv. Bioref. https://doi.org/10.1007/s13399-021-01442-9 5. Rao M, Bast A, de Boer A (2021) Valorized food processing by-products in the EU: finding the balance between safety, nutrition, and sustainability. Sustainability 13:4428. https://doi.org/10. 3390/su13084428 6. Ramadan MF (2019) Chemistry and functionality of fruit oils: an introduction. In: Ramadan M (ed) Fruit oils: chemistry and functionality. Springer, Cham. https://doi.org/10.1007/978-3-03012473-1_1 7. Pudel F, Wiesen S (2017) Vegetable oil-biorefinery. In: Wagemann K, Tippkötter N (eds) Biorefineries. Advances in biochemical engineering/biotechnology, vol 166. Springer, Cham. https://doi.org/10.1007/10_2016_65 8. Caldeira C, De Laurentiis V, Corrado S, van Holsteijn F, Sala S (2019) Quantification of food waste per product group along the food supply chain in the European Union: a mass flow analysis. Resour Conserv Recycl 149:479–488 9. FAO (2014) Food wastage footprint: full cost-accounting. FAO, Rome, p 98 10. Chang S, Tan C, Frankel EN, Barrett DM (2000) Low-density lipoprotein antioxidant activity of phenolic compounds and polyphenol oxidase activity in selected clingstone peach cultivars. J Agric Food Chem 48(2):147–151 11. Şahin S, Elhussein EAA (2018) Valorization of a biomass: phytochemicals in oilseed by-products. Phytochem Rev 17:657–668. https://doi.org/10.1007/s11101-018-9552-6 12. Bodoira R, Velez A, Maestri D et al (2020) Bioactive compounds obtained from oilseed by-products with subcritical fluids: effects on Fusarium verticillioides growth. Waste Biomass Valor 11:5913–5924. https://doi.org/10.1007/s12649-019-00839-y 13. Rodríguez-Roque MJ, Sánchez R, Pérez-Leal R, Soto Caballero M, Salazar NA, Flores Cordova M (2021) By-products from oilseed processing and their potential applications. https://doi.org/10.1002/9781119575313.ch9 14. Zhou Y, Zhao W, Lai Y, Zhang B, Zhang D (2020) Edible plant oil: global status, health issues, and perspectives. Front Plant Sci 11:1315 15. Smeu I, Dobre AA, Cucu EM, Mustăt‚ea G, Belc N, Ungureanu EL (2022) Byproducts from the vegetable oil industry: the challenges of safety and sustainability. Sustainability 14:2039. https://doi.org/10.3390/su14042039 16. European Commission (2022) SDG POLICY MAPPING. Available online: https://ec.europa. eu/sustainable-development/goal12_en#target-12-3. Accessed 17 Apr 2022 17. European Commission (2022) Oilseeds and protein crops statistics. Available online: https://ec. europa.eu/info/food-farming-fisheries/farming/facts-and-figures/markets/overviews/marketobservatories/crops/oilseeds-and-protein-crops_en. Accessed 17 Apr 2022 18. EUROSTAT (European Statistical Office) (2022) Crop production in national humidity. Available online: https://ec.europa.eu/eurostat/databrowser/view/APRO_CPNH1__custom_ 1725550/default/table?lang¼en

10

M. F. Ramadan Hassanien

19. Ramadan MF (2021) Introduction to black cumin (Nigella sativa): chemistry, technology, functionality and applications. In: Ramadan MF (ed) Black cumin (Nigella sativa) seeds: chemistry, technology, functionality, and applications. Food bioactive ingredients. Springer, Cham. https://doi.org/10.1007/978-3-030-48798-0_1 20. Kalaydzhiev H, Ivanova P, Stoyanova M et al (2020) Valorization of rapeseed meal: influence of ethanol antinutrients removal on protein extractability, amino acid composition and fractional profile. Waste Biomass Valor 11:2709–2719. https://doi.org/10.1007/s12649-018-00553-1 21. Vilariño MV, Carol F, Caitlin Q (2017) Food loss and waste reduction as an integral part of a circular economy. Front Environ Sci 5:21. https://doi.org/10.3389/fenvs.2017.00021 22. Elimam DM, Ramadan MF, Elshazly AM, Farag MA (2022) Introduction to Mediterranean fruits bio-wastes: chemistry, functionality and techno-applications. In: Ramadan MF, Farag MA (eds) Mediterranean fruits bio-wastes. Springer, Cham. https://doi.org/10.1007/978-3-03084436-3_1

Part II Phytochemicals from Common Vegetable Oil and Oilseed Processing By-products

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products Onur Ketenoglu, Su¨ndu¨z Sezer Kiralan, and Mustafa Kiralan

Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Chemical Composition and Bioactive Compounds of Extracts from Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Biological and Functional Properties of Extracts and Bioactive Compounds from Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Food and Non-food Applications of Extracts and Bioactive Compounds from Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Valorization of Oil Processing By-products for Biogas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

14 17 21 21 22 22 23

Abstract

Soybean is of great importance among all harvested oil crops worldwide due to its high protein and oil contents. Also, soybeans are good sources for such minor components as phytosterols, squalene, phenolic components, and lecithin, which are positively proven to benefit human health. Soybean oil is used for either food or non-food applications such as biodiesel or lubricant production. After the oil extraction process, soybean by-products such as cake, meal, hull, or deodorizer distillate also have great interest due to their bioactive components, which are not transferred to the oil. Many extraction techniques and approaches have been studied so far, and the increasing demand for such components for health purposes is raising the number of studies for this aim. In this chapter, the usage O. Ketenoglu Department of Food Engineering, Faculty of Agriculture, Eskisehir Osmangazi University, Eskisehir, Turkey e-mail: [email protected] S. S. Kiralan · M. Kiralan (*) Department of Food Engineering, Faculty of Engineering, Balikesir University, Balikesir, Turkey © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_2

13

14

O. Ketenoglu et al.

areas of soybean by-products are thoroughly discussed in addition to a general overview of this valuable crop. Keywords

Bioactive compounds · Glycine max · Lecithin · Processing · Waste

1

Introduction

Soybeans are one of the main oil crops harvested globally and constitute approximately 90% of the United States’ oilseed production [1]. The importance of this crop raises from its oil content, an essential source for the food industry, and used in different biodiesel and lubricant manufacturing sectors. According to the United States Department of Agriculture (USDA), soybean, rapeseed, sunflower, peanut, cottonseed, palm kernel, and copra are the major oilseeds worldwide [2]. Figure 1 exhibits the total production capacity of oilseeds according to years. According to the USDA [2], the production capacity of soybean is far ahead of other oilseeds, with a total production of 336.69 million metric tons in 2019/2020. Among all soybean producers, Brazil and the United States are the two pioneers with their soybean production capacities of 126,000 and 96,667 thousand metric tons in 2019/2020, respectively [2]. Soybean oil is generally produced using solvent extraction and mechanical oil extraction (or pressing). When the solvent extraction method is used, most of the oil can be extracted with an extraction efficiency of approximately 99%. On the other hand, when the mechanical system is used, oil extraction yield is very low as oil extraction efficiency is also less than 70% [3]. The major soybean oil producer

Fig. 1 Production of major oilseeds worldwide. (Source: USDA [2])

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products

15

Fig. 2 Production of major protein meals worldwide. (Source: USDA [2])

countries are China and the United States. According to the data from USDA for 2019/2020, the total production of soybean oil was 16,397 thousand metric tons in China, followed by the United States with the production of 11,300 thousand metric tons [2]. Soybean meal is a by-product of the oil extraction process of soybean oilseeds. Soybean meal is generally utilized in animal diets, particularly poultry diets, due to its high nutrition values, protein quality, excellent amino acid profile, and high amino acid digestibility [4]. The worldwide production capacity of major protein meals is exhibited in Fig. 2. The major protein meal is the soybean meal among the meals from other oilseeds, and the highest production capacity belongs to China with 72,468 thousand metric tons, followed by the United States with a production capacity of 46,358 thousand metric tons in 2019/2020 [2]. Soybean meal contains a variety of valuable bioactive phytochemicals. According to de Oliveira Silva [5], the total isoflavones content of soybean meal is 154.4 mg 100 g 1 dry weight basis (dwb), and the most abundant isoflavones are β-glycosides, which constitute 66% of the total isoflavones, followed by malonylglycosides (16%), aglycones (12%), and acetylglycosides (6%). Various extraction systems and different solvents can be used in the extraction of phenolic compounds. These compounds can be used in the food industry as valuable ingredients. Freitas et al. [6] reported the presence of genistin, daidzin, glycitin, and malonyl genistin as major isoflavones in the aqueous extract of soybean meal. The predominant phenolics among identified 16 phenolics were caffeic acid, 5-caffeoylquinic chlorogenic acid, and hesperidin. In their study, soybean meal extract showed intense inhibition activity toward lipid peroxidation compared with natural and synthetic food antioxidants. In addition to the oil extraction, various by-products such as phosphatides, unsaponifiable materials, glycerides, free fatty acids, and soap occur at the end of the refining process. For example, soybean soapstock (SS) is a by-product formed

16

O. Ketenoglu et al.

a

b

Fig. 3 Compositions of crude (a) and deoiled (b) soybean lecithins. (Adapted from Wu and Wang [11])

during the vegetable oil refining process, containing a high amount of saponified fatty acids. Due to the chemical composition and large production capacity, SS was reported to produce different non-edible products such as biodiesel [7]. Lecithin is an important by-product and generally includes varying proportions of phosphatidylcholine (PC), phosphatidylethanolamine (PE), and phosphatidylinositol (PI) [8]. Soybean oil by-products are good sources for the production of commercial lecithin. Commercial lecithin is produced from crude soybean oil extracted from soybean flakes with hexane. Lecithin is widely used in the food, pharmaceutical, and cosmetic industries as a surfactant. The compositions of crude (a) and deoiled (b) soybean lecithins are presented in Fig. 3.

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products

17

Fig. 4 By-product valorization of soybean oil processing

Table 1 Chemical composition of defatted soybean meals

Component Moisture Protein Fat Ash Total dietary fiber Soluble dietary fiber Insoluble dietary fiber

% (wet weight basis) 3.71 45.12 1.27 5.95 16.29 4.83 11.46

Adapted from Korkerd et al. [12]

Tocols, sterols, and squalene are also known as bioactive compounds, and these valuable compounds are present in deodorizer distillate, which is a by-product obtained in the last step of oil refining, namely, deodorization [9, 10]. A graphical abstract regarding the by-product valorization of soybean oil processing is presented in Fig. 4.

2

Chemical Composition and Bioactive Compounds of Extracts from Oil Processing By-products

Soybean meal is a rich source of dietary fibers. The chemical composition of defatted soybean meals is given in Table 1. Soybean cake is an important by-product containing functional compounds that positively contribute to human health. Kao and Chen [13] extracted four fractions of isoflavones. Malonylglucoside and glucoside fractions were isolated using preparative chromatography, while acetylglucoside and aglycone fractions were separated with preparative chromatography and a silica gel column. The most abundant component in the malonylglucoside fraction was malonyl daidzin with a concentration of 48.8 μg mL 1, while the glucoside fraction included genistin at a concentration of 45.9 μg mL 1. The acetylgenistin concentration in the acetylglucoside fraction was 69.0 μg mL 1 as the highest, and the aglycone fraction mainly included daidzein with a concentration of 47.3 μg mL 1. Free and bound phenolics extracted from soybean hulls are also important by-products of soybean oil processing. According to Niño-Medina et al. [14], soybean hull free fraction included a high content of total phenolics and condensed

18

O. Ketenoglu et al.

Fig. 5 Chemical structure of lecithin

tannins (1.75 mg chlorogenic acid equivalents (CAE) g 1 and 7.91 mg catechin equivalents (CatE) g 1, respectively) compared with soybean hull bound fraction (0.33 mg CAE g 1 and 6.47 mg CatE g 1, respectively). However, the content of total flavonoids was higher in the soybean hull bound fraction (1.21 mg CatE g 1) than in the soybean hull free fraction (0.73 mg CatE g 1). Lecithins have a great interest in the food and feed industry for emulsification purposes. Most lecithins are obtained from by-products during the degumming step of crude soybean oil refining [15]. The chemical structure of soybean lecithin is exhibited in Fig. 5. Deodorizer distillate is rich in valuable bioactive compounds such as tocopherol and sterols. According to Torres et al. [16], the deodorizer distillate from soybean oil refining mainly contained 27% sterols followed by acylglycerols (21%), tocopherols (20%), and free fatty acids (20%). Tocopherols are lipid-soluble compounds and constitute a significant part of most vegetable oils. Tocopherols are subgrouped into α-, β-, γ-, and δ-tocopherols according to the methylation status of the chromanol structure. Thus, these compounds act as antioxidants in food applications. Besides, these compounds have vitamin E activity and are reported to positively affect human health [17, 18]. Deodorization is the final stage of crude oil refining. Deodorizer distillates, which are valuable by-products rich in bioactive compounds as tocopherols, are produced during the deodorization step. According to Ramamurthi and McCurdy [19], the percentage of total tocopherol content in soya deodorizer distillate was 12.7. γ-Tocopherol fraction had the highest concentration with 7.16%, followed by δ(4.73%), α- (0.68%), and β- (0.18%). Shimada et al. [20] used molecular distillation and lipase reactions to obtain high purity tocopherols. In the first stage, the molecular distillation method was used to remove substances having high boiling points, such as steryl esters from soybean oil deodorizer distillate (SODD). In the second step, a lipase reaction using Candida rugosa lipase was applied to obtain a high yield of tocopherols. This step provides the esterification of sterols with free fatty acids. After that, the molecular distillation method was used to recover tocopherols and FFA. Under the same reaction conditions, this distillate was reacted again with lipase to enhance tocopherol’s purity. At the end of the process, high purity tocopherols were obtained with approximately 90% yield. In a similar study by Nagao et al. [10], a multi-stage distillation procedure was performed to obtain high purity of tocopherols. First, the researchers

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products

19

Fig. 6 Chemical structure of squalene

pre-distilled the SODD, and their distillate was mainly formed by free fatty acids (FFAs), sterols, and tocopherols. Then, this fraction was treated with lipase to catalyze the sterol esterification with FFAs. After the sequential distillations, the researchers achieved purifying the tocopherols up to 72%. Molecular distillation is used in industrial and laboratory scale applications to obtain tocopherols with high purities. However, this method has some disadvantages: lower separation yield, high costs for expensive equipment, and high energy consumption due to high temperature and high vacuum [21]. For these reasons, alternative methods have been developed in recent years; one of them is supercritical fluid extraction (SFE). Fang et al. [22] concentrated tocopherols from methyl esterified deodorizer distillate with supercritical CO2. The researchers optimized the feed location, initial pressure, temperature gradient, and the CO2 ratio for the separation of fatty acid methyl esters (FAME), and they concluded that high tocopherol purity (80%) with high recovery (more than 50%) was obtained when the pressure was set to 20 MPa for 5.5 h. Liu et al. [23] used deep eutectic solvents (DESs) as green solvents to extract tocopherols from SODD. The authors emphasized that phenolic DESs interacted with tocopherols via π–π bonds interaction. Therefore, a two-step extraction method was applied. In the first step, DESs were used to extract total tocopherols from SODD. In the second step, re-extraction with hexane was used to separate tocopherols from the DES phase. Among all tested eight solvents, ChCl-p-cresol was more suitable for extracting total tocopherols (87 g kg 1) using vortex-assisted extraction. At the end of their processes, the extraction efficiencies of α-tocopherol, γ-tocopherol, δ-tocopherol, and total tocopherols were 70.7%, 80.4%, 75.2%, and 77.6%, respectively. Squalene (Fig. 6), a triterpene compound with a similar structure to β-carotene, is a precursor of cholesterol biosynthesis. Squalene exhibits protective effects on some diseases such as cancer and cardiovascular diseases [24–26]. Squalene is generally obtained from shark liver oil due to its high concentration. To protect the environment, vegetable sources have been preferred in squalene production in recent years. SODD was reported to be an excellent alternative to marine animals in terms of being a source of squalene [27]. Gunawan et al. [9] isolated and purified squalene from soybean oil deodorizer distillate using a modified soxhlet extraction and silica gel column chromatography. Modified soxhlet extraction ensured obtaining one fraction rich in fatty acid steryl esters and squalene. In addition, the combination of a modified soxhlet extraction and the silica gel column chromatography was provided to obtain high purity

20

O. Ketenoglu et al.

(95.9%) and high recovery (93.1%) of squalene from soybean oil deodorizer distillate. Fatty acid steryl esters (FASEs) are significant components in the production of hormones and vitamins, and they have gained increasing importance due to their health concerns, such as lowering serum cholesterol levels [27]. FASEs have been widely used in the cosmetic, nutraceutical, and pharmaceutical industries [28, 29]. Hirota et al. [30] used molecular distillation and lipase-catalyzed hydrolysis methods to get purified steryl esters. In the first stage, SODD was separated into two fractions using molecular distillation. Next, the fraction rich in steryl esters (DAG: 11.2 wt%, TAG: 32.1 wt%, and steryl esters: 45.4 wt%) is reacted with lipase to perform the hydrolysis, followed by the separation of steryl esters. The authors concluded that they achieved 97.3% purity and 87.7% recovery of steryl esters after a final molecular distillation of their lipase-treated samples. Plant sterols are minor bioactive compounds in vegetable oils, which have positive effects on human health. They are value-added additives preferred in the food and cosmetic industries due to their favorable health properties, such as reducing serum cholesterol and preventing heart diseases [31, 32]. Various extraction techniques of phytosterols have been utilized, including chemical treatment, solvent extraction, crystallization, column chromatography, and molecular distillation procedures. Yang et al. [33] used conventional methods such as a catalytic decomposition and crystallization process to recover phytosterols from SODD. They used several solvents for their crystallization purpose, and they stated that a mixture of acetone and ethanol with a volume ratio of 4:1 is suitable for good crystallization of phytosterols, high purity, and yield. The researchers achieved a purity of 91.8 wt% and a yield of 22.9 wt% for their phytosterols after crystallization under their optimized conditions. Nagao et al. [10] emphasized that a two-step in situ reaction aided by a short-path distillation approach exerted positive effects to obtain high yields and purities for steryl esters. According to the authors, the purity and yield of steryl esters were both 97%. Additionally, the researchers concluded that the purified steryl esters had a similar sterol composition (27 wt% of campesterol, 29 wt% of stigmasterol, and 44 wt% of β-sitosterol) with their SODD concentrate sample. Gunawan et al. [27] used modified Soxhlet extraction, modified silica gel column chromatography, and water/acetone extraction to obtain high purity (86.7%) and a high total recovery (85.3%) of FASEs from SODD. The authors emphasized that this separation process was sensitive for FASEs fractions and did not degrade them. Torres et al. [34] used enzymatic esterification and supercritical fluid extraction to obtain phytosterol esters from SODD. SODD was first modified by oleic acid, and then the product was subjected to a two-step enzymatic reaction. Sterol esterification and ethyl esterification were carried out using lipases from Candida rugosa and Candida antarctica, respectively. This product contained mainly phytosterol esters, tocopherols, and fatty acid ethyl esters at the end of enzymatic reactions. The researchers utilized supercritical carbon dioxide to purify sterol esters from this mixture. They concluded that they achieved a final yield of 72% and a concentration

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products

21

degree of 82.4 wt% of phytosterol esters under 250 bar, 55  C, and 35 kg 1 solventto-feed ratio conditions. As it can be concluded from these studies, the importance of the valorization of by-products from soybean oil processing is apparent for the food and pharmaceutical industries.

3

Biological and Functional Properties of Extracts and Bioactive Compounds from Oil Processing By-products

Soybean cake is also a by-product formed after soybean oil processing and is considered a rich source of isoflavones. Kao and Chen [13] determined four isoflavone fractions (malonylglucoside fraction, glucoside fraction, acetylglucoside fraction, and aglycone fraction) in soybean cake. Antioxidant activities of these fractions were determined using assays such as DPPH
, TEAC, reducing power, metal ion chelating, conjugated diene, and TBARS. The glucoside fraction had the lowest radical scavenging activity in the DPPH
assay, while the highest metal ion chelating was observed in this fraction. TEAC results showed that the aglycone fraction had the highest value. Acetylglucoside fraction was reported to have the highest value in conjugated diene assay, and the highest TBARS value was found in the aglycone fraction. Niño-Medina et al. [14] evaluated the antioxidant activity of the free and bound fraction of soybean hull, another valuable by-product obtained from soybean oil processing. According to their findings, the soybean hull free fraction had the highest value in ABTS assay (14.8 μmolTE g 1), while the highest value in DPPH
assay was observed in soybean hull bound fraction (5.28 μmolTE g 1).

4

Food and Non-food Applications of Extracts and Bioactive Compounds from Oil Processing By-products

Korkerd et al. [12] investigated the utilization of defatted soybean meal (DSM) to produce fortified extruded snacks. According to their results, the addition of DSM with a mixture ratio of 1.0 (without the addition of other tested by-products) resulted in higher total dietary fiber (TDF) and protein contents compared to the control. The TDF and protein contents of the DSM-added group were 8.06 and 13.3% wb, while the control group had a TDF level of 4.82% wb and a protein level of 5.03% wb. Viñado et al. [35] used soybean lecithin as an alternative energy source in broiler feeding. They applied different diets, including varying proportions of soybean oil, soybean lecithin, and a blend of vegetable acid oil. The authors concluded that the soybean lecithin was appropriate for the utilization in diets of broiler chickens in the grower-finisher period. SODD contains remarkable concentrations of free fatty acids, which are mainly formed by oleic and linoleic acids. Such high amounts of free fatty acids are suitable

22

O. Ketenoglu et al.

for conversion to partial glycerides. Agapay et al. [36] used SODD to produce diglycerides (DG) as structured triglyceride precursors using different glycerol dosing strategies and solvent-free lipase-catalyzed esterification. The highest amount of 1,3-DG (63.9 g 100 g total DG 1) was obtained with a DG yield of 30.6 g 100 g 1 raw material and FFA conversion of 57.8%. It can be concluded that more studies should be conducted in order to understand better the importance of by-product reutilization and the food or non-food applications of soybean oil by-products.

5

Valorization of Oil Processing By-products for Biogas

Soapstock (SS) is reported as a suitable raw material to produce biodiesel because of its easy collection [7]. Wang et al. [7] developed acid oil (AO) production technology from SS using only sulfuric acid and water under the ambient temperature. They achieved to reach a recovery yield of 97% (w/w) of AO. According to their findings, the purified biodiesel yield was 94% (w/w) based on the total fatty acids of the soapstock at the end of the reaction. Also, the authors concluded that the reaction time could be shortened to nearly one-third. Wang et al. [37] stıudied the conversion of soapstocks using microwave-assisted catalytic pyrolysis, a promising technology to obtain hydrocarbon-rich bio-oil. The maximum yield of bio-oil from soybean oil soapstock was 60.4% under pyrolysis conditions using HZSM-5 catalyst at 300  C. Rhamnolipids are a member of biosurfactants that have the ability of surface activity. Biosurfactants could be used in different sectors such as food, cosmetics, medicine, petroleum [38–41]. For example, Lopes et al. [42] used soybean soapstock to produce rhamnolipids using a fermentation process via a mutant microorganism, Pseudomonas aeruginosa LBI. The results for rhamnolipids are satisfactory in the emulsification of used automotive lubricating oil, being very close to the synthetic alternative Tween80.

6

Conclusion

Soybean is an important oilseed crop harvested worldwide due to its rich composition of oil and protein. In addition, a wide range of minor components such as bioactive phytochemicals, squalene, lecithin, and phenolic components also increase the value of soybeans due to their positively proven health aspects. Soybean oil processing generates value-added by-products since some minor components are not transferred to the oil phase. The processing of these by-products is also important for the food industry to recover and reuse the valuable components present in such by-products as cake, meal, and deodorizer distillate. Since consumers have a great demand for healthy products nowadays, newer techniques and methods have been studied to recover the nutrients and minor components from soybean by-products, correspondingly. In addition to the food industry, soybean by-products are also

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products

23

important for their utilization in such non-food applications as biogas production. Depending on the increasing production capacity of this valuable crop, it is believed that the importance of the reutilization of soybean by-products will be better understood with the help of developing technology.

References 1. USDA (2020) Oil crops yearbook. United States Department of Agriculture, Washington, DC. http://www.ers.usda.gov/data-products/oil-crops-yearbook.aspx. Accessed 13 Dec 2020 2. USDA (2020) Oilseeds: world markets and trade. United States Department of Agriculture, Washington, DC (issue: November 2020). https://downloads.usda.library.cornell.edu/usdaesmis/files/tx31qh68h/9w032s71k/jh344h54j/oilseeds.pdf. Accessed 17 Dec 2020 3. Grieshop CM, Kadzere CT, Clapper GM, Flickinger EA, Bauer LL, Frazier RL, Fahey GC (2003) Chemical and nutritional characteristics of United States soybeans and soybean meals. J Agric Food Chem 51:7684–7691. https://doi.org/10.1021/jf034690c 4. Ravindran V, Abdollahi MR, Bootwalla SM (2014) Nutrient analysis, metabolizable energy, and digestible amino acids of soybean meals of different origins for broilers. Poult Sci 93:2567– 2577. https://doi.org/10.3382/ps.2014-04068 5. de Oliveira Silva F, Miranda TG, Justo T, da Silva Frasão B, Conte-Junior CA, Monteiro M, Perrone D (2018) Soybean meal and fermented soybean meal as functional ingredients for the production of low-carb, high-protein, high-fiber and high isoflavones biscuits. LWT Food Sci Technol 90:224–231. https://doi.org/10.1016/j.lwt.2017.12.035 6. Freitas CS, Alves da Silva G, Perrone D, Vericimo MA, Dos S Baião D, Pereira PR, Paschoalin VMF, M del Aguila E (2019) Recovery of antimicrobials and bioaccessible isoflavones and phenolics from soybean (Glycine max) meal by aqueous extraction. Molecules 24:74. https:// doi.org/10.3390/molecules24010074 7. Wang ZM, Lee JS, Park JY, Wu CZ, Yuan ZH (2007) Novel biodiesel production technology from soybean soapstock. Korean J Chem Eng 24:1027–1030. https://doi.org/10.1007/s11814007-0115-6 8. Kuligowski J, Quintás G, Garrigues S, de la Guardia M (2008) Determination of lecithin and soybean oil in dietary supplements using partial least squares–Fourier transform infrared spectroscopy. Talanta 77:229–234. https://doi.org/10.1016/j.talanta.2008.06.029 9. Gunawan S, Kasim NS, Ju YH (2008) Separation and purification of squalene from soybean oil deodorizer distillate. Sep Purif Technol 60:128–135. https://doi.org/10.1016/j.seppur.2007. 08.001 10. Nagao T, Kobayashi T, Hirota Y, Kitano M, Kishimoto N, Fujita T, Watanabe Y, Shimada Y (2005) Improvement of a process for purification of tocopherols and sterols from soybean oil deodorizer distillate. J Mol Catal B Enzym 37:56–62. https://doi.org/10.1016/j.molcatb.2005. 09.005 11. Wu Y, Wang T (2003) Soybean lecithin fractionation and functionality. J Am Oil Chem Soc 80: 319–326. https://doi.org/10.1007/s11746-003-0697-x 12. Korkerd S, Wanlapa S, Puttanlek C, Uttapap D, Rungsardthong V (2016) Expansion and functional properties of extruded snacks enriched with nutrition sources from food processing by-products. J Food Sci Technol 53:561–570. https://doi.org/10.1007/s13197-015-2039-1 13. Kao TH, Chen BH (2006) Functional components in soybean cake and their effects on antioxidant activity. J Agric Food Chem 54:7544–7555. https://doi.org/10.1021/jf061586x 14. Niño-Medina G, Muy-Rangel D, Urías-Orona V (2017) Chickpea (Cicer arietinum) and soybean (Glycine max) hulls: byproducts with potential use as a source of high value-added food products. Waste Biomass Valor 8:1199–1203. https://doi.org/10.1007/s12649-016-9700-4

24

O. Ketenoglu et al.

15. Erickson DR (1995) Degumming and lecithin processing and utilization. In: Erickson DR (ed) Practical handbook of soybean processing and utilization. AOCS Press, Urbana, pp 174– 183. https://doi.org/10.1016/B978-0-935315-63-9.50014-0 16. Torres CF, Torrelo G, Señoráns FJ, Reglero G (2007) A two steps enzymatic procedure to obtain sterol esters, tocopherols and fatty acid ethyl esters from soybean oil deodorizer distillate. Process Biochem 42:1335–1341. https://doi.org/10.1016/j.procbio.2007.07.005 17. Schwartz H, Ollilainen V, Piironen V, Lampi AM (2008) Tocopherol, tocotrienol and plant sterol contents of vegetable oils and industrial fats. J Food Compos Anal 21:152–161. https:// doi.org/10.1016/j.jfca.2007.07.012 18. Thompson MD, Cooney RV (2020) The potential physiological role of γ-tocopherol in human health: a qualitative review. Nutr Cancer 72:808–825. https://doi.org/10.1080/01635581.2019. 1653472 19. Ramamurthi S, McCurdy AR (1993) Enzymatic pretreatment of deodorizer distillate for concentration of sterols and tocopherols. J Am Oil Chem Soc 70:287–295. https://doi.org/10. 1007/BF02545310 20. Shimada Y, Nakai S, Suenaga M, Sugihara A, Kitano M, Tominaga Y (2000) Facile purification of tocopherols from soybean oil deodorizer distillate in high yield using lipase. J Am Oil Chem Soc 77:1009–1013. https://doi.org/10.1007/s11746-000-0160-z 21. Ketenoglu O (2021) Molecular distillation in the extraction, recovery, and concentration of food molecules. In: Knoerzer K, Muthukumarappan K (eds) Innovative food processing technologies: a comprehensive review, vol 3. Elsevier, Amsterdam, pp 122–134. https://doi.org/10.1016/ B978-0-08-100596-5.22996-X 22. Fang T, Goto M, Wang X, Ding X, Geng J, Sasaki M, Hirose T (2007) Separation of natural tocopherols from soybean oil byproduct with supercritical carbon dioxide. J Supercrit Fluids 40: 50–58. https://doi.org/10.1016/j.supflu.2006.04.008 23. Liu W, Fu X, Li Z (2019) Extraction of tocopherol from soybean oil deodorizer distillate by deep eutectic solvents. J Oleo Sci 68:951–958. https://doi.org/10.5650/jos.ess19146 24. Ibrahim NI, Fairus S, Zulfarina MS, Naina Mohamed I (2020) The efficacy of squalene in cardiovascular disease risk – a systematic review. Nutrients 12:414. https://doi.org/10.3390/ nu12020414 25. Smith TJ (2000) Squalene: potential chemopreventive agent. Expert Opin Investig Drugs 9: 1841–1848. https://doi.org/10.1517/13543784.9.8.1841 26. Rao CV, Newmark HL, Reddy BS (1998) Chemopreventive effect of squalene on colon cancer. Carcinogenesis 19:287–290. https://doi.org/10.1093/carcin/19.2.287 27. Gunawan S, Fabian C, Ju YH (2008) Isolation and purification of fatty acid steryl esters from soybean oil deodorizer distillate. Ind Eng Chem Res 47:7013–7018. https://doi.org/10.1021/ ie800346x 28. Gunawan S, Vali SR, Ju YH (2006) Purification and identification of rice bran oil fatty acid steryl and wax esters. J Am Oil Chem Soc 83:449–456. https://doi.org/10.1007/s11746-0061225-8 29. Piironen V, Lindsay DG, Miettinen TA, Toivo J, Lampi AM (2000) Plant sterols: biosynthesis, biological function and their importance to human nutrition. J Sci Food Agric 80:939–966. https://doi.org/10.1002/(SICI)1097-0010(20000515)80:73.0.CO;2-C 30. Hirota Y, Nagao T, Watanabe Y, Suenaga M, Nakai S, Kitano A, Sugihara A, Shimada Y (2003) Purification of steryl esters from soybean oil deodorizer distillate. J Am Oil Chem Soc 80:341– 346. https://doi.org/10.1007/s11746-003-0700-6 31. Feng S, Belwal T, Li L, Limwachiranon J, Liu X, Luo Z (2020) Phytosterols and their derivatives: potential health-promoting uses against lipid metabolism and associated diseases, mechanism, and safety issues. Compr Rev Food Sci Food Saf 19:1243–1267. https://doi.org/10. 1111/1541-4337.12560 32. Uddin MS, Ferdosh S, Haque Akanda MJ, Ghafoor K, Rukshana AH, Ali ME, Kamaruzzaman BY, Fauzi MB, Hadijah S, Shaarani S, Islam Sarker MZ (2018) Techniques for the extraction of

2

Bioactive Phytochemicals from Soybean (Glycine max) Oil Processing By-products

25

phytosterols and their benefits in human health: a review. Sep Sci Technol 53:2206–2223. https://doi.org/10.1080/01496395.2018.1454472 33. Yang H, Yan F, Wu D, Huo M, Li J, Cao Y, Jiang Y (2010) Recovery of phytosterols from waste residue of soybean oil deodorizer distillate. Bioresour Technol 101:1471–1476. https://doi.org/ 10.1016/j.biortech.2009.09.019 34. Torres CF, Fornari T, Torrelo G, Señoráns FJ, Reglero G (2009) Production of phytosterol esters from soybean oil deodorizer distillates. Eur J Lipid Sci Technol 111:459–463. https://doi.org/10. 1002/ejlt.200800141 35. Viñado A, Castillejos L, Rodriguez-Sanchez R, Barroeta AC (2019) Crude soybean lecithin as alternative energy source for broiler chicken diets. Poult Sci 98:5601–5612. https://doi.org/10. 3382/ps/pez318 36. Agapay RC, Ju YH, Tran-Nguyen PL, Angkawijaya AE, Santoso SP, Go AW (2020) Synthesizing precursors for functional food structured lipids from soybean oil deodorized distillates. Waste Biomass Valor. https://doi.org/10.1007/s12649-020-01284-y 37. Wang Y, Zhang S, Wu Q, Duan D, Liu Y, Ruan R, Fu G, Dai L, Jiang L, Yu Z, Zeng Z, Tian X, Yang X (2019) Microwave-assisted pyrolysis of vegetable oil soapstock: comparative study of rapeseed, sunflower, corn, soybean, rice, and peanut oil soapstock. Int J Agric Biol Eng 12:202– 208. https://doi.org/10.25165/j.ijabe.20191206.4599 38. Vecino X, Cruz JM, Moldes AB, Rodrigues LR (2017) Biosurfactants in cosmetic formulations: trends and challenges. Crit Rev Biotechnol 37:911–923. https://doi.org/10.1080/07388551. 2016.1269053 39. Campos JM, Montenegro Stamford TL, Sarubbo LA, de Luna JM, Rufino RD, Banat IM (2013) Microbial biosurfactants as additives for food industries. Biotechnol Prog 29:1097–1108. https://doi.org/10.1002/btpr.1796 40. Perfumo A, Rancich I, Banat IM (2010) Possibilities and challenges for biosurfactants use in petroleum industry. In: Sen R (ed) Biosurfactants: advances in experimental medicine and biology, vol 672. Springer, New York, pp 135–145. https://doi.org/10.1007/978-1-4419-59799_10 41. Rodrigues L, Banat IM, Teixeira J, Oliveira R (2006) Biosurfactants: potential applications in medicine. J Antimicrob Chemother 57:609–618. https://doi.org/10.1093/jac/dkl024 42. Lopes PRM, Montagnolli RN, Cruz JM, Lovaglio RB, Mendes CR, Dilarri G, Contiero J, Bidoia ED (2021) Production of rhamnolipids from soybean soapstock: characterization and comparation with synthetics surfactants. Waste Biomass Valor 12:2013–2023. https://doi.org/ 10.1007/s12649-020-01159-2

3

Bioactive Phytochemicals from Rapeseed (Brassica napus) Oil Processing By-products Parisa Jafarian Asl and Razieh Niazmand

Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Byproducts of Rapeseed Oil Refining Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Rapeseed Meal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Soapstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Acid Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 Deodorizer Distillate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

28 29 29 37 39 39 44 45

Abstract

Rapeseed oil is currently the third source of vegetable oils. Crude oils generally contain undesirable substances which need to be removed to produce a stable and edible product. So, rapeseed oil is subjected to industrial treatments such as extraction, degumming, bleaching, deodorization, and subsequently produces large quantities of byproducts like hull and fibers, rapeseed meal, rapeseed cake, deodorizer distillate, acid oil, soapstock, etc. If these byproducts are not used for any beneficial activity, they can harm the environment. At the same time, they can be a promising source of high-value products and uses. For example, rapeseed cake and rapeseed meal is a protein-rich ingredient widely used to feed all classes of livestock. Moreover, they can be used as fuel, biogas substrate or fertilizer, or a source of natural antioxidants. Soapstock usually uses in animal feed, biodiesel synthesis, and producing soaps and detergents. Deodorizer distillate is potentially utilized to produce biodiesel as raw material and is a source of highly valuable phytochemicals. As a result, the wastes of rapeseed oil that may P. Jafarian Asl · R. Niazmand (*) Department of Food Chemistry, Research Institute of Food Science and Technology (RIFST), Mashhad, Iran e-mail: [email protected]; [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_3

27

28

P. Jafarian Asl and R. Niazmand

be considered commercially insignificant are useful for extracting or isolating valuable industrial compounds with broad applications. This chapter reviewed the various byproducts resulting from the industrial extraction process of rapeseed oil and up-to-date data. In addition, the phytochemicals of rapeseed oil’s byproducts and the technologies applied for the revalorization of rapeseed oil byproducts have been discussed. Finally, the applications of rapeseed oil byproducts have been presented. Keywords

Biodiesel · Glycerol · Rapeseed cake · Soapstocks · Squalene · Vegetable oils · Vitamin E

1

Introduction

Rapeseed (Brassica napus L.) (Figure 1a) is a plant in the family of Cruciferae (Brassicaceae), which is a member of the bivalves group (Dicotyledoneae) of the significant blooming plant groups (Phaneroganeae) and got three main varieties: Brassica nigra, Brassica oleracea, and Brassica campestris. Turnip rape (Brassica campestris) is the most variable and abundant species of Brassica. Rapeseed contains oilseeds (Fig. 1b) in spherical shapes with a diameter of 1.5–3.2 mm and a weight of 2.5–6.5 grams, varying from brown and black to red. Rapeseeds hulls are layered and contain 12–16% (based on weight) of the seeds. The seeds have a protein content from 15% to 18%. Determination of oil content of seeds (Brassica napus and Brassica campestris) by extraction shows the wide variation in the amounts [1]. Rapeseed is a significant oilseed in the world. It is traditionally utilized to produce edible oil since it is the third most valuable source of vegetable oil (after soy and palm) as well as oil meal (after soy and cotton) [2]. Currently, most species of the cultivated rapeseed have a low level of erucic acid and glucosinolates with a high amount of oleic acid. The global manufacturing of rapeseed oil is almost 27.6 million metric tons in 2019/2020. Leading producing countries of rapeseed in 2019/2020are

a

b

Fig. 1 (a)Rapeseed (Brassica napus) plant; (b) Rapeseeds

3

Bioactive Phytochemicals from Rapeseed (Brassica napus) Oil Processing. . .

29

Canada, the European Union (EU), China, and India with 19, 16.8, 13.1, and 7.7 million metric tons, respectively [3, 4]. The amount of oil in rapeseed is about 40%, and the rest, known as byproducts, is used in the cosmetics and pharmaceutical industries, animal feed, and biofuel productions. Raw rapeseed oil principally consists of triacylglycerol, but it has many non-edible substances, which should be eliminated using the refining procedures before human utilization [5]. Chemical and physical refining are two main ways of refining procedures for raw rapeseed oil. One of the most common methods for refining vegetable oils that significantly reduces free fatty acids (FFA), phospholipids, waxes, aldehydes, and ketones is chemical refining. However, physical refining is also extensively utilized [6]. Significant quantities of byproducts like rapeseed meal, soapstocks (SS), deodorizer distillates (DOD), and less important by-products such as acid oil (AO) are generated through oil refining procedures. Rapeseed meal is a waste product produced when rapeseeds are pressed for making raw oil. It is known for its high level of fatty acids, natural antioxidants (vitamins, e.g., E, B1, B2, B6, folic acid, biotin, and choline), protein (lysine, methionine, cysteine, threonine, and tryptophan), minerals (phosphorus), and raw fibers [7]. The soapstock is a side product of the neutralizing phase produced by the reaction of fatty acids with an alkaline solution and is continuously isolated from the raw oil using centrifugation [8]. At the end of the chemical refining procedures, DOD as a byproduct is produced. It has a high level of bioactive compounds such as FFA and mono-, di-triglycerides, phytosterols, tocopherols, and hydrocarbons [6]. Worldwide production of these significant byproducts (rapeseed meal, soap stocks, and rapeseed deodorizer distillates) has been 40.9, 13.5, 25 million tons in 2020/2021, respectively [9]. If these byproducts are not applied for functional or industrial purposes, they will negatively affect the environment. In addition, as a result of global population growth and increased use of refined vegetable oils, production of these by-products also increased. Therefore, scientists have presented many types of research related to various utilizations of by-products like extraction of antioxidants, biofuel manufacturing, and livestock feeds. This chapter aims to cover the significant byproducts of the edible oil refining process (rapeseed meal, soapstock, acid oil, and deodorized distillate) and review their bioactive compounds and their usage in various fields.

2

Byproducts of Rapeseed Oil Refining Process

2.1

Rapeseed Meal

Rapeseed meal (Fig. 2), referred to as canola meal in North America, Australia, and other countries, is a byproduct of rapeseed oil extraction. (Brassica napus L., Brassica rapa L., Brassica juncea L., and their crosses). It is a high protein ingredient extensively applied for feeding all livestock categories; additionally, it can be applied as fuel, biogas bed, or fertilizer [10]. World manufacture of rapeseed meal ranks second behind soybean meal. Rapeseed oil had less well known for its

30

P. Jafarian Asl and R. Niazmand

Fig. 2 Rapeseed meal

erucic acid with bitter-tasting, which later causes health issues. Due to glucosinolates in rapeseed meals, which are harmful anti-nutritional agents for animal function, its use as animal feed was limited. During the1960–1970s, species with low-erucic (“0”) and low-erucic, low-glucosinolate (“00”, double-zero, double low, canola) were expanded, enabling rapeseed oil to develop into a main edible oil and rapeseed meal to increase as animal feed. The first varieties of “00” were commercialized in Canada in the middle of the 1970s [11]. In certain countries, like France, “00” varieties were marketed at the end of the 1980s [1]. Today the species developed worldwide for edible oil, biofuel, industrial oil, and lubricants applications are low-erucic and low-glucosinolate species. There are strains with high erucic cultivated for particular industrial uses [12]. Although rapeseed meal extracted by the solvent is still the major type of rapeseed meal available for commercial use, high oil rapeseed meals produced using mechanical pressure have obtained popularity since the beginning of the century with the expansion of organic farming and oil production on the farm. The world production of rapeseed meal in 2020–2021 (40.9 million tons) was slightly less than the production in 2019–2018 (41.1 million tons) [9]. In 2020, European Union (16.4 million tons), followed by China (12.6 million tons), Canada (5.3 million tons), and India (4.0 million tons), were the leading producing countries of rapeseed meal. Moreover, the most critical consumers of rapeseed meal were the EU, China, North America (USA and Canada), and India [3, 4].

2.1.1 Solvent-Extracted Rapeseed Meal Rapeseeds have 40–45% oil, and when wholly crushed and extracted by solvent, produce about 60–55% oil meal. Rapeseed cake, as a residue, usually has 10–25% oil, but rapeseed meal subjected to extraction has only a few percent of the oil [13]. Seed cleaning, seed pre-conditioning, rolling, and flaking, seed cooking and pressing to mechanically remove a portion of the oil, solvent extraction (hexane) of the press-cake to eliminate the rest of the oil, desolventizing, and toasting are the significant steps of the extraction process (Fig. 3) [12]. One of the important agents that affect the quality of rapeseed meal is temperature. Inactivation of myrosinase,

3

Bioactive Phytochemicals from Rapeseed (Brassica napus) Oil Processing. . .

31

Mechanical Extrusion/ Flaking Rolls Seed Storage

Solvent Extractor

Desolventizer

Marc Pellet and Meal Storage Solvent Strippers

Seed Cleaner Crushing Rolls

Meal Cooler Meal Storage

Cooker Crude Oil Gums/Soapstock from Refining

Expeller

Degummed Crude Oil Storage Filter Centrifuge

Fig. 3 Schematic of the pre-press solvent extraction process

the enzyme that decomposes glucosinolates into toxic aglycones, is done by heating that causes to degrade of about 30–70% of them. Protein quality is affected by high temperatures, which is detrimental to monogastric since it decreases the digestibility of amino acids still; as it decreases the breakdown of ruminal protein, it is beneficial for ruminants. Nevertheless, excess thermal treatment of rapeseed meal repressed the breakdown of phytate in the rumen and led to less access to phosphorus in the diet [14]. Vapor processing also decreases the digestibility of protein in poultry. Overheating can happen within desolventizing, so temperatures should not exceed 100
C. At the end of the extraction process, the remaining oil in the rapeseed meal extracted by solvent must not exceed 2–3% [15].

2.1.2 Expeller or Cold-Extracted Rapeseed Meal Mechanical extraction of seeds that are treated by temperature produces expeller rapeseed meal. That is also known as rapeseed press-cake, canola press-cake, or double-pressed canola. Due to increasing consumer interest in cold-pressed rapeseed oil, the other method that involves pressing the seeds at low temperature (60
C) results in cold-pressed rapeseed press-cake [14]. The amount of oil remaining in these types of rapeseed meal can be very variable and typically more than 5%–20% or more [16]. These are especially worth in organic agriculture (where hexane usage is forbidden) for the protein supply. Due to heat-dependent degradation of glucosinolates followed by inactivation of mycosinase, cold-pressed canola meal may have more glucosinolates than the solvent-extracted meal [17]. By changing the processing conditions in the crushing plant, the meal quality can both increase and decrease. Minimal treatment temperatures are required for deactivating the myrosinase enzyme, which, if not deactivated, will decompose glucosinolate into their toxic metabolites (aglucones) in the animal’s gastrointestinal

32

P. Jafarian Asl and R. Niazmand

tract. The crushing process of rapeseed can also result in a thermal breakdown of 30 to 70% of the glucosinolate content in the meal [18]. Nevertheless, if temperatures remain too high for a prolonged period, a decrease in the protein quality of the meal can occur. In Canada, most crushers have very similar treatment conditions, and rapeseed meal quality is not significantly different. However, in some countries, temperatures applied during the processing of rapeseed meal can vary considerably. In such cases, it is essential for rapeseed meal consumers to monitor the protein quality of the meal regularly or check and endorse providers [19]. In addition, sometimes adding back some of the byproducts of rapeseed processing, such as gums and soapstock (high-oil ingredients), to rapeseed meal will enhance the energy content of the meal. Moreover, the quality of the meal may decline if screenings and foreign material are added. A practical component quality control program will highlight these differences in manufacturing practices.

2.1.3 Rapeseed Meal Nutrient Composition Environmental conditions during the growth of crops, harvesting conditions, and to some extent, cultivar, seed, and meal processing (mentioned in the previous section) may affect the nutrient composition of rapeseed meal. Table 1 provides the main nutritional composition of different rapeseed meal. Rapeseed meal presents a good amino acid profile for livestock feed (Table 2). As with many sources of vegetable protein, rapeseed meal is restricting in lysine, but it is considered due to its high levels of methionine and cysteine. Therefore, there is a difference between Amino acid content and protein content and can be computed by multiplying the raw protein content of the meal by the ratio of amino acid expressed as a percentage of protein indicated in Table 2. As a feedstock for cattle, for instance, Table 1 Chemical composition of rapeseed meal

Component Crude protein (N  6.25%) Oil (%) Ash Crude fiber (%) Tannins (%) Sinapine (%) Phytic acid (%) Glucosinolates (μmolg1) a

Concentrationa RM1 RM2 [20] [17] 36  2.4 36.1  1.3

RM6 [21] 36.3  0.1

RM4 [22] 39.86  0.03

RM5 [23] 37.41  0.47

3.5  2.6 6.1  2.2 12.0  3.5 1.5  0.1 1.0  0.04 3.3  1.8 7.21  1.9

11.1  0.34 6.3  0.24 10.6  0.12 nd nd nd 5.5

2.30  0.17 7.07  0.02 37.6  0.21 nd 1.13  0.04 nd 25.0% 21.0% 18.4%

0.035–0.045%

radical scavenger during oil oxidation compared to other tocopherol isomers [24]. In general, the tocopherol amount in peanut oil is affected by four factors: the oil-processing conditions, conditions used to analyze tocol components, the analytical methods, and the varietal differences of peanuts. To date, there are a limited number of studies on the health-promoting characteristics of peanut oil and peanut oil-processing by-products, which render a prospective research gap in this field. Peanut oil is linked with the enhancement of cardiovascular biomarkers such as the reduction in low-density lipoprotein (LDL)cholesterol and total triacylglycerol levels as well as the increment of high-density lipoprotein (HDL)-cholesterol level [1, 25, 26]. This could be because peanut oil is rich in unsaturated fatty acids [27]. Pelkman et al. [27] discovered that moderate consumptions of oils rich in unsaturated fatty acids (i.e., peanut oil) among overweight subjects showed an improved cardiovascular disease risk profile. In addition,

6

Bioactive Phytochemicals from Peanut Oil Processing By-products

111

regular consumption of peanuts and other oilseeds has been shown to be associated with body weight management, as demonstrated by several studies [1, 28–30]. Peanut skin is rich in A-type proanthocyanidins, whereby these bioactive compounds were discovered to inhibit hyaluronidase activity, an enzyme that increased in the presence of certain cancers [18]. In addition, resveratrol (3,5,4trihydroxystillbene), a polyphenol present in both the peanut root and skin, was found to possess chemopreventive properties [31]. Moreover, peanut skins have been utilized by traditional Chinese medicine to treat chronic hemorrhages and bronchitis [18]. In short, all the extracts and bioactive compounds from peanut oil-processing by-products possessed some health benefits to the human being. However, more research is needed to provide more conclusive evidence to support the current findings on the health benefits of the various bioactive compounds discovered thus far. This research gap is an invaluable area that warrants further investigations by scientists interested in this subject matter from all around the world.

4

Food and Nonfood Applications of Extracts and Bioactive Compounds from Peanut Oil-Processing By-Products

Yu et al. [32] investigated the impact of roasting on the functional and physicochemical traits of peanut flour processed from peanut-defatted meal. Roasting decreased the oil and water-binding capacities of the defatted flour (Table 2). This could be due to the irreversible denaturation resulted from high temperature applied during roasting that decomposed peanut protein’s hydrophilic and hydrophobic groups. Nevertheless, roasted and raw defatted peanut flours could be adopted as food emulsifiers as they contained low foaming capacity (87 mL/g). Furthermore, Yu et al. [32] reported the viability of peanut protein concentrate (PPC) by employing the defatted meal (Fig. 2), in view that PPC might be an excellent ingredient for product formulation and protein fortification. Besides, the alkali-solution and acid-isolation method was adopted to eliminate the nonprotein components from the defatted peanut meal, leading to the production of peanut protein isolate (PPI) [16]. The soluble saccharides and insoluble glycan were removed in the PPI as compared to PPC. Thus, PPI is characterized by highprotein solubility, which in turn, might potentially be utilized as a raw ingredient to prepare protein-rich bakery products and beverages [33]. Table 2 Functional traits of raw and roasted defatted peanut flour

Functional traits (mL/g) Oil binding capacity Water binding capacity Emulsifying capacity Foaming capacity Source: Yu et al. [32].

Raw 2.67 1.67 87.08 0.06

Roasted 1.67 1.00 87.50 0.03

112

S. S. Tan et al.

Fig. 2 Production of peanut protein concentrate using defatted peanut meal. Source: Tan et al. [35]

Due to the high smoke point (>150  C) nature of crude peanut oil, the oil is suitable for deep-frying [34]. Furthermore, peanut oil is often used to prepare mayonnaise, shortening, and margarine due to its pleasant nut-like aroma. In addition, peanut oil is usually used in the formulation of a vegetable ghee substitute (Vanaspati) produced in India [1]. On the other hand, either refined or crude peanut oil is commonly used in producing of soft conditioning soap with long-lasting lather traits. Furthermore, peanut oil has a high content of tocols, which is appropriate for cosmetic formulations. In summary, the extracts and bioactive compounds from peanut oil-processing by-products could be further utilized for both food and nonfood application upon subsequent formulation. Furthermore, the high numbers of peanut oil-processing by-products produced worldwide annually justify the benefit and, in turn, the necessity of more advanced technology in supporting this formulation exercise.

5

Valorization of Oil-Processing By-Products for Nonhealth Purposes (i.e., Bioenergy)

The peanut skin is rich in tannin, a bioactive compound that is well known for its metal-chelating property. Peanut skins were reported as an economical source that could be complexed and utilized to remove heavy metals from wastewater [18]. The peanut hulls are an abundant, inexpensive, and renewable resource used for

6

Bioactive Phytochemicals from Peanut Oil Processing By-products

113

incineration purposes, given the estimation of 230–300 g of peanut hull production per kg peanut [5]. The limited information available at present, particularly on the valorization of peanut oil-processing by-products, warrants the value of further investigation in this area. Furthermore, more research should be conducted to explore the possible benefits of peanut oil-processing by-products from the aspect of bioenergy to resolve the high and increasing numbers of possible environmental pollutants after peanut oil processing.

6

Conclusion

In conclusion, the understudy of peanut oil-processing by-products, particularly the bioactive phytochemicals, has contributed directly to the underutilization of all the peanut oil-processing by-products. However, the vast production and consumption of peanuts across countries worldwide render a platform for further investigation on the potential benefits of the bioactive phytochemicals from peanut oil-processing by-products. Therefore, more research contributions are required from scientists worldwide to gather stronger scientific evidence to support the health-promoting claims available at present pertaining to the extracts and bioactive compounds from peanut oil-processing by-products.

References 1. Dean LL, Davis JP, Sanders TH (2011) Groundnut (Peanut) oil. In: Gunstone FD (ed) Vegetable oils in food technology: composition, properties, and uses. Blackwell Publishing Ltd., West Sussex, pp 225–242 2. Sahdev RK (2015) Present status of peanuts and progression in its processing and preservation techniques. Agric Eng Int CIGR J 17:309–327 3. Suri K, Singh B, Kaur A, Singh N (2019) Impact of roasting and extraction methods on chemical properties, oxidative stability, and Maillard reaction products of peanut oils. J Food Sci Technol 56:2436–2445 4. International Nut and Dried Fruit (2020) Nuts and dried fruits statistical year book 2019/2020 5. Zhao X, Chen J, Du F (2012) Potential use of peanut by-products in food processing: a review. J Food Sci Technol 49(5):521–529 6. Akcali ID, Ince A, Guzel E (2006) Selected physical properties of peanuts. Int J Food Prop 9: 25–37 7. Wang Q, Liu H, Hu H, Mzimbiri R, Yang Y, Chen Y (2016) Peanut oil processing technology. In: Wang Q (ed) Peanuts: processing technology and product development. Academic Press, London, pp 63–81 8. Wang Q, Liu L, Wang L, Guo Y, Wang J (2016) Introduction. In: Wang Q (ed) Peanuts: processing technology and product development. Academic Press, London, pp 1–22 9. Olajide JO, Igbeka JC (2003) Some physical properties of groundnut kernels. J Food Eng 58: 201–204 10. Kim NK, Hung YC (1991) Mechanical properties and chemical composition of peanuts as affected by harvest date and maturity. J Food Sci 56:1378–1381 11. Bansal UK, Satija DR, Ahuja KL (1993) Oil composition of diverse groundnut (Arachis hypogaea L) genotypes in relation to different environments. J Sci Food Agric 63:17–19

114

S. S. Tan et al.

12. Grosso NR, Lamarque A, Maestri DM, Zygadlo JA, Guzman CA (1994) Fatty acid variation of runner peanut (Arachis hypogaea L.) among geographic localities from Córdoba (Argentina). J Am Oil Chem Soc 71:541–542 13. Musa ÖM (2011) Some nutritional characteristics of kernel and oil of peanut (Arachis hypogaea L.). J Oleo Sci 59:1–5 14. Arya SS, Salve AR, Chauhan S (2016) Peanuts as functional food: a review. J Food Sci Technol 53:31–41 15. Zheng L, Ren J, Su G, Yang B, Zhao M (2013) Comparison of in vitro digestion characteristics and antioxidant activity of hot- and cold-pressed peanut meals. Food Chem 141:4246–4252 16. Liu H, Shi A, Liu L, Wu H, Ma T, He X, Lin W, Feng X, Liu Y (2016) Peanut protein processing technology. In: Wang Q (ed) Peanuts: processing technology and product development. Academic Press, London, pp 83–209 17. Batal A, Dale N, Café M (2005) Nutrient composition of peanut meal. J Appl Poult Res 14:254– 257 18. Dean LL (2020) Extracts of Peanut skins as a source of bioactive compounds: methodology and applications. Appl Sci 10:8546 19. Du FY, Fu KQ (2008) Study on total flavonoids contents in peanut vines of different plant organs. Food Sci 1:137–140 20. Medina-Bolivar F, Condori J, Rimando AM, Hubstenberger J, Shelton K, O’Keefe SF, Bennet S, Dolan MC (2007) Production and secretion of resveratrol in hairy root cultures of peanut. Phytochemistry 68:1992–2003 21. Bail S, Stuebiger G, Krist S, Unterweger H, Buchbauer G (2008) Characterisation of various grape seed oils by volatile compounds, triacylglycerol composition, total phenols and antioxidant capacity. Food Chem 108:1122–1132 22. Tan CX, Chong GH, Hamzah H, Ghazali HM (2018) Characterization of virgin avocado oil obtained via advanced green techniques. Eur J Lipid Sci Technol 120:e1800170 23. Siger A, Nogala-Kalucka M, Lampart-Szczapa E (2008) The content and antioxidant activity of phenolic compounds in cold-pressed plant oils. J Food Lipids 15:137–149 24. Ananth DA, Deviram G, Mahalakshmi V, Sivasudha T, Tietel Z (2019) Phytochemical composition and antioxidant characteristics of traditional cold pressed seed oils in South India. Biocatal Agric Biotechnol 17:416–421 25. Kris-Etherton PM (1999) Monounsaturated fatty acids and risk of cardiovascular disease. Circulation 100:1253–1258 26. Kris-Etherton PM, Hu FB, Ros E, Sabaté J (2008) The role of tree nuts and peanuts in the prevention of coronary heart disease: multiple potential mechanisms. J Nutr 138:1746–1751 27. Pelkman CL, Fishell VK, Maddox DH, Pearson TA, Mauger DT, Kris-Etherton PM (2004) Effects of moderate-fat (from monounsaturated fat) and low-fat weight-loss diets on the serum lipid profile in overweight and obese men and women. Am J Clin Nutr 79:204–212 28. Coelho SB, de Sales RL, Iyer SS, Bressan J, Costa NMB, Lokko P, Mattes R (2006) Effects of peanut oil load on energy expenditure, body composition, lipid profile, and appetite in lean and overweight adults. Nutrition 22:585–592 29. Fraser GE, Sabate J, Beeson WL, Strahan TM (1992) A possible protective effect of nut consumption on risk of coronary heart disease: the Adventist health study. Arch Intern Med 152:1416–1424 30. Traoret CJ, Lokko P, Cruz ACRF, Oliveira CG, Costa NMB, Bressan J, Alfenas RCG, Mattes RD (2008) Peanut digestion and energy balance. Int J Obes 32:322–328 31. Aggarwal BB, Bhardwaj A, Aggarwal RS, Seeram NP, Shishodia S, Takada Y (2004) Role of resveratrol in prevention and therapy of cancer: preclinical and clinical studies. Anticancer Res 24:2783–2840

6

Bioactive Phytochemicals from Peanut Oil Processing By-products

115

32. Yu J, Ahmedna M, Goktepe I (2007) Peanut protein concentrate: production and functional properties as affected by processing. Food Chem 103:121–129 33. Shafiqur R, Islam A, Rahman MM, Uddin MB, Mazumder AR (2018) Isolation of protein from defatted peanut meal and characterize their nutritional profile. Chem Res J 3:187–196 34. BaselineFoundation (2019). Healthiest cooking oil comparison chart with smoke points and omega 3 fatty acid ratios [WWW Document]. https://www.jonbarron.org/diet-and-nutrition/ healthiest-cooking-oil-chart-smoke-points. Accessed 30 Apr 2021 35. Tan SS, Tan CX, Tan ST (2020) Cold pressed peanut (Arachis hypogaea L.) oil. In: Ramadan MF (ed) Cold pressed oils: green technology, bioactive compounds, functionality, and application. Academic Press, London, pp 357–364

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products Tainara Leal de Sousa, Josemar Gonc¸alves de Oliveira Filho, Mirella Romanelli Vicente Bertolo, Gabrielle Victoria Gaute´rio, Giovana Maria Navarro de Mendonc¸a, Ailton Cesar Lemes, and Mariana Buranelo Egea

Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Biocompounds of Corn Germ Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Protein and Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Lipids and Fatty Acid Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Fiber and Monomeric Sugar Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

118 121 121 122 123

T. L. de Sousa Institute of Tropical Pathology and Public Health, IPTSP – UFG, Goiás Federal University (UFG), Goiânia, Brazil J. G. de Oliveira Filho School of Pharmaceutical Sciences, São Paulo State University (UNESP), Araraquara, SP, Brazil Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, Brazil M. R. V. Bertolo São Carlos Institute of Chemistry (IQSC), University of São Paulo (USP), São Carlos, Brazil e-mail: [email protected] G. V. Gautério · A. C. Lemes School of Chemistry, Department of Biochemical Engineering, Federal University of Rio de Janeiro (UFRJ), Rio de Janeiro, RJ, Brazil e-mail: [email protected]; [email protected] G. M. N. de Mendonça School of Pharmaceutical Sciences, São Paulo State University (UNESP), Araraquara, Brazil M. B. Egea (*) Institute of Tropical Pathology and Public Health, IPTSP – UFG, Goiás Federal University (UFG), Goiânia, Brazil Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, GO, Brazil e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_7

117

118

T. L. de Sousa et al.

3 Phenolic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Carotenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

125 129 133 133

Abstract

Corn (Zea mays L.) is one of the most relevant and cultivated cereals. During the processing of corn, especially in obtaining edible oil, large quantities of by-products are generated, called corn germ oil processing by-products. In this sense, this chapter provides an overview of the main components, including phytochemical components found in corn germ oil processing by-products, to provide information and increase utilization, especially in food products. Corn oil processing by-product has a crude protein around 10.6 g 100 g
1 mainly with methionine, lysine, and tryptophan amino acids, the crude fiber of 4.6 g 100 g
1, and lipids of 1.34 g 100 g
1 primarily with linoleic and palmitic fatty acids. In addition, these by-products are a source of phenolic and carotenoid compounds that are responsible for their antioxidant activity. Thus, the synergistic action of these compounds seems to confer the biological activity of this by-product in the human body. Keywords

Carotenoids · Dietary fiber · Fatty acids · Protein · Tryptophan · Zea mays L.

1

Introduction

Corn (Zea mays L.) is one of the most relevant and cultivated cereals globally, presenting excellent adaptation to different ecosystems, being extremely important to human food and the global economy [1–3]. The structure of the corn grain is comprised of different fractions, including the pericarp (hull/bran), endosperm, germ (embryo), and the tip [4], which are used as raw material in several sectors to obtain various products [2] (Fig. 1). These products can be for (i) human consumption such as oil [5] from the germ [4], starch [6], proteins [7], and beverages [8], (ii) for animal fed [9] or (iii) for biodiesel production, among others [10]. Concerning the market, world corn production reached about 1148.50 million tons in the 2019/2020 harvest with export values close to $30 billion, demonstrating the substantial economic impact in the world. Among the largest producers are the United States, China, Brazil, Argentina, Ukraine, India, Mexico, Canada, Indonesia, and South Africa, which are responsible for up to 860,917 tons of world production [11]. The main industrial applications of corn include (i) oil production, which is predominant in the germ fraction, about up to 85% of the total corn grain oil [2, 12]; (ii) starch production that is produced from the starchy endosperm (~70% of dry matter) [13, 14]; and (iii) fuel production from the conversion of starch to ethanol using biotechnological processes [15]. During the processing of corn,

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

119

Fig. 1 Different fractions of corn and products made from each of them

Fig. 2 Generic scheme for processing corn germ to obtain refined oil and by-products sources of bioactive phytochemicals

especially in obtaining edible oil, large quantities of by-products are generated, called corn germ oil processing by-products [16] (Fig. 2). Thus, it is essential to create mechanisms to take advantage of the by-product, reduce environmental impacts, and expand access to food. Despite the global demand for food, the better use of the resources already produced and available could contribute to human food – since up to 30% of cereals

120

T. L. de Sousa et al.

are lost or wasted along the production chain – impacting the food supply and, mainly, the environment [17]. Thus, care during the production chain and, mainly, the adoption of appropriate practices for the full use of the generated by-products, could contribute to (i) reduction of waste generation; (ii) adequate distribution of food to the population; (iii) inclusion of nutritional components of the by-products in the human diet; (iv) reducing the need to increase cereal production; and (v) manufacture of products with higher added value and income generation, among others [18–21]. Different compositions are verified for corn germ oil processing by-products, mainly due to the diversity of extraction processes to which the corn is submitted. In general, it is verified that corn oil processing by-product has a dry matter content of 89.0%, crude protein around 10.6%, the crude fiber of 4.6%, ether extract close to 1.34%, in addition to calcium, phosphorus, several amino acids such as methionine, lysine, and tryptophan [22–24]. In addition, the presence of several phenolic compounds, flavonoids, and other bioactive phytochemical components are observed that confer diverse bioactivities to this by-product, including antioxidant [25] and antimicrobial [26] activities, among others. In this sense, several researches report the incorporation in animal feeds and, still, in the elaboration of various food products – in the sense of increasing the nutritional value – including the development of flour [27], cookies [28], bread [29], and pasta [30]. Furthermore, from the use of corn germ oil processing by-products, the authors reported that this raw product is expected to confer distinct technological, sensory, and nutritional properties in the final product. In this sense, this chapter provides an overview of the main components, including phytochemical components found in corn germ oil processing by-products, to provide information, and increase utilization, especially in food products. Figure 3 presents a summary of the main findings that will be discussed in this chapter.

Fig. 3 Main findings discussed in this chapter

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

121

2

Biocompounds of Corn Germ Oil Processing By-products

2.1

Protein and Amino Acids

After carbohydrates, protein is the second macronutrient found in abundance in corn, with ~6–12 g 100 g
1 protein (dry basis) located especially in the endosperm and ~72 g 100 g
1 of the total protein in the germ [31, 32]. As with other nutritional components, the protein content found in corn and the quality of its amino acids are affected by climatic conditions during harvest, genetic factors, and separation methods [33]. Corn kernel proteins include ~6 g 100 g
1 of globulins and albumin (watersoluble proteins and alkaline solution), 34 g 100 g
1 of glutens (insoluble proteins in water and 70% alcohol), and 60 g 100 g
1 of prolamins (water-insoluble proteins and soluble in alcohol 70%) [32, 34]. The endosperm has 7–10 g 100 g
1 protein, with the presence of reserve proteins of the prolamins type, called zeins. These proteins have the function of producing the protein bodies that are part of the matrix that lines the starch granules inside the endosperm and are used in the manufacture of biodegradable packaging [31, 32, 35]. Corn germ has about 12–21 g 100 g
1 predominance of protein, with albumin, globulin. Corn germ proteins have emulsifying and foaming properties and are of paramount importance for the food industry [33, 36]. The by-products generated from the manufacturing processes of corn-based products use dry, wet grinding, and distillation. Among the by-products originated are corn gluten feed, corn gluten meal, corn germ meal, and corn steep liquor, distillers dried grains, and distillers dried grains with soluble that have the following protein levels of 19.9, 64.7, 25.9, 40, 31.3, and 30.6 g 100 g
1 (dry matter), respectively [37, 38]. The percentage of amino acids (dry matter) found in corn kernels are lysine (0.28%), methionine (0.20%), cystine (0.20%), tryptophan (0.07%), threonine (0.32%), isoleucine (0.32%), leucine (1.09%), phenylalanine (0.44%), tyrosine (0.29%), valine (0.43%), histidine (0.27%), arginine (0.42%), glycine (0.35%), serine (0.43%), alanine (0.68%), aspartic acid (0.61%), glutamic acid (1.68%), and proline (0.80%) [38]. Corn has low levels of lysine and tryptophan, which interferes with the protein quality of corn. Furthermore, the concentrations of these amino acids can be affected by heat and anti-nutritional factors such as tannins and phytates [32]. The amino acid profile of corn gluten is similar to that of fresh corn, and both corn gluten feed and corn gluten meal have protein quality similar to that of soybean meal. The corn steep liquor contains large amounts of organic nitrogen, where half of this nitrogen is present in the form of free amino acids [38]. The corn germ meal has a satisfactory amount of lysine and can be helpful as a protein supplement [39]. Table 1 shows the composition of essential and non-essential amino acids in corn by-products. Due to their low cost, corn grains and their by-products are considered important sources of protein in the diet, being widely consumed [40, 41], for example, in Africa, reaching an average per capita consumption of 50 kg and

122

T. L. de Sousa et al.

Table 1 Content of essential and non-essential amino acids in corn by-productsa

Amino acid (%) Lysine Methionine Methionine + cystine Threonine Tryptophan Arginine Histidine Isoleucine Leucine Phenylalanine Valine Cystine Alanine Aspartic acid Glutamic acid Glycine Serina Tyrosine Proline a

Corn gluten feed 0.9 0.8 2.2 1.3 0.1 1.1 0.8 1.6 6.3 2.4 1.1 0.6 3.3 2.3 8.2 1.0 2.0 1.9 1.8

Corn gluten meal 0.5 0.6 0.9 1.1 0.3 0.9 0.8 1.2 4.9 1.8 1.5 0.6 2.5 1.7 6.1 0.9 1.3 1.4 3.3

Corn germ meal 1.2 0.7 0.4 0.7 0.9 1.2 0.8 0.5 0.9 0.4 0.6 0.2 1.0 1.3 1.0 1.9 0.8 0.5 1.6

Distillers’ dried grains 0.8 0.6 – 1.1 0.2 1.5 0.9 1.1 4.8 1.9 1.5 0.6 2.4 2.1 4.8 1.3 1.5 1.3 2.4

Distillers’ dried grains with solubles 0.9 0.6 – 1.1 1.2 1.3 0.8 1.1 3.5 1.5 1.5 0.6 2.2 2.0 4.9 1.2 1.3 1.2 2.3

Rodrigues et al. [43], Loy and Lundy [38], and Pereira and Oliva-Teles [40]

guaranteeing up to 80% of the total calories of individuals. However, the poor quality of protein due to the amount of essential amino acids and the consumption of corn as the main staple food has brought deficiencies, especially in children [42]. Several studies have been carried out to improve the quality of protein offered by this grain since corn is consumed in large quantities by several populations around the world, and highlight the development of species of special high-quality protein maize or QPM (quality protein maize) rich in essential amino acids lysine and tryptophan, which in turn, influence the enzymatic hydrolysis of starch, increasing its digestibility, and consequently resulting in greater energy supply when compared to common species of corn [44–47].

2.2

Lipids and Fatty Acid Composition

Corn is composed of endosperm and germ that can be used as raw material for the production of corn oil [48]. Corn oil, produced by solvent extraction or pressing, is a type of high-quality vegetable oil containing polyunsaturated fatty acid (PUFA) [49]. Although corn has great industrial potential, its grains are rich in starch and oil [12]. Fatty acids found in corn are found in the germ with a value of approximately 85% [50]. Fatty acids make up 30% of the dry weight of this structure;

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

123

approximately 95.6% of fatty acids are triglycerides, and 1.7% are free fatty acids [51]. Pure starch is industrially isolated from corn kernels by a dry or wet milling process, which allows corn germ to be the main residue [33]. The composition of the germ in lipids is 18–41% and can be influenced by the climatic conditions of the harvest, the method of separating the germ, and the genetic factors [52, 53]. Corn oil is usually extracted from the germ, it can also be recovered from whole grains, and by-product flows in ethanol production [54]. Thus, corn germ oil is used in food, cosmetic, and pharmaceutical production [12]. Lately, it has been considered raw material for biodiesel production, particularly in integrated production with ethanol [10]. Corn oil is rich in PUFA. It has a low content of saturated fatty acids, which has the advantages of being easy to digest, providing healthy fat to the heart, reducing the risk of chronic diseases, preventing macular degeneration, and is also suitable for hair treatment [55]. The main fatty acids in corn germ oil are linoleic (39–63%), oleic (20–42%), and palmitic (9–17%) [12]. According to the same authors, several methods are used for the recovery of corn germ oil, such as pressing, solvent, extraction of aqueous, enzymatic, and supercritical fluid. Corn oil production reached 1.5 million tons, mainly because it became an essential type of edible oil in China [48]. After extracting corn oil, some co-products are generated, such as corn germ bran [56]. Corn by-products are generally used as a starting raw material for feed and food products [57, 58]. Corn bran is a co-product of the commercial dry milling process for corn and can also be called corn pericarp fiber, as it originates only from that portion of the grain [59] and contains ~7.9% of total lipids [60, 61], depending on the type and regulation of equipment used in the separation of the endosperm. From the wet grind, the total amount of lipids ranged from 0.24 to 0.43 g 100 g
1 (dry matter), and the lipid content increased according to the grain size of the corn fiber [59]. Evaluating these lipids in HPLC, the authors identified sterol esters, triacylglycerols, and free fatty acids (palmitic and oleic acids). Omega-9 fatty acids are essential for reducing plasma triglycerides, VLDL, and cholesterol in diabetic patients [62]. They also improve insulin sensitivity and decrease inflammation [63]. Kokubun et al. [64] evaluated the lipid content of corn fiber gum without oil and starch, used hexane in the extraction stage of non-covalently associated lipids and the levels of lipids, and evaluated the sample using HPLC with UV and Evaporative Light Scattering detections. The authors reported a total amount of lipids of 0.017 g 100 g
1 of which 13.70 μg g
1 was palmitic acid. The authors discussed that among the factors influenced in the identification is the presence of small amounts of sodium dodecyl sulfate and other reagents used for processing.

2.3

Fiber and Monomeric Sugar Contents

Corn germ meal, the main by-product of corn germ oil extraction, has an average crude fiber and dietary fiber contents of 11.5% and 45.8%, respectively (Table 2).

1.0–1.8

8.6–11.6

1.4

10.1

38.6

10.4

48.8

11.5–16.6

14.1

31.6–44.2

8.8–13.2

42.1–60.1

42.6–53.5

45.8

9.5–13.6

11.5

NDF neutral detergent fiber, ADF acid detergent fiber

Corn germ Corn germ meal Corn bran Corn gluten meal Corn gluten feed

% Dietary fiber Average Range 22.1 19.4–24.8

% Crude fiber Average Range 4.3 3.7–4.9

Table 2 Average of fiber content in corn by-products

10.5–12.3

30.9–42.7

38.6

40.6–56.9

37.4–61.1

Range 16.7–27.4

11.6

48.7

49.1

% NDF Average 22.0

10.1

6.6

11.8

12.3

% ADF Average 5.4

7.7–12.7

5.2–7.6

10.5–13.1

11.1–14.4

Range 4.7–6.1

References Almeida et al. [76], Anderson et al. [72], Gutierrez et al. [74], Jaworski et al. [66], Jiang et al. [77], Li et al. [78], Liu et al. [75], Nandakumar et al. [79], Navarro et al. [68], Rochell et al. [73], Rojas et al. [80], de Sousa et al. [36], Lakshmi et al. [69], Weber et al. [70], Yadav et al. [81], and Zhang et al. [71]

124 T. L. de Sousa et al.

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

125

These values are comparable with other corn by-products such as corn bran (14.1% and 48.8%), corn gluten feed (10.1% and 38.6%), higher than corn germ (4.3% and 22.1%), and corn gluten meal (1.4% and 10.4%) (Table 2). In addition, a higher dietary fiber content (53.9%) was reported by a study involving ten different samples of corn germ meal [65]. On the other hand, Jaworski et al. [66] mentioned a dietary fiber content of 36.7% for corn germ meal, which is slightly lower than the average value in Table 2. Differences in fiber contents in corn germ mean can be attributed to the oil extraction method, corn variety, cultivation area, and climatic condition [67]. According to Navarro et al. [68], corn germ meal shows a higher percentage of dietary fiber than soybean (14.4%) and canola (26.4%) meals. The fiber content in corn germ meal can also be expressed as fiber soluble in neutral and acid detergents, corresponding to the average values of 49.1% and 12.3%, respectively (Table 2). Similar values are reported for corn bran and corn gluten feed, while lower contents are observed in corn germ and corn gluten meals (Table 2). Neutral (NDF) and acid (ADF) detergent fibers comprise the structural cell wall carbohydrates, and they differ in the extractive process of the fibers and the content of hemicellulose, presented only in the first one. Contents of NDF and ADF in corn germ meal have promoted its extensive use in animal diets [68–71]. Based on previous studies [66, 68, 70, 72, 73], corn germ meals present higher content of hemicellulose (34.7–43.3%) than cellulose (8.1–10.4%) and lignin (1.1–4.5%). Similar percentages are observed for corn bran, as follows: 30.1–33.3% of hemicellulose, 10.1–12.7% of cellulose, and 0.9–3.9% lignin [66, 72, 74, 75]. Regarding the sugar monomers in the soluble fraction of corn germ meal, Jaworski et al. [66] reported the presence of arabinose (2.3%), xylose (1.6%), glucose (0.7%), and galactose (0.8%). As mentioned by the authors, xylose and arabinose mainly originate from soluble arabinoxylan, whereas glucose originates from β-glucans. In the insoluble fraction, arabinose (7.1%) and xylose (7.5%) are in high quantities, agreeing with the high hemicellulose content in corn germ meal. Furthermore, glucose (0.8%), galactose (1.7%), and mannose (0.4) are present in smaller amounts. Similarly, Gutierrez et al. [74] show that monomeric sugars in the soluble fraction of corn germ meal are mainly composed of arabinose (5.4%), xylose (3.5%), and glucose (1.5%). However, the insoluble fraction of corn germ meal shows high amounts of these sugar monomers, as follows: 10.4% of arabinose, 9.9% of xylose, and 10.8% of glucose.

3

Phenolic Compounds

The major phenolic compounds present in corn are flavonoids and phenolic acids. Corn can present an average of 282 mg of gallic acid equivalent (GAE) 100 g
1 of dry weight (DW) of total phenolic content (TPC), and this content may vary according to the variety of the corn [82]. Among the water-soluble flavonoids, anthocyanins stand out as being the most prevalent in purple corn, such as perlargonidin-3-glucoside, cyanidin-3-glucoside, delphinidin-3-glucoside, among

126

T. L. de Sousa et al.

others [83]. Among the phenolic acids present in corn flour, the predominant ones are cis and trans-ferulic, p-coumaric, and syringic acids, responsible for sour, bitter, and astringent taste [84, 85]. The phenolic compounds mentioned above are still present in high concentrations in the so-called by-products of the industrial processes of removing the germ from corn and producing low-fat finished products. In particular, the corn germ, which has been attracting attention due to its oil content, is a good source of free and bounded phenolics [86–88]. Moreover, this high phenolic content is maintained even in the corn germ meal, another by-product from oil extraction from the germ. Thus, for example, Smuda et al. [25] compared the TPC of the three main by-products from corn: bran, germ, and germ meal; while the average phenolic content of the bran was around 1764 mg GAE 100 g
1 DW, that of the germ was 946 mg GAE 100 g
1 DW, and that of the germ meal was 1021 mg GAE 100 g
1 DW (Table 3). It is also important to note that there are different methods of extracting phenolics and different solvents used for this purpose, which can also affect the composition of the extracts obtained. Regardless of the method chosen, however, it is necessary to employ low-cost and environmentally friendly strategies, which respect the principles of green chemistry and make the process of recovering by-products economically and environmentally viable; the simplicity of the extraction process, as well as its efficiency, must also be considered [86, 87]. Smuda et al. [25] analyzed the effects of using four different solvents in the extraction of corn by-products; in relation to the germ meal, it can be said that the order of TPC extraction was: acetone < distilled water < methanol < ethanol, in a range of values from 638 to 1356 mg GAE 100 g
1 DW (Table 3). The greater efficiency of ethanol in the extraction of phenolics may be related to the greater solubility of some high molecular weight phenolics in ethanol than in water; the polarity of the extracted compounds and their affinity for the solvent are also decisive factors for the efficiency of the extraction [89]. Burlini et al. [86] compared different strategy germ extraction of white corn germ and yellow corn germ: ultrasound-assisted extraction (UAE), extraction using alkaline hydrolysis, alkaline hydrolysis associated with sonication, and enzymatic hydrolysis. In both corn germs, the UAE extracts showed the highest yields (about 12%), followed by the extracts obtained by alkaline hydrolysis + sonication (about 5%) and by alkaline hydrolysis (about 3%). Enzymatic hydrolysis was the extraction method with lower yields (less than 1%) in both corn germs. Despite the higher yields demonstrated by UAE, the alkaline extracts showed the highest TPC values, and for both germs, the association of sonication improved the content of phenolics (844 mg GAE g
1 dry extract for yellow corn germ extract and 742 mg GAE g
1 dry extract for white corn germ extract) (Table 3). One of the greatest interests in the phenolic compounds present in the corn by-products is their antioxidant potential, composed of a series of simultaneous mechanisms that involve the scavenging of free radicals, minimizing the formation of peroxides, and the chelation of metal ions [90]. As the origin of the by-product

Corn germs (yellow and white) Corn bran, corn germ and corn germ meal

Corn germplasm

Byproduct Corn germ protein flour

–

–

Major phenolics p-hydroxybenzoic, p-hydroxyphenylacetic, vanillic, o-coumaric, syringic, p-coumaric, ferulic, caffeic acids –

Extraction with distilled water, ethanol, methanol, and acetone, separately, water bath, 50  C

Six different solvent mixtures: methanol: water (7:3), acetone: water (7:3), acetone: methanol:water (4:4:2), acetone:ethanol:water (4:5:1), acetone: methanol (1:1), and aqueous:ethanol (95%) with a solvent-corn ratio of 10:1, sonic bath UAE, alkaline, alkaline + sonication, enzymatic

Extraction method Extraction with diethyl ether-ethyl acetate, 1:1, 3

–

1764 mg GAE 100 g
1 DW for bran, 946 mg GAE 100 g
1 DW for germ, 1021 mg GAE 100 g
1 DW for germ meal

42.8–844 mg GAE g
1 dried extract

26.1–71.3% RSA for bran, 27.6–52.1% RSA for germ, 25.7–59.5% RSA form germ meal

IC50 ¼ 11.4–680 μg mL
1

21.2 μmol Trolox g
1 DW

120 mg GAE 100 g
1 DW

–

15.9–636 mg ferulic acid g
1 dried extract

AOA –

TPC –

Concentration 121.5 ppm

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products (continued)

Smuda et al. [25]

Burlini et al. [86]

SyeddLeón et al. [92]

References Huang and Zayas [91]

Table 3 Type of corn by-product, major identified phenolics, mode of extraction, concentration, total phenolic content (TPC) and antioxidant activity (AOA)

7 127

Byproduct Yellow dent corn flour

Major phenolics p-hydroxybenzoic acid, ( p-hydroxyphenyl) acetic acid, Vannilic acid, Protocatechuic acid, Syringic acid, quinic acid, cis-pcoumaric acid, trans-pcoumaric acid, cisferulic acid, transferulic acid, Caffeic acid, cis-ferulic acid, trans-sinapic acid, Chlorogenic acid

Table 3 (continued)

Extraction method Extraction 6 with ethanol:acetone:water (7:7:6)

Concentration 78.7 ppm total

TPC –

AOA –

References Sosulski et al. [84]

128 T. L. de Sousa et al.

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

129

and the extraction process can alter its phenolic composition, its antioxidant activity can also be affected, and therefore a quantitative assessment is essential. Smuda et al. [25] compared the antioxidant activity of different cereal milling by-products, including bran, germ, and corn germ meal, using three different antioxidant tests: DPPH(2,2-Diphenyl-1-picrylhydrazyl), ABTS (2.20-Azino-bis (3-ethylbenzthiazoline-6-sulphonic acid)), and FRAP (ferric reducing antioxidant power). In general, the methanolic extracts of these by-products showed the highest antioxidant potential, regardless of the essay with the high antioxidant potential of the corn bran of 71% RSA (radical scavenging activity) using the DPPH method. Regarding the corn germ meal, it can be said that it was the only corn by-product to present significantly equal and high antioxidant activity values for both DPPH and ABTS radicals for the methanolic extract (59.1% and 59.5% RSA, respectively) (Table 3).

4

Carotenoids

Carotenoids are phytochemicals with several biological effects such as protection against cancer, cardiovascular diseases, degenerative macular diseases, immunomodulatory effect, and anti-inflammatory and photoprotective activities [25, 93, 94]. Thus, these bioactive molecules contribute to the prevention and therapeutic effects, act as enhancers in health, and therefore are very attractive to the food, pharmaceutical, and cosmetics industries [95, 96]. Carotenoids are derived from the C40 acyclic isoprenoid lycopene, which is classified as a tetraterpene. There are about 700 known carotenoids divided into carotenes such as α-carotene, β-carotene, and lycopene, and xanthophylls that are the oxygenated carotenoids lutein, zeaxanthin, and β-cryptoxanthin. In addition, some carotenoids are promoters of vitamin A, such as β-carotene, α-carotene, and β-cryptoxanthin [97]. Most of the carotenoids present in nature are in trans form, and because these compounds have a long chain of conjugated double bonds in their structure, carotenoids can absorb light and can eliminate singlet oxygen [98]. Table 4 presents a survey of the main carotenoids present in by-products of oil extraction from corn and the methods used for their extraction, and their main bioactive properties. Corn germ oil processing by-products seem to have significant levels of carotenoids, higher than by-products of other cereals. Smuda et al. [25] related total carotenoids content of 57.9 and 32 μg g
1 for corn germ flour and corn bran, respectively, which was higher than what was found for wheat bran (4.2 μg g
1). Xanthophylls (zeaxanthin and lutein) differ from other carotenoids in that they do not have the conversion mechanism to vitamin A. The xanthophyll average content in whole corn (yellow) was 20.09 μg g
1 (sum of β-cryptoxanthin, zeaxanthin, and lutein), in the residue was 1.88 μg g
1 (sum of β-cryptoxanthin, zeaxanthin, and lutein), in defatted corn (yellow) was 17.9 μg g
1 (sum of β-cryptoxanthin, zeaxanthin, and lutein) (Table 4). The highest value found for total xanthophyll content was

130

T. L. de Sousa et al.

Table 4 Types of corn by-products, mode of extraction, and the type of identified carotenoid By-product Whole corn, residue, and deoiled corn

Corn

Corn milling by-products (bran, germ, germ meal)

Cornmeal

Extraction method 600 mg of sample was mixed with 6 ml of BHT – 1% EtOH, kept at 85  C for 5 min. 120 mL of 80% KOH was homogenized, and the temperature was maintained for 10 min, followed by cooling in an ice bath. The mixture was homogenized with 3 mL of deionized water and 3 mL of hexane and centrifuged at 2500 rpm for 10 min. The supernatant was removed and washed twice with hexane, and the residual hexane was evaporated by nitrogen flow injection for 2 h. Evaluated in HPLC The extraction was carried out in an Erlenmeyer, using the solvent: solids ratio of 4:1 (4 L of 70% ethanol/kg of corn), at a temperature of 40  C for 30 min (a heated stirring plate was used for temperature control and constant mixing, to avoid any precipitation), this mixture was filtered, stored at 40  C at a stable temperature, to avoid precipitation, the extract was microfiltered, and the reading was done in spectroscopy at 450 nm 1 g of sample was mixed with n-butanol and distilled water (8:2) and 10 mL of butyl alcohol and maintained for 16 h. The filtration of the mixture was performed, and the reading was performed on a 440 nm spectrophotometer 1 g of sample was homogenized with 5 mL of methanol and maintained for 16 h. The mixture was centrifuged with the addition of 5 mL of THF, centrifuged which was recovered by mixing with methanol (3).

Carotenoids β-cryptoxanthin, lutein, and zeaxanthin

References Moros et al. [94]

β-cryptoxanthin

Kale et al. [93]

β-carotene

Smuda et al. [25]

trans-lutein, trans-β-carotene, transzeaxanthin, L/Z, cis-lutein, cis-zeaxanthin, cryptoxanthin

Perry et al. [100]

(continued)

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

131

Table 4 (continued) By-product

Extraction method

Carotenoids

References

The extract was resuspended in 500 mL of ethanol; the extraction was repeated ethanol:MTBE (2:1, v/v) or MTBE:methanol (2:1, v/v), stirred for 30 s, and evaluated using HPLC BHT butylated hydroxytoluene, HPLC high-performance liquid chromatography, THF tetrahydrofuran, MTBE methyl tert-butyl ether, L/Z Ratio of all-trans lutein to all-trans-zeaxanthin

a

b

c

d

Fig. 4 Chemical structure of the main carotenoids found in the by-products from the extraction of oil from corn germ: β-carotene (a), β-cryptoxanthin (b), lutein (c), and zeaxanthin (d)

for corn gluten meal (145.9 μg g
1), which was superior to dry-grind corn (16.1 μg g
1), inbred corn A632 (12.6 μg g
1), and White corn (0.12 μg g
1) [94]. Figure 4 shows the chemical structure of the main carotenoids found in the by-products of oil extraction from corn germ. Salazar-López et al. [99] reported β-carotene values for corn germ of 20 μg g
1, which was higher than that reported for rice (5 μg g
1 DW) and oat wheat (15 μg g
1 DW). However, β-carotene appears to be in smaller amounts when the oil processing by-product is evaluated. Perry et al. [100] evaluated the carotenoid profile in corn

132

T. L. de Sousa et al.

by-products and found for cornmeal (yellow): trans-zeaxanthin (531 μg 100 g
1), cis-lutein (63 μg 100 g
1), cis-zeaxanthin (25 μg 100 g
1), cryptoxanthin (46 μg 100 g
1), trans-β-carotene (29 μg 100 g
1), cis-β-carotene (not detected), α-carotene (not detected), and trans-lutein (0.01 μg 100 g
1). The same author’s related carotenoid profile for corn meal (white) including trans-zeaxanthin (13 μg 100 g
1) and trans-lutein (13 μg 100 g
1). The extraction of carotenoids carried out in the matrices allows the use of these compounds in foods due to their appeal for healthiness, food additives, medicines, and cosmetics. However, one of the significant challenges is the elimination of the solvent used in the extraction process. The presence of these solvents ends up making it impossible to use the carotenoid extract. In addition, another difficulty is the low efficiency in the extraction process related to the difficulty of the solvent molecules in penetrating plant tissues, which makes it impossible to solubilize the carotene found in the chromoplast structure [97]. Several extraction methods can be used to extract bioactive compounds from by-products, such as ultrasound, pulsed electric field, microwave-assisted extraction (MAE), pressurized liquid extraction (PLE), pressurized fluid/solvent extraction or solvent extraction accelerated (ASE), supercritical fluid extraction (SCF), enzyme assisted extraction (EAE), high hydrostatic pressure/high-pressure extraction (HHP/HPE), and instant controlled pressure drop (DIC) extraction [101]. For the extraction of carotenoids from the by-products of corn oil extraction, chemical methods have been used using solvents such as methanol [93], n-butanol [25], ethanol/hexane, hydroxide potassium [94], and methanol [93] (Table 3). There are some studies that related the biological activities of the main carotenoids detected in corn by-products (Table 4). There are studies that suggest that the multiplication of cancer cells was effectively suppressed by β-carotene [102, 103]. In another work, it was verified that these pigments are able to activate cellular communication and the immune system [104]. Few studies demonstrated that β-cryptoxanthin, when supplemented, is able to increase alkaline phosphatase activity and calcium content in metaphyseal tissue and cortical bone, which leads to minimizing the chances of osteoporosis [105]. β-Cryptoxanthin is recognized as a precursor to pro-vitamin A, which also positively regulated communication between cells and also demonstrated improved immunity [106, 107]. There are several biological effects of carotenoids that are described in the literature, including the fact that they are: anti-inflammatory, immunomodulatory, anticancer, inhibition of mutagenesis and antioxidant [108]. Studies have shown that a diet with an intake of 6 mg/day of lutein and zeaxanthin would be related to reducing the risk of age-related macular degeneration (AMD); a longitudinal study was carried out with plasma zeaxanthin, demonstrating that the risk of cataracts has been reduced, making it clear that both lutein and zeaxanthin are essential antioxidant compounds for delaying the onset of cataracts and AMD [109], in the study carried out by Stahl [110], where epidemiological studies are investigated, this provided some evidence that the consumption of zeaxanthin and lutein in the diet, may be related to a reduced risk of age-related macular degeneration. This disease has a high incidence in the elderly.

7

5

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

133

Conclusion

The processing of corn produces the corn germ oil processing by-products that have high protein content with essential amino acids and essential fatty acids like linoleic and palmitic fatty acids. In addition, these by-products are also a source of phenolic compounds such as cis and trans-ferulic, p-coumaric, and syringic acids and carotenoid compounds such as β-carotene, β-cryptoxanthin, lutein, and zeaxanthin compounds that are responsible for their antioxidant activity. Thus, the synergistic action of these compounds seems to confer the biological activity of this by-product in the human body.

References 1. García-Lara S, Serna-Saldivar SO (2019) Chapter 1. Corn history and culture. In: SernaSaldivar SO (ed) Corn, 3rd edn. AACC International Press, Oxford, UK, pp 1–18. https://doi. org/10.1016/B978-0-12-811971-6.00001-2 2. Rajendran A, Singh N, Mahajan V, Chaudhary DP, Kumar RS (2012) Corn oil: an emerging industrial product, vol 8. Technical Bulletin, New Delhi 3. Cai Z, Wei Y, Zhang H, Rao P, Wang Q (2021) Holistic review of corn fiber gum: structure, properties, and potential applications. Trends Food Sci Technol. https://doi.org/10.1016/j.tifs. 2021.03.034 4. Naves MMV, Castro MVL, Mendonça AL, Santos GG, Silva MS (2011) Corn germ with pericarp in relation to whole corn: nutrient contents, food and protein efficiency, and protein digestibility-corrected amino acid score. Food Sci Technol 31:264–269 5. Savva SC, Kafatos A (2016) Vegetable oils: dietary importance. In: Caballero B, Finglas PM, Toldrá F (eds) Encyclopedia of food and health. Academic, Oxford, UK, pp 365–372. https:// doi.org/10.1016/B978-0-12-384947-2.00709-1 6. Rahimi A, Naserian AA, Valizadeh R, Tahmasebi AM, Dehghani H, Sung KI, Nejad JG (2020) Effect of different corn processing methods on starch gelatinization, granule structure alternation, rumen kinetic dynamics and starch digestion. Anim Feed Sci Technol 268:114572. https://doi.org/10.1016/j.anifeedsci.2020.114572 7. Kongo-Dia-Moukala JU, Zhang H (2011) Defatted corn protein extraction: optimization by response surface methodology and functional properties. Am J Food Technol 6:870–881 8. Pauline M, Alexandre O, Andoseh BK, Abeline MTS, Agatha T (2017) Production technique and sensory evaluation of traditional alcoholic beverage based maize and banana. Int J Gastron Food Sci 10:11–15. https://doi.org/10.1016/j.ijgfs.2017.09.003 9. Ovi FK, Hauck R, Grueber J, Mussini F, Pacheco WJ (2021) Effects of prepelleting whole corn inclusion on feed particle size, pellet quality, growth performance, carcass yield, and digestive organ development and intestinal microbiome of broilers between 14 and 42 d of age. J Appl Poult Res 30(1):100113. https://doi.org/10.1016/j.japr.2020.10.012 10. Veljković VB, Biberdžić MO, Banković-Ilić IB, Djalović IG, Tasić MB, Nježić ZB, Stamenković OS (2018) Biodiesel production from corn oil: a review. Renew Sust Energ Rev 91:531–548. https://doi.org/10.1016/j.rser.2018.04.024 11. FDA (2019) Production quantities of maize by country. Food and Agriculture Organization (FAO). http://www.fao.org/. Accessed 29 Mar 2021 12. Stamenković OS, Kostić MD, Tasić MB, Djalović IG, Mitrović PM, Biberdžić MO, Veljković VB (2020) Kinetic, thermodynamic and optimization study of the corn germ oil extraction process. Food Bioprod Process 120:91–103. https://doi.org/10.1016/j.fbp.2019.12.013 13. Bustillos-Rodríguez JC, Tirado-Gallegos JM, Ordóñez-García M, Zamudio-Flores PB, Ornelas-Paz JJ, Acosta-Muñiz CH, Gallegos-Morales G, Páramo-Calderón DE, Rios-Velasco

134

T. L. de Sousa et al.

C (2019) Physicochemical, thermal and rheological properties of three native corn starches. Food Sci Technol 39:149–157 14. Zilic S, Milasinovic M, Terzic D, Barac M, Ignjatovic-Micic D (2011) Grain characteristics and composition of maize specialty hybrids. Span J Agric Res 9(1):230–241 15. Prajapati V, Trivedi U, Patel KC (2015) Bioethanol production from the raw corn starch and food waste employing simultaneous saccharification and fermentation approach. Waste Biomass Valor 6(2):191–200. https://doi.org/10.1007/s12649-014-9338-z 16. Dijkstra AJ (2016) Vegetable oils: types and properties. In: Caballero B, Finglas PM, Toldrá F (eds) Encyclopedia of food and health. Academic, Oxford, UK, pp 381–386. https://doi.org/ 10.1016/B978-0-12-384947-2.00706-6 17. FAO (2016) Chapter 1. Cereals and us: time to renew an ancient bond. In: Murra W (ed) Save and grow in practice: maize, rice, wheat. Food and Agriculture Organization of the United Nations, Rome, p 111 18. Chen C, Chaudhary A, Mathys A (2020) Nutritional and environmental losses embedded in global food waste. Resour Conserv Recycl 160:104912. https://doi.org/10.1016/j.resconrec. 2020.104912 19. Lemes AC, Sala L, Ores JC, Braga AR, Egea MB, Fernandes KF (2016) A review of the latest advances in encrypted bioactive peptides from protein-rich waste. Int J Mol Sci 17(6):1–24. https://doi.org/10.3390/ijms17060950 20. Lemes AC, Alvares GT, Egea MB, Brandelli A, Kalil SJ (2016) Simultaneous production of proteases and antioxidant compounds from agro-industrial by-products. Bioresour Technol 222:210–216. https://doi.org/10.1016/j.biortech.2016.10.001 21. Lemes AC, Paula LC, Oliveira Filho JG, Prado DMF, Medronha GA, Egea MB (2020) Bioactive peptides with antihypertensive property obtained from agro-industrial byproducts – mini review. Austin J Nutr Metab 7(3):1–5 22. Soares LLP, Silva CA, Pinheiro JW, Fonseca NAN, Cabrera L, Hoshi EH, Silva MAA, Canteri RC (2004) Farelo de gérmen de milho desengordurado na alimentação de suínos em crescimento e terminação. Rev Bras Zootec 33:1768–1776 23. Moreira I, Ribeiro CR, Furlan AC, Scapinello C, Kutschenko M (2002) Utilização do farelo de germe de milho desengordurado na alimentação de suínos em crescimento e terminação: digestibilidade e desempenho. Rev Bras Zootec 31:2238–2246 24. Brunelli SR, Pinheiro JW, Silva CA, Fonseca NAN, Oliveira DD, Cunha GE, Souza LFA (2006) Inclusão de farelo de gérmen de milho desengordurado na alimentação de frangos de corte. Rev Bras Zootec 35:1349–1358 25. Smuda SS, Mohsen SM, Olsen K, Aly MH (2018) Bioactive compounds and antioxidant activities of some cereal milling by-products. J Food Sci Technol 55(3):1134–1142. https://doi. org/10.1007/s13197-017-3029-2 26. Ahmad N, Hussain M, Sameen A, Saeed F, Hussain A, Imran A, Ahmed Z, Rehman A, Manzoor MF, Karrar E (2021) Extraction and enrichment of maize bran cell wall in bread and its textural, and microbial assessment. Food Sci Nutr 1(1):1–8. https://doi.org/10.1002/fsn3. 2147 27. Granito M, Guerra M (1996) The use of deffated corn germ in flour manufactured to bakery products. Arch Latinoam Nutr 45:322–328 28. Froes LO, Falqueto MAO, Castro MVL, Naves MMV (2012) Gérmen com pericarpo de milho desengordurado na formulação de biscoitos tipo cookie. Ciênc Rural 42:744–750 29. Siddiq M, Nasir M, Ravi R, Butt MS, Dolan KD, Harte JB (2009) Effect of defatted maize germ flour addition on the physical and sensory quality of wheat bread. LWT Food Sci Technol 42(2):464–470. https://doi.org/10.1016/j.lwt.2008.09.005 30. Lucisano M, Casiraghi EM, Barbieri R (1984) Use of defatted corn germ flour in pasta products. J Food Sci 49(2):482–484. https://doi.org/10.1111/j.1365-2621.1984.tb12446.x 31. Shukla R, Cheryan M (2001) Zein: the industrial protein from corn. Ind Crop Prod 13(3):171–192 32. Ai Y, Jane JL (2016) Macronutrients in corn and human nutrition. Compr Rev Food Sci Food Saf 15(3):581–598

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

135

33. Espinosa-Pardo F, Savoire R, Subra-Paternault P, Harscoat-Schiavo C (2020) Oil and protein recovery from corn germ: extraction yield, composition and protein functionality. Food Bioprod Process 120:131–142 34. Anderson B, Almeida H (2019) Corn dry milling: processes, products, and applications. In: Corn. Elsevier, New York, pp 405–433 35. Egea M, Oliveira Filho J, Braga A, Di-Medeiros M, Lemes A, Frías J (2021) Zein based blends and composites. In: Sanjay MR (ed) Biodegradable polymers, blends and composites. Elsevier, New York 36. de Sousa MF, Guimarães RM, de Oliveira AM, Barcelos KR, Carneiro NS, Lima DS, Dos Santos DC, de Aleluia BK, Fernandes KF, Lima MCPM (2019) Characterization of corn (Zea mays L.) bran as a new food ingredient for snack bars. LWT Food Sci Technol 101:812–818 37. Nisa MU, Khan M, Sarwar M, Lee W, Lee H, Ki K, Ahn B, Kim H (2006) Influence of corn steep liquor on feeding value of urea treated wheat straw in buffaloes fed at restricted diets. Asian Australas J Anim Sci 19(11):1610–1616 38. Loy DD, Lundy EL (2019) Chapter 23. Nutritional properties and feeding value of corn and its coproducts. In: Serna-Saldivar SO (ed) Corn, 3rd edn. AACC International Press, Oxford, UK, pp 633–659. https://doi.org/10.1016/B978-0-12-811971-6.00023-1 39. Sharma S, Gupta J, Nagi H, Kumar R (2012) Effect of incorporation of corn byproducts on quality of baked and extruded products from wheat flour and semolina. J Food Sci Technol 49 (5):580–586 40. Pereira T, Oliva-Teles A (2003) Evaluation of corn gluten meal as a protein source in diets for gilthead sea bream (Sparus aurata L.) juveniles. Aquac Res 34(13):1111–1117 41. Yiğit M, Bulut M, Ergün S, Güroy D, Karga M, Kesbiç O, Yilmaz S, Acar Ü, Güroy B (2012) Utilization of corn gluten meal as a protein source in diets for gilthead sea bream (Sparus aurata L.) juveniles. J Fish Sci 6(1):63–73 42. Raffi M (2018) Sustainable agriculture and the role of biofertilizers. J Acad Ind Res 7(4):51 43. Rodrigues P, Rostagno H, Albino L, Gomes P, Barboza W, Santana R (2001) Energy values of millet, corn and corn byproducts, determined with broilers and adult cockerels. Rev Bras Zootec 30(6):1767–1778 44. Hasjim J, Srichuwong S, Scott M, J-l J (2009) Kernel composition, starch structure, and enzyme digestibility of opaque-2 maize and quality protein maize. J Agric Food Chem 57(5): 2049–2055 45. Lopes J, Shaver R, Hoffman P, Akins M, Bertics S, Gencoglu H, Coors J (2009) Type of corn endosperm influences nutrient digestibility in lactating dairy cows. J Dairy Sci 92(9):4541– 4548 46. Larson J, Hoffman P (2008) A method to quantify prolamin proteins in corn that are negatively related to starch digestibility in ruminants. J Dairy Sci 91(12):4834–4839 47. Ladely S, Stock R, Klopfenstein T, Sindt M (1995) High-lysine corn as a source of protein and energy for finishing calves. J Anim Sci 73(1):228–235 48. Xu L-L, Wen Y-Q, Liu Y-L, Ma Y-X (2018) Occurrence of deoxynivalenol in maize germs from North China Plain and the distribution of deoxynivalenol in the processed products of maize germs. Food Chem 266:557–562 49. Bhat R, Reddy K (2017) Challenges and issues concerning mycotoxins contamination in oil seeds and their edible oils: updates from last decade. Food Chem 215:425–437 50. Rojas L, Molina I, Cortez E, Londoño N, Osorio A, López A, García M (2017) Physicochemical properties of nixtamalized corn flours with and without germ. Food Chem 220:490–497 51. Watson S (2003) Description, development, structure, and composition of the corn kernel. In: Corn: chemistry and technology, 2nd edn. American Association of Cereal Chemists, St Paul, pp 69–106 52. Johnston D, McAloon A, Moreau R, Hicks K, Singh V (2005) Composition and economic comparison of germ fractions from modified corn processing technologies. J Am Oil Chem Soc 82(8):603–608

136

T. L. de Sousa et al.

53. Navarro S, Capellini M, Aracava K, Rodrigues C (2016) Corn germ-bran oils extracted with alcoholic solvents: extraction yield, oil composition and evaluation of protein solubility of defatted meal. Food Bioprod Process 100:185–194 54. Zabed H, Boyce A, Sahu J, Faruq G (2017) Evaluation of the quality of dried distiller’s grains with solubles for normal and high sugary corn genotypes during dry-grind ethanol production. J Clean Prod 142:4282–4293 55. Shende D, Sidhu G (2015) Effect of process parameters on the oil recovery of maize germ oil. Int J Sci Adv Res Technol 1(8):147–154 56. Yadav S, Malik A, Pathera A, Islam R, Sharma D (2016) Development of dietary fibre enriched chicken sausages by incorporating corn bran, dried apple pomace and dried tomato pomace. Nutr Food Sci 46(1):16–29 57. Aniołowska M, Steininger M (2014) Determination of trichothecenes and zearalenone in different corn (Zea mays) cultivars for human consumption in Poland. J Food Compos Anal 33(1):14–19 58. Escobar J, Lorán S, Giménez I, Ferruz E, Herrera M, Herrera A, Ariño A (2013) Occurrence and exposure assessment of Fusarium mycotoxins in maize germ, refined corn oil and margarine. Food Chem Toxicol 62:514–520 59. Yadav M, Johnston D, Hotchkiss A Jr, Hicks K (2007) Corn fiber gum: a potential gum arabic replacer for beverage flavor emulsification. Food Hydrocoll 21(7):1022–1030 60. de Almeida A, Santos N, de Lima T, Santana R, de Oliveira FJ, Peres D, Egea M (2021) Pigment bioproduction by Monascus purpureus using corn bran, a byproduct of the corn industry. Biocatal Agric Biotechnol 32:101931 61. Aktaş K, Akın N (2020) Influence of rice bran and corn bran addition on the selected properties of tarhana, a fermented cereal based food product. LWT Food Sci Technol 129:109574 62. Brehm B, Lattin B, Summer S, Boback J, Gilchrist G, Jandacek R, D’alessio D (2009) One-year comparison of a high-monounsaturated fat diet with a high-carbohydrate diet in type 2 diabetes. Diabetes Care 32(2):215–220 63. Finucane O, Lyons C, Murphy A, Reynolds C, Klinger R, Healy N, Cooke A, Coll R, McAllan L, Nilaweera K (2015) Monounsaturated fatty acid-enriched high-fat diets impede adipose NLRP3 inflammasome-mediated IL-1β secretion and insulin resistance despite obesity. Diabetes 64(6):2116–2128 64. Kokubun S, Yadav M, Moreau R, Williams P (2014) Components responsible for the emulsification properties of corn fibre gum. Food Hydrocoll 41:164–168 65. Shi M, Liu Z, Wang H, Shi C, Liu L, Wang J, Li D, Zhang S (2019) Determination and prediction of the digestible and metabolizable energy contents of corn germ meal in growing pigs. Asian Australas J Anim Sci 32(3):405 66. Jaworski N, Lærke H, Bach Knudsen K, Stein H (2015) Carbohydrate composition and in vitro digestibility of dry matter and nonstarch polysaccharides in corn, sorghum, and wheat and coproducts from these grains. J Anim Sci 93(3):1103–1113 67. Lakshmi R, Kumari K, Reddy P (2017) Corn germ meal (CGM)-potential feed ingredient for livestock and poultry in India – a review. Int J Livest Res 7(8):39–50 68. Navarro D, Bruininx E, de Jong L, Stein H (2018) The contribution of digestible and metabolizable energy from high-fiber dietary ingredients is not affected by inclusion rate in mixed diets fed to growing pigs. J Anim Sci 96(5):1860–1868 69. Lakshmi R, Gloridoss R, Singh K, Murthy H (2015) Effect of inclusion of corn germ meal in diets of colored (Raja-II) broilers with phytase enzyme supplementation. Bioscan 10:1581– 1584 70. Weber T, Trabue S, Ziemer C, Kerr B (2010) Evaluation of elevated dietary corn fiber from corn germ meal in growing female pigs. J Anim Sci 88(1):192–201 71. Zhang Z, Liu Z, Zhang S, Lai C, Ma D, Huang C (2019) Effect of inclusion level of corn germ meal on the digestible and metabolizable energy and evaluation of ileal AA digestibility of corn germ meal fed to growing pigs. J Anim Sci 97(2):768–778

7

Bioactive Phytochemicals from Corn (Zea mays) Germ Oil Processing By-products

137

72. Anderson P, Kerr B, Weber T, Ziemer C, Shurson G (2012) Determination and prediction of digestible and metabolizable energy from chemical analysis of corn coproducts fed to finishing pigs. J Anim Sci 90(4):1242–1254 73. Rochell S, Kerr B, Dozier W III (2011) Energy determination of corn co-products fed to broiler chicks from 15 to 24 days of age, and use of composition analysis to predict nitrogen-corrected apparent metabolizable energy. Poult Sci 90(9):1999–2007 74. Gutierrez N, Serão NV, Kerr B, Zijlstra R, Patience JF (2014) Relationships among dietary fiber components and the digestibility of energy, dietary fiber, and amino acids and energy content of nine corn coproducts fed to growing pigs. J Anim Sci 92(10):4505–4517 75. Liu P, Zhao J, Guo P, Lu W, Geng Z, Levesque C, Johnston L, Wang C, Liu L, Zhang J (2017) Dietary corn bran fermented by Bacillus subtilis MA139 decreased gut cellulolytic bacteria and microbiota diversity in finishing pigs. Front Cell Infect Microbiol 7:526 76. Almeida F, Petersen G, Stein H (2011) Digestibility of amino acids in corn, corn coproducts, and bakery meal fed to growing pigs. J Anim Sci 89(12):4109–4115 77. Jiang X, Cui Z, Wang L, Xu H, Zhang Y (2020) Production of bioactive peptides from corn gluten meal by solid-state fermentation with Bacillus subtilis MTCC5480 and evaluation of its antioxidant capacity in vivo. LWT Food Sci Technol 131:109767 78. Li M, Tian X, Jin R, Li D (2018) Preparation and characterization of nanocomposite films containing starch and cellulose nanofibers. Ind Crop Prod 123:654–660 79. Nandakumar S, Ambasankar K, Ali S, Syamadayal J, Vasagam K (2017) Replacement of fish meal with corn gluten meal in feeds for Asian seabass (Lates calcarifer). Aquac Int 25(4): 1495–1505 80. Rojas O, Liu Y, Stein H (2013) Phosphorus digestibility and concentration of digestible and metabolizable energy in corn, corn coproducts, and bakery meal fed to growing pigs. J Anim Sci 91(11):5326–5335 81. Yadav MP, Hicks KB, Johnston DB, Hotchkiss AT Jr, Chau HK, Hanah K (2016) Production of bio-based fiber gums from the waste streams resulting from the commercial processing of corn bran and oat hulls. Food Hydrocoll 53:125–133 82. Siyuan S, Tong L, Liu R (2018) Corn phytochemicals and their health benefits. Food Sci Human Wellness 7(3):185–195 83. Ramos-Escudero F, Muñoz A, Alvarado-Ortíz C, Alvarado A, Yánez J (2012) Purple corn (Zea mays L.) phenolic compounds profile and its assessment as an agent against oxidative stress in isolated mouse organs. J Med Food 15(2):206–215 84. Sosulski F, Krygier K, Hogge L (1982) Free, esterified, and insoluble-bound phenolic acids. 3. Composition of phenolic acids in cereal and potato flours. J Agric Food Chem 30(2):337–340 85. Maga J, Lorenz K (1973) Taste threshold values for phenolic acids which can influence flavor properties of certain flours, grains and oilseeds. Cereal Sci Today 18(10):326–328 86. Burlini I, Grandini A, Tacchini M, Maresca I, Guerrini A, Sacchetti G (2020) Different strategies to obtain corn (Zea mays L.) germ extracts with enhanced antioxidant properties. Nat Prod Commun 15(1):1934578X20903562 87. Chemat F, Vian M, Cravotto G (2012) Green extraction of natural products: concept and principles. Int J Mol Sci 13(7):8615–8627 88. Das AK, Singh V (2015) Antioxidative free and bound phenolic constituents in pericarp, germ and endosperm of Indian dent (Zea mays var. indentata) and flint (Zea mays var. indurata) maize. J Funct Foods 13:363–374 89. Do Q, Angkawijaya A, Tran-Nguyen P, Huynh L, Soetaredjo F, Ismadji S, Ju Y-H (2014) Effect of extraction solvent on total phenol content, total flavonoid content, and antioxidant activity of Limnophila aromatica. J Food Drug Anal 22(3):296–302 90. Zhou K, Yu L (2004) Antioxidant properties of bran extracts from Trego wheat grown at different locations. J Agric Food Chem 52(5):1112–1117 91. Huang C, Zayas J (1991) Phenolic acid contributions to taste characteristics of corn germ protein flour products. J Food Sci 56(5):1308–1310

138

T. L. de Sousa et al.

92. Syedd-León R, Orozco R, Álvarez V, Carvajal Y, Rodríguez G (2020) Chemical and antioxidant characterization of native corn germplasm from two regions of Costa Rica: a conservation approach. Int J Food Sci 2020:2439541 93. Kale A, Zhu F, Cheryan M (2007) Separation of high-value products from ethanol extracts of corn by chromatography. Ind Crop Prod 26(1):44–53 94. Moros E, Darnoko D, Cheryan M, Perkins E, Jerrell J (2002) Analysis of xanthophylls in corn by HPLC. J Agric Food Chem 50(21):5787–5790 95. Bigliardi B, Galati F (2013) Innovation trends in the food industry: the case of functional foods. Trends Food Sci Technol 31(2):118–129 96. Martins N, Ferreira I (2017) Wastes and by-products: upcoming sources of carotenoids for biotechnological purposes and health-related applications. Trends Food Sci Technol 62:33–48 97. Arvayo-Enríquez H, Mondaca-Fernández I, Gortárez-Moroyoqui P, López-Cervantes J, Rodríguez-Ramírez R (2013) Carotenoids extraction and quantification: a review. Anal Methods 5(12):2916–2924 98. Garavelli M, Bernardi F, Olivucci M, Robb M (1998) DFT study of the reactions between singlet-oxygen and a carotenoid model. J Am Chem Soc 120(39):10210–10222 99. Salazar-López N, Ovando-Martínez M, Domínguez-Avila J (2020) Cereal/grain by-products. In: Campos-Vega R, Oomah BD, Vergara-Castañeda HA (eds) Food wastes and by-products: nutraceutical and health potential. Wiley, Hoboken, pp 1–34. https://doi. org/10.1002/9781119534167.ch1 100. Perry A, Rasmussen H, Johnson E (2009) Xanthophyll (lutein, zeaxanthin) content in fruits, vegetables and corn and egg products. J Food Compos Anal 22(1):9–15 101. Kumari B, Tiwari B, Hossain M, Brunton N, Rai D (2018) Recent advances on application of ultrasound and pulsed electric field technologies in the extraction of bioactives from agroindustrial by-products. Food Bioprocess Technol 11(2):223–241 102. Gallicchio L, Boyd K, Matanoski G, Tao X, Chen L, Lam T, Shiels M, Hammond E, Robinson K, Caulfield L (2008) Carotenoids and the risk of developing lung cancer: a systematic review. Am J Clin Nutr 88(2):372–383 103. Murakoshi M, Nishino H, Satomi Y, Takayasu J, Hasegawa T, Tokuda H, Iwashima A, Okuzumi J, Okabe H, Kitano H (1992) Potent preventive action of α-carotene against carcinogenesis: spontaneous liver carcinogenesis and promoting stage of lung and skin carcinogenesis in mice are suppressed more effectively by α-carotene than by β-carotene. Cancer Res 52(23):6583–6587 104. Singh A, Ahmad S, Ahmad A (2015) Green extraction methods and environmental applications of carotenoids – a review. RSC Adv 5(77):62358–62393 105. Yamaguchi M (2008) β-Cryptoxanthin and bone metabolism: the preventive role in osteoporosis. J Health Sci 54(4):356–369 106. Burri B (2015) Beta-cryptoxanthin as a source of vitamin A. J Sci Food Agric 95(9): 1786–1794 107. San Millán C, Soldevilla B, Martín P, Gil-Calderón B, Compte M, Pérez-Sacristán B, Donoso E, Peña C, Romero J, Granado-Lorencio F (2015) β-Cryptoxanthin synergistically enhances the antitumoral activity of oxaliplatin through ΔNP73 negative regulation in colon cancer. Clin Cancer Res 21(19):4398–4409 108. Rao A, Rao L (2007) Carotenoids and human health. Pharmacol Res 55(3):207–216 109. Abdel-Aal E-S, Akhtar H, Zaheer K, Ali R (2013) Dietary sources of lutein and zeaxanthin carotenoids and their role in eye health. Nutrients 5(4):1169–1185 110. Stahl W (2005) Macular carotenoids: lutein and zeaxanthin. Nutr Eye 38:70–88

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil Processing By-products Josemar Gonc¸alves de Oliveira Filho, Mirella Romanelli Vicente Bertolo, Gabrielle Victoria Gaute´rio, Giovana Maria Navarro de Mendonc¸a, Ailton Cesar Lemes, and Mariana Buranelo Egea Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Macrocomponents of Cottonseed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Proteins and Amino Acids of Cottonseed Oil Processing By-products . . . . . . . . . . . . . 2.2 Lipids and Fatty Acids of Cottonseed Oil Processing By-products . . . . . . . . . . . . . . . . . 2.3 Carbohydrate and Fiber of Cottonseed Oil Processing By-products . . . . . . . . . . . . . . . . . 3 Phenolic Content of Cottonseed Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

140 142 143 144 146 147 149 150

J. G. de Oliveira Filho School of Pharmaceutical Sciences, São Paulo State University (UNESP), Araraquara, SP, Brazil Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, Brazil M. R. V. Bertolo São Carlos Institute of Chemistry (IQSC), University of São Paulo (USP), São Carlos, Brazil e-mail: [email protected] G. V. Gautério · A. C. Lemes Department of Biochemical Engineering, School of Chemistry, Federal University of Rio de Janeiro (UFRJ), Rio de Janeiro, Brazil e-mail: [email protected]; [email protected] G. M. N. de Mendonça School of Pharmaceutical Sciences, São Paulo State University (UNESP), Araraquara, Brazil M. B. Egea (*) Institute of Tropical Pathology and Public Health, IPTSP – UFG, Goiás Federal University (UFG), Goiânia, Brazil Instituto Federal de Educação, Ciência e Tecnologia Goiano, Rio Verde, GO, Brazil e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_8

139

140

J. G. de Oliveira Filho et al.

Abstract

Cotton (Gossypium hirsutum L.) is an important species used as a source of fiber for the textile industry and oil for biodiesel agro-industries. The main by-product generated from the oil extraction from cottonseed is cottonseed oil processing by-products, mainly used as animal feed or fertilizer. Although cottonseed by-product has a low price, one of the limitations of its application is its toxicity due to the presence of gossypol, which limits its use for human consumption. However, techniques for removing gossypol have been developed, allowing the application of cottonseed by-products and their fractions in food products. Therefore, research on the application of cottonseed by-product is a new advance and of great relevance for utilizing a by-product generated in significant quantities by the industry and is still undervalued. The by-product of cotton oil extraction has a high content of compounds of interest, such as protein (~41.2 g 100 g
1), fiber (~16.1 g 100 g
1), ash (~5.9 g 100 g
1), potassium (~1.5 g 100 g
1), phosphorus (~1.0 g 100 g
1), iron (~7.6 mg kg
1), and zinc (~56.4 mg kg
1) and also high composition in bioactive phytochemicals, including phenolic compounds and other molecules with biological potentials, such as antioxidant, antimicrobial, antihypertensive, neuroprotective, and antidepressant properties, among others. In this sense, this chapter provides an overview of the main components, including phytochemical components found in cottonseed oil processing by-products, to provide information and increase utilization, especially in food products. Keywords

Bioactive peptides · Gossypol · Phenolic compounds · Sunflower meal

1

Introduction

Cotton is produced in more than 30 countries and is considered one of the main non-food species in the world due to its various industrial and agricultural applications [1]. In addition, this species has been used for over 5000 years as an essential source of fiber for the textile industry [2]. Among the more than 50 cotton species found in nature, Gossypium hirsutum represents ~90–97% of all world cotton production due to its high productivity and adaptability under different environmental conditions [3, 4]. The processing of cotton generates lint and seed as marketable products. Cotton seeds represent ~60% of the biomass of cotton bolls and are considered low-cost raw materials since the primary source of the cotton crop is lint. In addition, the cottonseed, due to its high lipid content, is used as a raw material for the extraction of vegetable oil widely used for the production of biodiesel [5]. To obtain the cottonseed oil (Fig. 1), the fiber is first removed from the seeds. Then, the oil is extracted from the seeds, using pressing, and what remains as a residue of this process is called fat cottonseed meal [6]. After pressing, the fatty cottonseed meal is subjected to a new extraction process using chemical solvents such as petroleum ether, hexane, and methanol, generating the defatted cottonseed meal as residue.

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

141

Cottonseed

Fiber withdrawal

Crushing Defatted cottonseed meal

Whole cottonseed meal

Solvent extraction Cottonseed oil

Fig. 1 Defatted cottonseed meal production from the cottonseed oil industry Fig. 2 Cottonseed meal main by-product of cottonseed oil extraction

Cottonseed meal (Fig. 2) is the main by-product of cottonseed oil extraction and is intended primarily for use as fertilizer or animal feed [5]. In this sense, the use of agro-industrial by-products as raw materials for the development of new products could add value to these by-products that are underutilized, increasing the profit of cotton producers and processors. Potential value-added products include the use of chemical components such as protein hydrolysates with antioxidant, antimicrobial, and antihypertensive activities [7, 8], which can be applied to bioplastics and films [9], adhesives for wood [10], and absorbent hydrogel [11].

142

J. G. de Oliveira Filho et al.

Oil extraction

Proteins Fiber

Source

Lipid Ash

Oil processing byproduct

Phenolic compounds

Functional foods

Fig. 3 The potential use of cottonseed oil processing by-products

The presence of gossypol, a toxic polyphenolic alkaloid, limits the use of cottonseed meal and its components for food applications, resulting in the underutilized waste that is intended mainly for animal feed since ruminants can degrade this compound during the ruminal fermentation [12]. Fortunately, gossypol can be removed by solvent extraction and reduced to less than 0.045% – during the preparation of an edible cottonseed protein – a concentration less than the upper limit set by the Food and Drug Administration [13]. In this sense, food products, such as meat products, baked goods, and cereals, have been developed using cottonseed meal and its cotton protein concentrates such as meat, bakery, and cereal products (Fig. 3) [14, 15]. Thus, the cottonseed meal and its fractions, with low gossypol content, due to their high nutritional value should be considered as potential alternative ingredients for incorporation into food products and may improve the nutritional and functional profile of these foods, in addition, to contribute by minimizing the negative environmental impact associated with the disposal of these by-products in the environment. This chapter provides an overview of the main components, including phytochemicals found in cottonseed oil processing by-products, as a way of providing information for their application in food and other products of interest.

2

Macrocomponents of Cottonseed Oil Processing By-products

Table 1 presents an average of the macro- and micronutrients of cottonseed oil by-products. The available literature highlights the high content of protein (~41.2 g 100 g
1), fiber (~16.1 g 100 g
1), ash (~5.9 g 100 g
1), potassium (~1.5 g 100 g
1), phosphorus (~1.0 g 100 g
1), iron (~7.6 mg kg
1), zinc (~56.4 mg kg
1), and other nutrients. Cottonseed meal seems to be a good source of minerals such as potassium, phosphorus, iron, and zinc [18], showing values higher than those reported for wheat flour [19] and cashew nut flour [20]. Due to its

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

Table 1 Average of macro- and micronutrients of cottonseed oil by-producta

Composition Protein (g 100 g
1) Carbohydrate (g 100 g
1) Crude fiber (g 100 g
1) Lipids (g 100 g
1) Ash (g 100 g
1) Potassium (g 100 g
1) Magnesium (g 100 g
1) Sodium (g 100 g
1) Phosphorus (g 100 g
1) Copper (mg kg
1) Iron (mg kg
1) Manganese (mg kg
1) Zinc (mg kg
1)

Average 41.2 42.5 16.1 2.2 5.9 1.5 0.6 0.1 1.0 12.4 72.6 21.0 56.4

143 Range 29.2–58.7 40.0–52.2 11.5–27.0 0.3–6.2 5.3–5.9 1.2–1.7 0.56–0.57 0.01–0.1 0.9–1.1 11.0–13.0 53.0–100.0 17.5–23.0 52.5–61.0

a

He et al. [5, 16, 17], Cheng and Hardy [18], Oliveira Filho et al. [7], and Egea et al. [8]

high nutritional value, the by-product of cottonseed oil extraction has demonstrated the bioactive potential discussed in this chapter. Potassium is an essential mineral that supports nerve function and muscle contraction, maintains a regular heartbeat, and moves nutrients into human cells [21]. Phosphorus plays an essential role in forming bones and teeth and contributes to how the body uses carbohydrates and fats and in the production of proteins for the growth, maintenance, and repair of cells and tissues [22]. Iron is essential in immune function, cognitive development, temperature regulation, and metabolism [23]. Zinc participates in cell division, gene expression, and physiological processes such as growth and development, genetic transcription, cell death, acting as a stabilizer for membrane structures and cell components. In addition, zinc participates in immune function and cognitive development [24].

2.1

Proteins and Amino Acids of Cottonseed Oil Processing By-products

Approximately 70% of the proteins (Table 1) found in cottonseed meals are soluble, and the main ones are albumin and globulin [25], where the vicillin and legumin families are the main components of the protein fraction. The proteins extracted from the cotton by-product have activities of antioxidant (30.3–32.4% inhibition of DPPH radical and 0.11–0.13 mg TE/mg sample by the FRAP method), antimicrobial (12.7–15.0% growth inhibition of Colletotrichum gloeosporioides and 4.8–5.4% growth inhibition of Staphylococcus aureus), and antihypertensive (89.9–97.9% of ACE inhibitory) [7, 8]. The amino acid profile of cottonseed meal is composed of the essential amino acids such as arginine (4.46–5.00%), histidine (1.06–1.20%), isoleucine (1.18–1.34%), leucine (2.18–2.46%), lysine (1.68–1.90%),

144

J. G. de Oliveira Filho et al.

methionine (0.57–0.63%), phenylalanine (1.97–1.25%), threonine (1.17–1.30%), tryptophan (0.42–0.47%), and valine (1.63–1.88%), as well as non-essential amino acids such as alanine (145–1.64%), aspartic acid (3.33–3.82%), cysteine (0.69–1.50%), glutamic acid (7.29–8.26%), glycine (1.50–1.70%), proline (1.33–1.51%), serine (1.35–1.56%), and tyrosine (1.04–1.18%) [18]. The physicochemical properties of cottonseed meal proteins can be affected by the method used for oil extraction. Ma et al. [26] studied the physicochemical properties of proteins isolated from cottonseed meal after extraction with hot-pressed solvent, cold-pressed solvent, and subcritical fluid. Proteins extracted using hot-pressed solvent showed relatively more β leaf (38.3–40.5%) and less β turn (22.2–25.8%) and α helix (15.8–19.5%), indicating the presence of highly denatured protein molecules. Proteins extracted using cold-pressed solvent and subcritical fluid exhibited high water/oil absorption capacity, emulsification capacity, surface hydrophobicity, and fluorescence intensity, suggesting that proteins have potential as functional ingredients in the food industry. Proteins from the by-product of cotton oil extraction can be used for peptide production through enzymatic hydrolysis and microbial fermentation and have demonstrated several biological activities [7, 8, 27]. Gao et al. [27] produced peptides with high antioxidant capacity (DPPH method, inhibition of linoleic acid autoxidation, and scavenging effect on radical superoxide) using in vitro enzymatic hydrolysis of cottonseed meal proteins using the Neutrase enzyme. Sun et al. [28] produced bioactive peptides from the fermentation of cottonseed meal proteins with Bacillus subtilis BJ-1. The hydrolysate had an amino acid profile composed mainly of glutamic acid (211.7 g kg
1), aspartic acid (81.4 g kg
1), and arginine (97.5 g kg
1), resulting in antioxidant activity dependent on concentration by DPPH methods, hydroxyl radical activity, metal chelating capacity, and reducing power with IC50 values of 3.41, 3.28, 1.80, and 1.66 mg mL
1, respectively. Oliveira Filho et al. [7] demonstrated that hydrolysate protein from the cottonseed by-product hydrolyzed using commercial microbial proteins Alcalase®, Neutrase®, and Flavorourme® after thermal pretreatment could have antioxidant activity evaluated by the DPPH and FRAP methods, antihypertensive properties (99.5%), and antimicrobial activity against Colletotrichum gloeosporioides and Staphylococcus aureus. The proteins and amino acids present in the by-product of cottonseed oil extraction have the potential for several applications in the food, pharmaceutical, agrochemical, and cosmetic industries, allowing a noble application of this component.

2.2

Lipids and Fatty Acids of Cottonseed Oil Processing By-products

In quality and quantity, lipids can vary according to different cottonseed varieties, growing conditions, and processing methods used. Cottonseed meal shows low-fat content ranging from 0.3% to 3.7% [5, 18, 29, 30]. In a study involving 12 samples from five cottonseed meals, the lipid contents from ether extraction achieved values between 0.4% and 1.2% [26]. On the other hand, higher lipid contents in cottonseed meals, i.e., 6.2%, 7.9%, and 10.2%, were observed by Oliveira Filho et al. [7],

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

145

Tavares-Samay et al. [31], and Dadgar et al. [32], respectively. Glandless cottonseed meal also showed a high crude fatty percentage (14.5%) [33]. Based on the average proximal composition of cottonseed meals (Table 1), the lipid content is comparable with the contents in sunflower and soybean by-products [30, 34, 35]. Among the saturated fatty acids (SFAs) in cottonseed meals, the palmitic acid is present in more expressive amounts, followed by the stearic acid (Table 2). The oleic acid also stands out among the monounsaturated fatty acids (MUFA) in the cottonseed meal. Meanwhile, linoleic acid, a member of the polyunsaturated fatty acids (PUFA) group, comprises nearly 60% of the total fatty acids in cottonseed meals. The percentages of stearic, palmitic, oleic, and linoleic acids in the cottonseed by-product reflect the amounts of these in the cottonseed oil (Table 3). The high level of linoleic acid in the oil and the meal (Table 3) can be responsible for the low Table 2 Composition of fatty acids in cottonseed meal Fatty acid

References [30]

% Saturated fatty acid (SFA) C14:0 C15:0 C16:0 C17:0 C18:0 C20:0 C21:0 C22:0 C24:00 % Monounsaturated fatty acids (MUFA) C16:1 C18:1ω9 C18:1ω7 % Polyunsaturated fatty acids (PUFA) 18:2ω6 18:3ω3 20:5ω3 22:6ω3

[33]

Myristic Pentadecylic Palmitic Heptadecanoic Stearic Arachidic Heneicosylic Behenic Lignoceric

0.46 0.03 19.54 – 2.43 0.36 0.05 – –

0.52

Palmitoleic Oleic Vaccenic

0.38 13.44 –

0.52 15.37 0.83

Linoleic Linolenic Eicosapentaenoic Docosahexaenoic

61.76 1.24 0.16 0.15

57.40 0.25 – –

21.79 0.09 2.3 0.27 0.20 0.04

Table 3 Comparison of an average of fatty acids in cottonseed oil and meal

Material Cottonseed oil Cottonseed meal

Average of fatty acid (%) C16: C18: C18: C18: 0 0 1ω9 2ω6 24.79 2.56 18.95 51.25 20.67

2.37

14.41

59.58

References Kouser et al. [36], Matthäus and Musazcan Özcan [37]; and Okonkwo and Okafor [38] Delgado et al. [33] and Yu et al. [30]

146

J. G. de Oliveira Filho et al.

oxidative stability of these materials. On the other hand, the inclusion of a low-cost source rich in PUFA, such as cottonseed meals, can contribute to their lipid profile in food products and diets. Some studies have been performed aiming to include lipid-rich by-products of some products, evaluating their effectiveness in modulating the lipid profile of the meal. Especially for cottonseed meals, studies have been shown that its addition in diets for ruminants and poultry contributes positively to the lipid composition of meat [30, 39, 40]. In comparison to the whole seed, the cottonseed meal has similar levels of palmitic (25.52%) and stearic (2.84%) acids and higher levels of linoleic acid (43.26%). In addition, some cottonseeds have higher contents of vaccenic acid (C18:1ω7) than oleic acid (C18:1ω9) depending on their variety [41], which can eventually impact cottonseed meal composition. Cottonseed oil presents three primary cyclopropenoid fatty acids (CPFAs) -dihydrosterculic, malvalic, and sterculic acids-, which are considered antinutritional compounds [42]. Sterculic and malvalic acids are found in meals after oil extraction of seeds, and their level depends on the amount of residual oil in the meal, which is about 0.01% [43]. The analysis of six varieties of cottonseed meal demonstrated that the concentration of CPFAs in this by-product is low, with averages varying between 55 and 88 μg/g for sterculic acid, 76–131 μg/g for malvalic acid, and 30–51 μg/g for dihydrosterculic acid [44].

2.3

Carbohydrate and Fiber of Cottonseed Oil Processing By-products

The cottonseed carbohydrate content, especially fiber, comes mainly from two components: the hull and the remaining lint from the cotton harvesting process. According to the USDA [45], the average carbohydrate content found in the partially defatted cottonseed meal is 38.43 g/100 g. However, the percentage composition of crude fiber in cottonseed meals varies from 7% to 25% [46–50]. Tang et al. [51] evaluated the effects of fermentation in solid-state of cottonseed meal by B. subtilis to improve the nutritional value of the by-product; regarding the composition of crude fiber, there was a reduction from 102.1 to 90.3 g kg
1 (10.2–9.0%) after fermentation, a fact that the authors associated with a possible production of cellulase by the fermenting bacteria [50, 51]. Regardless of the reduction, however, the dietary fiber composition of cottonseed meal remained higher than that of soybean meal (62.1 g kg
1), by-product that the authors wished to replace [51]. In general, the content of dietary fiber in the cottonseed meal will depend on both the original characteristics of the seed itself (with or without lint) and the process of extracting the oil from the seed, which can occur using mechanical or solvent extractions [52]. Moreover, the fiber content can also be expressed as the acid (ADF) and neutral (NDF) detergent fiber, which differs in the extractive process of the fibers where hemicellulose content can be determined only by NDF. Usually,

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

147

both ADF and NDF contents decrease from ~37% to 27% and ~26% to 17%, respectively, after extracting the oil from the cottonseed [46]. As NDF detects hemicellulose, its value tends to be higher than that of ADF. Tavares-Samay et al. [31] reported values of 435.6 and 318 g kg
1 of NDF and ADF (43.5% and 31.8%), respectively, for cottonseed meals. He et al. [5] characterized the percentage of NDF, ADF, and acid detergent lignin in glanded and glandless cottonseed meal and their water-soluble and insoluble fractions. These authors reported the order of NDF > ADF > ADL for these values for both types of meals, and in the water-soluble portion no fibers were detected. Glanded seed meal showed a NDF percentage significantly higher than the glandless seed meal (11.5% and 7.88%, respectively). He et al. [5] identified and quantified seven other carbohydrates in the cottonseed meals and their soluble and insoluble isolates using anionic chromatography coupled with amperometric detection. The order of quantification of the carbohydrates for glanded meal that were similar to those found for the glandless meal was: galactose (4.43%), arabinose (4.40%), glucose (4.39%), xylose (1.93%), rhamnose (0.74%), mannose (0.61%), and fucose (0.07%). Regarding the soluble and insoluble fractions, the presence of the seven carbohydrates differed between the samples, with the insoluble fraction showing more arabinose, rhamnose, and xylose. The high content of dietary fiber found in the by-product of cottonseed oil extraction, and the other carbohydrates present in its composition, demonstrate the potential of this by-product to improve the nutritional and functional quality, increasing the availability of fiber of food products.

3

Phenolic Content of Cottonseed Oil Processing By-products

Agro-industrial by-products are generated in large quantities and can be an important source of many phytochemicals such as phenolic compounds [53]. Cottonseed meal, the main by-product of cottonseed oil extraction, showed a value of 1.5 mg gallic acid equivalent g
1 DW, 0.15% (w/w) of phenolic compounds in its composition [54]. The main phenolic compounds identified in the cottonseed meal were kaempferol (113 μg g
1) (Fig. 4a), naringenin (178 μg g
1) (Fig. 4b), rutin (209 μg g
1) (Fig. 4c), and gossypol (2 g 100 g
1) (total and free) (Fig. 4d) [54]. As described in Table 4, the levels of free gossypol reported for cottonseed are higher than those found for cottonseed meals. The consumption of phenolic compounds has been associated with beneficial effects on human health [53]. Kaempferol has demonstrated activities neuroprotective [63]; antidepressant for interfering with the inhibition capacity of monoamine oxidase enzymes [64]; and antiproliferative in cancer cells of the lung, leukemia, prostate, oral cavity, and colon [65]. Furthermore, studies have already reported the positive effect of kaempeferol in diseases such as liver damage, obesity, and diabetes [66, 67]. Furthermore, this compound has anti-inflammatory properties and has been used to treat many diseases induced by acute and chronic inflammation,

148

J. G. de Oliveira Filho et al.

a

b

c

d

Fig. 4 Chemical structure of phenolic compounds: kaempferol (a), naringenin (b), rutin (c), and gossypol (d) Table 4 Gossypol mean values in cottonseed and/or its by-products Cottonseed by-product Cottonseed meal (gossypol free)

Amount (mg kg
1) ~1235.99

Cottonseed meal (gossypol total) Cottonseed (gossypol free)

~3948.27 ~2446.92

References Salas et al. [55], He et al. [5], Gilani et al. [56], Qian et al. [29], Kumar et al. [57], Conceição et al. [58], Câmara et al. [59], and Tegtmeier et al. [60] Salas et al. [55], Qian et al. [29], He et al. [5], Grewal et al. [61], and Câmara et al. [59] Conceição et al. [58] and Knutsen et al. [62]

such as intervertebral disc degeneration and colitis, postmenopausal bone loss, and acute lung injury [68]. Naringenin has demonstrated broad biological effects on human health such as antioxidant, antitumor, antibacterial, antiadipogenic, and cardioprotective effects [69, 70]. It has also been reported that this compound could decrease lipid peroxidation and protein carbonyl biomarkers, promote carbohydrate metabolism, increase antioxidant defenses, eliminate reactive oxygen species, has modulated immune system activity, and exert anti-inflammatory effects [71, 72]. A great property of modulating the signaling pathways related to the metabolism of fatty acids has also been reported, which favors the oxidation of fatty acids, impairs the accumulation of lipids in the liver, and, therefore, prevents the accumulation of lipids in the plasma [73, 74], in addition to efficiently impairing the accumulation of lipids and lipoproteins in the plasma [74]. Rutin has properties to prevent neurodegenerative, cardiovascular, vasoprotective diseases [75–77], Parkinson’s disease, Alzheimer’s disease, myocardial

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

149

infarction, and chronic venous insufficiency [78], and anti-inflammatory, antimicrobial, antitumor, antiasthmatic, antioxidant [79], antihypertensive, antithrombogenic, antidepressant [78], antidiabetic [80], and antiallergic [81] activities. Gossypol (1,10 ,6,60 ,7,70 -hexahydroxy-5,50 -diisopropry 1-3,30 -dimethyl-[2,20 binapthalene]-8,80 -dicarboxaldehyde) is a polyphenolic compound present in all cotton species and all parts of the plant such as cotton leaves, stems, seeds, and flower buds [43]. This phenolic aldehyde shows antioxidant activity produced by pigment glands as a defense mechanism against pathogens, pests, and an environmental adapter for the plant [82, 83]. Gossypol has different important biological activities, such as contraceptive, antiviral, antimicrobial, antiparasitic, antitumor, and antioxidant [84]. Because it is a nonspecific enzyme inhibitor, thus altering cell division, gossypol started to be used to treat endometriosis [83] and control cancer, mainly of the breast and genitals, presenting good results [85]. This compound is also used as a fertility control agent due to its toxicity to sperm [86]. However, from a food standpoint, gossypol is the main limiting factor for the use of cottonseed meal in food, as depending on its quantity, it can be toxic, and its ingestion can cause liver damage (hepatotoxicity), anemia, poisoning, and interruption of reproduction (affects fertility and embryogenesis) [87]. Therefore, the Food and Drug Administration (FDA) established a limit of consumption of free gossypol of 450 mg kg
1 in products for human consumption and ingredients, and the FDA and WHO define the maximum allowed of 12,000 mgkg–1 of total gossypol [88]. To ensure the ingestion of gossypol-free products, technological processes can be carried out to minimize toxic effects such as heat treatment, extrusion process, gamma radiation treatment, or electron beam irradiation [89]. For example, Romero et al. [90] demonstrated that the processing of cottonseed meal with ozone was able to degrade 56% (homogenized) and 25% (static) of free gossypol. In another study, Neto et al. [91] demonstrated that the physical treatment (autoclaving) could exert a detoxification effect of 96% of the free gossypol without affecting the crude protein content. Furthermore, the fermentation process for 6 days using the microorganisms Ganoderma lucidum CC351, Panus lecomtei CC40, Pleurotus ostreatus CC389, Pleurotus sapidus CC28, and Pycnoporus sanguineus CC400 allowed a 99.6% detoxification; however, there was a reduction in crude protein content. The presence of these phenolic compounds resulted in high antioxidant activity (~60.72%) – measured in terms of DPPH radical scavenging activity (RSA) [41, 57] – indicating potential use as a natural antioxidant, mainly due to its antioxidant activity in meats submitted to the cooking process [15].

4

Conclusion

The by-product of the extraction of oil from cottonseed is a valuable source of biomolecules with high nutritional value and bioactive properties, mainly concerning the content of proteins that are a source for obtaining bioactive peptides, fatty acids, fibers, and phenolic compounds, mainly kaempferol, naringenin, rutin, and gossypol. Furthermore, the by-product of extracting oil from cottonseed with

150

J. G. de Oliveira Filho et al.

low gossypol content can be used in food production to increase the nutritional and functional value of food products, contributing to reducing waste generation. In this chapter, we demonstrate that the by-product of extracting oil from cottonseed and its fractions can be used in isolation (such as proteins, phenolic compounds, fibers, etc.) or as a raw material to enrich food products and as a source of bioactive ingredients for the cosmetic and pharmaceutical industries. Furthermore, the cotton by-product and its fractions demonstrated an essential role in producing compounds with bioactivity and functionality.

References 1. Rojo-Gutiérrez E, Buenrostro-Figueroa JJ, López-Martínez LX, Sepúlveda DR, Baeza-Jiménez R (2020) Biotechnological potential of cottonseed, a by-product of cotton production. In: Zakaria Z, Aguilar C, Kusumaningtyas R, Binod P (eds) Valorisation of agro-industrial residues – volume II: non-biological approaches, Applied environmental science and engineering for a sustainable future. Springer, New York 2. Dugan M (2009) Cotton. J Agric Food Inf 10(2):92–101. https://doi.org/10.1080/ 10496500902802742 3. Avci U, Pattathil S, Singh B, Brown V, Hahn M, Haigler C (2013) Cotton fiber cell walls of Gossypium hirsutum and Gossypium barbadense have differences related to loosely-bound xyloglucan. PLoS One 8(2):e56315 4. Nix A, Paull C, Colgrave M (2017) Flavonoid profile of the cotton plant, Gossypium hirsutum: a review. Plants 6(4):43 5. He Z, Zhang H, Olk D (2015) Chemical composition of defatted cottonseed and soy meal products. PLoS One 10(6):e0129933 6. Panagiotopoulos I, Pasias S, Bakker R, De Vrije T, Papayannakos N, Claassen P et al (2013) Biodiesel and biohydrogen production from cotton-seed cake in a biorefinery concept. Bioresour Technol 136:78–86 7. Oliveira Filho J, Rodrigues J, Valadares A, de Almeida A, Valencia-Mejia E, Fernandes K et al (2021) Bioactive properties of protein hydrolysate of cottonseed byproduct: antioxidant, antimicrobial, and angiotensin-converting enzyme (ACE) inhibitory activities. Waste Biomass Valor 12(3):1395–1404 8. Egea M, Oliveira Filho J, Lemes A, Valencia-Mejia E, Fernandes K, de Figueiredo Sousa H et al (2020) Bioactive properties of protein hydrolysate of cottonseed byproduct: antioxidant, antimicrobial, and angiotensin-converting enzyme (ACE) inhibitory activity. FASEB J 34(S1):1 9. Oliveira Filho J, Rodrigues J, Valadares A, Almeida A, Lima T, Takeuchi K et al (2019) Active food packaging: alginate films with cottonseed protein hydrolysates. Food Hydrocoll 92:267– 275. https://doi.org/10.1016/j.foodhyd.2019.01.052 10. He Z, Chapital D, Cheng H, Dowd M (2014) Comparison of adhesive properties of water- and phosphate buffer-washed cottonseed meals with cottonseed protein isolate on maple and poplar veneers. Int J Adhes Adhes 50:102–106 11. Zhang B, Cui Y, Yin G, Li X, You Y (2010) Synthesis and swelling properties of hydrolyzed cottonseed protein composite superabsorbent hydrogel. Int J Polym Mater 59(12):1018–1032 12. González J, Faría-Mármol J, Rodríguez C, Ouarti M, Alvir M, Centeno C (2006) Protein value for ruminants of a sample of whole cottonseed. Anim Sci 82(1):75–81 13. Gerasimidis K, Fillou D, Babatzimcpoulou M, Tassou K, Katsikas H (2007) Preparation of an edible cottonseed protein concentrate and evaluation of its functional properties. Int J Food Sci Nutr 58(6):486–490 14. Zhuge Q, Posner E, Deyoe C (1988) Production study of a low-gossypol protein product from cottonseed meal. J Agric Food Chem 36(1):153–155

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

151

15. Rhee K, Ziprin Y, Calhoun M (2001) Antioxidative effects of cottonseed meals as evaluated in cooked meat. Meat Sci 58(2):117–123 16. He Z, Cheng H, Chapital D, Dowd M (2014) Sequential fractionation of cottonseed meal to improve its wood adhesive properties. J Am Oil Chem Soc 91(1):151–158 17. He Z, Klasson K, Wang D, Li N, Zhang H, Zhang D et al (2016) Pilot-scale production of washed cottonseed meal and co-products. Mod Appl Sci 10(2):25–33 18. Cheng Z, Hardy R (2002) Apparent digestibility coefficients and nutritional value of cottonseed meal for rainbow trout (Oncorhynchus mykiss). Aquaculture 212(1–4):361–372 19. Araujo R, Macedo S, Korn MG, Pimentel M, Bruns R, Ferreira S (2008) Mineral composition of wheat flour consumed in Brazilian cities. J Braz Chem Soc 19(5):935–942 20. Vincent O, Adewale I, Dare O, Rachael A, Bolanle J-O (2009) Proximate and mineral composition of roasted and defatted cashew nut (Anarcadium occidentale) flour. Pak J Nutr 8 (10):1649–1651 21. Peterson L (1997) Potassium in nutrition. In: Handbook of nutritionally essential minerals. Marcel Dekker, New York, pp 153–183 22. Russo D, Bellasi A, Pota A, Russo L, Di Iorio B (2015) Effects of phosphorus-restricted diet and phosphate-binding therapy on outcomes in patients with chronic kidney disease. J Nephrol 28(1):73–80 23. Asuk AA, Agiang MA, Dasofunjo K, Willie AJ (2015) The biomedical significance of the phytochemical, proximate and mineral compositions of the leaf, stem bark and root of Jatropha curcas. Asian Pac J Trop Biomed 5(8):650–657 24. Mafra D, Cozzolino S (2004) The importance of zinc in human nutrition. Rev Nutr 17(1):79–87 25. Heuze V, Tran G, Bastianelli D, Hassoun P, Lebas F (2013) Cottonseed meal. Feedipedia.org. A programme by INRA, CIRAD, AFZ and FAO 26. Ma X, Hu J, Shang Q, Liu H, Piao X (2019) Chemical composition, energy content and amino acid digestibility in cottonseed meals fed to growing pigs. J Appl Anim Res 47(1):280–288 27. Gao D, Cao Y, Li H (2010) Antioxidant activity of peptide fractions derived from cottonseed protein hydrolysate. J Sci Food Agric 90(11):1855–1860 28. Sun H, Yao X, Wang X, Wu Y, Liu Y, Tang J et al (2015) Chemical composition and in vitro antioxidant property of peptides produced from cottonseed meal by solid-state fermentation. CYTA J Food 13(2):264–272 29. Qian J, Wang F, Liu S, Yun Z (2008) In situ alkaline transesterification of cottonseed oil for production of biodiesel and nontoxic cottonseed meal. Bioresour Technol 99(18):9009–9012 30. Yu J, Yang H, Wan X, Chen Y, Yang Z, Liu W et al (2020) Effects of cottonseed meal on slaughter performance, meat quality, and meat chemical composition in Jiangnan White goslings. Poult Sci 99(1):207–213 31. Tavares-Samay A, Dutra Junior W, Palhares L, Lopes C, Rabello C-V, Coelho A (2019) Determination of nutrient and energy values of cottonseed meal supplemented or not with phytase and protease for broiler chicks. Rev Bras Zootec 48:e20180142 32. Dadgar S, Saad C, Alimon A, Kamarudin M, Nafisi Bahabadi M (2010) Comparison of Soybean meal and Cottonseed meal variety Pak (CSMP) on growth and feed using in rainbow trout (Oncorhynchus mykiss). Iran J Fish Sci 9(1):49–60 33. Delgado E, Valles-Rosales D, Flores N, Reyes-Jáquez D (2021) Evaluation of fish oil content and cottonseed meal with ultralow gossypol content on the functional properties of an extruded shrimp feed. Aquac Rep 19:100588 34. Bhise S, Kaur A (2013) Development of functional chapatti from texturized deoiled cake of sunflower, soybean and flaxseed. Int J Eng Res Appl 3(5):1581–1587 35. Sanz A, Morales A, De la Higuera M, Gardenete G (1994) Sunflower meal compared with soybean meals as partial substitutes for fish meal in rainbow trout (Oncorhynchus mykiss) diets: protein and energy utilization. Aquaculture 128(3–4):287–300 36. Kouser S, Mahmood K, Anwar F (2015) Variations in physicochemical attributes of seed oil among different varieties of cotton (Gossypium hirsutum L.). Pak J Bot 47(2):723–729

152

J. G. de Oliveira Filho et al.

37. Matthäus B, Musazcan Özcan M (2015) Oil content, fatty acid composition and distributions of vitamin-E-active compounds of some fruit seed oils. Antioxidants 4(1):124–133 38. Okonkwo S, Okafor E (2016) Determination of the proximate composition, physicochemical analysis and characterization of fatty acid on the seed and oil of Gossypium hirsutum. Int J Chem 8(3):57–61 39. do Prado Paim T, Viana P, Brandão E, Amador S, Barbosa T, Cardoso C, et al. (2014) Carcass traits and fatty acid profile of meat from lambs fed different cottonseed by-products. Small Rumin Res 116(2–3):71–77 40. Pereira E, Mizubuti I, Oliveira R, Pinto A, Ribeiro E, Gadelha C et al (2016) Supplementation with cashew nut and cottonseed meal to modify fatty acid content in lamb meat. J Food Sci 81(9):C2143–C21C8 41. Thirukkumar S, Hemalatha G, Vellaikumar S, Amutha S, Murugan M (2021) Studies on selected cotton seed (Gossypium sp) varieties nutrient profile for human consumption in Tamil Nadu. J Cotton Res Dev 35(1):79–87 42. Dowd M, Boykin D, Meredith W Jr, Campbell B, Bourland F, Gannaway J et al (2010) Fatty acid profiles of cottonseed genotypes from the national cotton variety trials. J Cotton Sci 14:64–73 43. Nagalakshmi D, Rao S, Panda A, Sastry V (2007) Cottonseed meal in poultry diets: a review. J Poult Sci 44(2):119–134 44. Obert J, Hughes D, Sorenson W, McCann M, Ridley W (2007) A quantitative method for the determination of cyclopropenoid fatty acids in cottonseed, cottonseed meal, and cottonseed oil (Gossypium hirsutum) by high-performance liquid chromatography. J Agric Food Chem 55(6): 2062–2067 45. USDA (2019) U.S. Department of Agriculture (USDA). Agricultural Research Service, 2019. Accessed 4 Apr 2021 46. NRC (2001) Nutrient requirements of dairy cattle. In: Committee on Animal Nutrition, Board on Agriculture, National Research Council (eds) National Research Council, 7th rev edn. National Academy Press, Washington, DC 47. Sterling K, Costa E, Henry M, Pesti G, Bakalli R (2002) Responses of broiler chickens to cottonseed- and soybean meal-based diets at several protein levels. Poult Sci 81(2):217–226 48. Watkins S, Saleh E, Waldroup P (2002) Reduction in dietary nutrient density aids in utilization of high protein. Int J Poult Sci 1(4):53–58 49. Sahin A, Duru M, Kaya S, Camci O (2006) Effects of raw material in finisher diet on broiler performance in choice feeding system. Arch Geflugelkd 70(1):8–13 50. Thirumalaisamy G, Purushothaman M, Kumar P, Selvaraj P, Natarajan A, Senthilkumar S et al (2016) Nutritive and feeding value of cottonseed meal in broilers – a review. Adv Anim Vet Sci 4(8):398–404 51. Tang J, Sun H, Yao X, Wu Y, Wang X, Feng J (2012) Effects of replacement of soybean meal by fermented cottonseed meal on growth performance, serum biochemical parameters and immune function of yellow-feathered broilers. Asian Australas J Anim Sci 25(3):393 52. Bernard J, Tao S, Smith T (2016) Production response of lactating cows to diets based on corn or forage sorghum silage harvested on two dates and supplemented with soybean meal or mechanically pressed cottonseed meal. J Anim Sci 94:700–701 53. Vázquez-Olivo G, Cabanillas-Bojórquez L, Elizalde-Romero C, Heredia J (2020) Phenolics from agro-industrial by-products. In: Plant phenolics in sustainable agriculture. Springer, Singapore, pp 331–346 54. Oskoueian E, Abdullah N, Hendra R, Karimi E (2011) Bioactive compounds, antioxidant, xanthine oxidase inhibitory, tyrosinase inhibitory and anti-inflammatory activities of selected agro-industrial by-products. Int J Mol Sci 12(12):8610–8625 55. Salas C, Ekmay R, England J, Cerrate S, Coon C (2013) The TMEn, proximate analysis, amino acid content and amino acid digestibility of glandless and commercial cottonseed meal for broilers. Int J Poult Sci 12(4):212–216

8

Bioactive Phytochemicals from Cotton (Gossypium hirsutum) Seed Oil. . .

153

56. Gilani A, Kermanshahi H, Golian A, Tahmasbi A (2013) Impact of sodium bentonite addition to the diets containing cottonseed meal on productive traits of HY-line W-36 hens. J Anim Plant Sci 23:411–415 57. Kumar M, Potkule J, Patil S, Saxena S, Patil P, Mageshwaran V et al (2021) Extraction of ultralow gossypol protein from cottonseed: characterization based on antioxidant activity, structural morphology and functional group analysis. LWT Food Sci Technol 140:110692 58. Conceição A, Soares Neto C, Ribeiro J, Siqueira F, Miller R, Mendonça S (2018) Development of an RP-UHPLC-PDA method for quantification of free gossypol in cottonseed cake and fungal-treated cottonseed cake. PLoS One 13(5):e0196164 59. Câmara A, Gadelha I, Borges P, de Paiva S, Melo M, Soto-Blanco B (2015) Toxicity of gossypol from cottonseed cake to sheep ovarian follicles. PLoS One 10(11):e0143708 60. Tegtmeier D, Hurka S, Klüber P, Brinkrolf K, Heise P, Vilcinskas A (2021) Cottonseed press cake as a potential diet for industrially farmed black soldier fly larvae triggers adaptations of their bacterial and fungal gut microbiota. Front Microbiol 12:563 61. Grewal J, Tiwari R, Khare S (2019) Secretome analysis and bioprospecting of lignocellulolytic fungal consortium for valorization of waste cottonseed cake by hydrolase production and simultaneous gossypol degradation. Waste Biomass Valor 11:1–16 62. Knutsen H, Alexander J, Barregård L, Bignami M, Brüschweiler B, Ceccatelli S et al (2017) Risks for animal health related to the presence of zearalenone and its modified forms in feed. EFSA J 15:e04851 63. Lago A, Neves I, Oliveira N, Botrel D, Minim L, de Resende J (2019) Ultrasound-assisted oilin-water nanoemulsion produced from Pereskia aculeata Miller mucilage. Ultrason Sonochem 50:339–353 64. Sloley B, Urichuk L, Morley P, Durkin J, Shan J, Pang P et al (2000) Identification of kaempferol as a monoamine oxidase inhibitor and potential neuroprotectant in extracts of Ginkgo biloba leaves. J Pharm Pharmacol 52(4):451–459 65. Berger A, Venturelli S, Kallnischkies M, Böcker A, Busch C, Weiland T et al (2013) Kaempferol, a new nutrition-derived pan-inhibitor of human histone deacetylases. J Nutr Biochem 24(6):977–985 66. Imran M, Rauf A, Shah Z, Saeed F, Imran A, Arshad M et al (2019) Chemo-preventive and therapeutic effect of the dietary flavonoid kaempferol: a comprehensive review. Phytother Res 33(2):263–275 67. Wong S, Chin K-Y, Ima-Nirwana S (2019) The osteoprotective effects of kaempferol: the evidence from in vivo and in vitro studies. Drug Des Devel Ther 13:3497 68. Ren J, Lu Y, Qian Y, Chen B, Wu T, Ji G (2019) Recent progress regarding kaempferol for the treatment of various diseases. Exp Ther Med 18(4):2759–2776 69. Salehi B, Fokou P, Sharifi-Rad M, Zucca P, Pezzani R, Martins N et al (2019) The therapeutic potential of naringenin: a review of clinical trials. Pharmaceuticals 12(1):11 70. Chin L, Hon C, Chellappan D, Chellian J, Madheswaran T, Zeeshan F et al (2020) Molecular mechanisms of action of naringenin in chronic airway diseases. Eur J Pharmacol 879:173139 71. Wang Q, Yang J, Zhang X-M, Zhou L, Liao X-L, Yang B (2015) Practical synthesis of naringenin. J Chem Res 39(8):455–457 72. NCBI (2020) National Center for Biotechnology Information, PubChem Compound Database, cid¼439246. Accessed 15 June 2020 73. Zobeiri M, Belwal T, Parvizi F, Naseri R, Farzaei M, Nabavi S et al (2018) Naringenin and its nano-formulations for fatty liver: cellular modes of action and clinical perspective. Curr Pharm Biotechnol 19(3):196–205 74. Jayachitra J, Nalini N (2012) Effect of naringenin (citrus flavanone) on lipid profile in ethanolinduced toxicity in rats. J Food Biochem 36(4):502–511 75. Frutos MJ, Rincón-Frutos L, Valero-Cases E (2018) Rutin. In: Mohammad S, Silva AS (eds) Nonvitamin and nonmineral nutritional supplements. Academic Press, London, pp 111–117 76. Ganeshpurkar A, Saluja A (2017) The pharmacological potential of rutin. Saudi Pharm J 25(2): 149–164

154

J. G. de Oliveira Filho et al.

77. Marin F, Frutos M, Perez-Alvarez J, Martinez-Sanchez F, Del Rio J (2002) Flavonoids as nutraceuticals: structural related antioxidant properties and their role on ascorbic acid preservation. In: Studies in natural products chemistry. Elsevier, New York, pp 741–778 78. Gullón B, Lú-Chau T, Moreira M, Lema J, Eibes G (2017) Rutin: a review on extraction, identification and purification methods, biological activities and approaches to enhance its bioavailability. Trends Food Sci Technol 67:220–235 79. Chua L (2013) A review on plant-based rutin extraction methods and its pharmacological activities. J Ethnopharmacol 150(3):805–817 80. Lee Y, Jeune K (2013) The effect of rutin on antioxidant and anti-inflammation in streptozotocin-induced diabetic rats. Appl Microsc 43(2):54–64 81. Kim H-Y, Nam S-Y, Hong S-W, Kim M-J, Jeong H-J, Kim H-M (2015) Protective effects of rutin through regulation of vascular endothelial growth factor in allergic rhinitis. Am J Rhinol Allergy 29(3):e87–e94 82. Tian X, Ruan J, Huang J, Fang X, Mao Y, Wang L et al (2016) Gossypol: phytoalexin of cotton. Sci China Life Sci 59(2):122–129 83. Scheffler J (2016) Evaluating protective terpenoid aldehyde compounds in cotton (Gossypium hirsutum L.) roots. Am J Plant Sci 7(7):1086 84. Lu Y, Li J, Dong C-E, Huang J, Zhou H-B, Wang W (2017) Recent advances in gossypol derivatives and analogs: a chemistry and biology view. Future Med Chem 9(11):1243–1275 85. Zhang Y, Han M, Wang Y (1994) Estrogen and progesterone cytosol receptor concentrations in patients with endometriosis and their changes after gossypol therapy. Zhonghua Fu Chan Ke Za Zhi 29(4):220–223. 53 86. Band V, Hoffer A, Band H, Rhinehardt A, Knapp R, Matlin S et al (1989) Antiproliferative effect of gossypol and its optical isomers on human reproductive cancer cell lines. Gynecol Oncol 32(3):273–277 87. Sung B, Ravindran J, Prasad S, Pandey M, Aggarwal B (2010) Gossypol induces death receptor-5 through activation of the ROS-ERK-CHOP pathway and sensitizes colon cancer cells to TRAIL. J Biol Chem 291(32):16923 88. Gadelha I, Fonseca N, Oloris S, Melo M, Soto-Blanco B (2014) Gossypol toxicity from cottonseed products. Sci World J 2014:231635 89. Piccinelli AL, Veneziano A, Passi S, De Simone F, Rastrelli L (2007) Flavonol glycosides from whole cottonseed by-product. Food Chem 100(1):344–349 90. Dai C, Ma H, Zhang L, Zhu S, Yin X, He R (2016) Effects of ultrafine grinding and pulsed magnetic field treatment on removal of free gossypol from cottonseed meal. Food Bioprocess Technol 9(9):1494–1501 91. Romero A, Calori-Domingues M, Abdalla A, Augusto P (2021) Evaluation of ozone technology as an alternative for degradation of free gossypol in cottonseed meal: a prospective study. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 38:1–11

9

Bioactive Phytochemicals from Sesame Oil Processing By-products Reham Hassan Mekky, Mostafa M. Hegazy, María de la Luz Ca´diz-Gurrea, A´lvaro Ferna´ndez-Ochoa, and Antonio Segura Carretero

Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Bioactive Metabolites Described in Sesame Cake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Phenolic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Nonphenolic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Total Phenol Content, Total Flavonoid Contents, Total Lignans Content . . . . . . . . . . . 2.4 Comparison Between Sesame Seed Cake and Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Proximate Composition of Sesame Cakes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Biological Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Antimutagenic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Antidepressant Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 Hypoglycemic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Antiaging Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5 Anti-inflammatory Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6 Estrogenic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

157 157 158 158 168 168 171 173 173 173 175 176 176 176

R. H. Mekky Department of Pharmacognosy, Faculty of Pharmacy, Egyptian Russian University, Badr City, Cairo, Egypt Research and Development Functional Food Centre (CIDAF), Bioregión Building, Health Science Technological Park, Granada, Spain e-mail: [email protected] M. M. Hegazy Department of Pharmacognosy, Faculty of Pharmacy, Al-Azhar University, Nasr City, Cairo, Egypt e-mail: [email protected] M. d. l. L. Cádiz-Gurrea (*) Research and Development Functional Food Centre (CIDAF), Bioregión Building, Health Science Technological Park, Granada, Spain Analytical Chemistry Department, Faculty of Sciences, University of Granada, Granada, Spain e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_9

155

156

R. H. Mekky et al.

3.7 Antimicrobial Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.8 Antihypertensive Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.9 Hypocholesterolemic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.10 Antioxidant Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Valorization Strategies of Sesame Oil Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 The Preservative Potential of Sesame Bio-waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2 Balancing of Food Product Contents and Its Health Impacts . . . . . . . . . . . . . . . . . . . . . . . . 4.3 Prospects for Treatment of Certain Diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4 Animal Feedstuffs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5 Substrate for Production of Valuable Ingredients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6 Agriculture Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.7 Environmental Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.8 Bioenergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

177 177 177 178 178 178 180 181 183 185 187 187 187 188 188

Abstract

Sesame (Sesamum indicum L.) is an oil crop that belongs to the family Pedaliaceae. It is cultivated all over the world. Sesame seeds possess nutritional value being a rich source of proteins, dietary fibers, carbohydrates, fats, and vitamins. Sesame seeds and oil have several biological potentials: antioxidant, antimutagenic, estrogenic, and hypolipidemic. Many phytochemical constituents were observed in sesame seeds and/or oil as phenolic acids, flavonoids, lignans, phytosterols, and unsaturated fatty acids. The total world production of sesame is around seven million tons with a production of two million tons of sesame oil with nearly 70% of agri-industrial by-product in the form of the cake counterpart. Some studies focused on the cake by-product’s phytochemical composition and biological potential, reflecting the valorization of such agri-industrial by-products where the effective utilization of them could lead to sustainability in the industry of food supplements, nutraceuticals, and non-food applications. Keywords

Bioactive compounds · Food by-products · Phytochemicals · Sesame cake · Valorization

Á. Fernández-Ochoa Analytical Chemistry Department, Faculty of Sciences, University of Granada, Granada, Spain Berlin Institute of Health Metabolomics Platform, Berlin, Germany Max Delbrück Center for Molecular Medicine in the Helmholtz Association, Berlin, Germany e-mail: [email protected] A. Segura Carretero Research and Development Functional Food Centre (CIDAF), Health Science Technological Park, Granada, Spain Analytical Chemistry Department, Faculty of Sciences, University of Granada, Granada, Spain e-mail: [email protected]

9

1

Bioactive Phytochemicals from Sesame Oil Processing By-products

157

Introduction

“Open Sesame!” was the secret magical phrase in “Ali Baba and the Forty Thieves” story for door opening, which exactly like the biological potentials of sesame that open the way for many health benefits. Sesame (Sesamum indicum L., Pedailaceae) is an oil-producing crop. It is cultivated all over the globe with a total production of seven million tons of seeds producing two million tons of oil with a remaining agri-food residue (agri-industrial by-product) corresponding to the cake counterpart, which represents nearly 70% of the total production in accordance to FAO statistics [1]. Anciently, it was originated in India and known in the Ancient Egyptian civilization in the treatment of asthma [2, 3]. Sesame seeds and/or oil are a source of valuable bioactive metabolites viz., lignans, flavonoids, phenolic acids, and pharmacologically active protein isolates [4–11]. Besides, sesame seeds, oil, and/or their isolated metabolites possess valuable biological activities, for example, antihypertensive, hypocholesterolemic, antidiabetic, antiinflammatory, antioxidant, anticancer, among others [4–6, 8–10, 12–19]. Preserving natural resources is a significant challenge, especially for food applications for their nutritional and functional properties. The recycling of vegetable oil processing by-products can offer an economical solution for the risk of natural resource exhaustion which emerged as a world research trend for managing this serious problem [20]. Furthermore, sesame waste such as cake, meal, and extract can be a source of many bioactive ingredients like antioxidants, protein, and dietary fiber with health benefits that make them suitable for the food and/or nutraceutical industries [9, 10, 21]. Sesame by-products can be used to preserve and balance nutritional properties of food [22–33], nutraceutical for the management of neurodegenerative diseases [34–38], and as a substrate for the production of valuable ingredients such as enzymes and antibiotics [39–50]. Other valorization strategies are in animal feedstuff [51–57], agricultural applications such as liquid fertilizers, seed priming and pathogens biocontrol agent [58–61], bioremediation of the environment [62–64], and in bioenergy production [65–67]. In this chapter, the different strategies for the revalorization of sesame cake in order to develop high value-added products are described.

2

Bioactive Metabolites Described in Sesame Cake

A wide array of bioactive metabolites was described in sesame cakes or defatted seeds, giving a prospect of the significance of such agri-food residue as a source of bioactive metabolites. Thus, the utilization of agri-food residue could contribute to the sustainable development of food industries and nutraceuticals [10, 68]. In this context, state-of-art techniques such as ultra/high-performance liquid chromatography coupled to high-resolution mass spectrometry allowed the detection of many phenolic compounds, namely, lignans, flavonoids, hydroxybenzoic acids, hydroxycinnamic acids, among others.

158

2.1

R. H. Mekky et al.

Phenolic Compounds

Several classes of phenolic compounds were observed in sesame cakes [7, 10, 21, 35, 69]. They were reviewed and classified into lignans, flavonoids, phenolic acids, among others, considering each metabolite name, molecular formula, occurrence, geographical origins, extraction, and analytical method. However, most of the reported studies focused on lignans as they possess valuable biological activities [14]. They are naturally occurring phenolics composing two phenyl propane units by a β-β linkage with several biological activities. Therefore, they are classified into furofuran, furans, dibenzylbutanes, arylnaphthalene, aryltetralin, and dibenzylbutyrolactone classes [70, 71]. Table 1 and Fig. 1 summarize the observed lignans in sesame cake.

2.1.1 Flavonoids As for flavonoids, Mekky et al. [10] performed untargeted metabolic profiling for the cake of sesame of the Egyptian cultivar Giza 32, describing 26 flavonoids being classified into flavan-3-ols, flavanones, flavones, flavonols. Most of the observed flavonoids were observed for the first time in sesame with a noticed occurrence of apigenin and luteolin C glycosides that accounted for around 48% qualitatively and 96% quantitatively of all the detected flavonoids [10]. C-conjugates enhance the antioxidant potential of flavones where the chelation sites are free, and hence, the radical scavenging activity is increased [10, 78, 79]. In this sense, Table 2 and Fig. 2 demonstrate the observed flavonoids in sesame cakes. 2.1.2 Phenolic Acids Several phenolic acids were detected, being classified into hydroxybenzoic and hydroxycinnamic acids. Furthermore, they were classified into monohydroxybenzoic acids, dihydroxybenzoic acids, and trihydroxybenzoic acids and presented either in free or glycosides forms. Regarding hydroxycinnamic acids, they were either free or conjugated with sugars, phenylethanoid glycosides, or quinic acid. Besides, umbelliferon was observed as an example of coumarins. In this regard, Table 3 and Fig. 3 illustrate the observed phenolic acids and coumarins.

2.2

Nonphenolic Compounds

In line with the nonphenolic compounds observed in sesame cakes, they were grouped into amino acids, peptides, nucleosides, organic acids, and sugars. In addition, aromatic amino acids and oxidized glutathione were observed in sesame seeds’ cake, giving an insight into their contribution to the antioxidant potential of the cake by-product [10, 81, 82]. Table 4 and Fig. 4 demonstrate the observed nonphenolic compounds in sesame cakes.

6

C20H22O6 Greece

Greece

Japan Thailand

Dehulled perisperms Seeds Seeds

Egypt

Dehulled seeds

Cv Giza 32

C41H52O24

Xanthoxylol trihexoside Xanthoxylol malonyl trihexoside Pinoresinol

4

5

Greece

Dehulled perisperms Egypt

Greece

Dehulled seeds

C20H20O6

Xanthoxylol

3

Cv Giza 32

China Greece

Sesame cake Dehulled perisperms

C13H14O6

Saminol

2

C38H50O21

Egypt

Cv Giza 32

C7H6O3

Geographical origin

Occurrence

Molecular formula

# Compound Furofuran lignans 1 Sesamol

Table 1 Lignans described in the cakes of sesame

Hot water

Methanol:water (80:20)

Methanol

Hydromethanolic hydroacetonic Hydromethanolic hydroacetonic Methanol

Methanol

Methanol

Hydromethanolic hydroacetonic Hydroethanolic Methanol

Extraction after defatting and/or oil pressing RP-HPLC-DADQTOF-MS-MS/MS HPLC XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS RP-HPLC-DADQTOF-MS-MS/MS RP-HPLC-DADQTOF-MS-MS/MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS Prep. HPLC, XAD-4 resin CC, MS Diaion HP-20 CC, 1H and 13C NMR

Method of analysis

Bioactive Phytochemicals from Sesame Oil Processing By-products (continued)

[73]

[72]

[7]

[69]

[10]

[10]

[7]

[69]

[35] [7]

[10]

Reference

9 159

Compound Pinoresinol O-β-Dglucopyranoside

Pinoresinol dihexoside

Pinoresinol malonyl dihexoside Sesaminol

Sesaminol dipentoside

# 7

8

9

10

11

Table 1 (continued)

C30H34O16

C20H18O7

C35H44O19

C32H42O16

Molecular formula C26H32O11

Japan South Korea

Seeds Fermented cake with Egypt

Greece

Dehulled perisperms

Cv Giza 32

Greece

Egypt

Egypt

Geographical origin Greece

Dehulled seeds

Cv Giza 32

Cv Giza 32

Occurrence Dehulled perisperms

Boiling with water, inoculated (1%, v/v Lactobacillus plantarum P8, 24 h, 37
C) Hydromethanolic hydroacetonic

Methanol:water (80:20)

Methanol

Hydromethanolic hydroacetonic Hydromethanolic hydroacetonic Methanol

Extraction after defatting and/or oil pressing Methanol

RP-HPLC-DADQTOF-MS-MS/MS

Method of analysis XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS RP-HPLC-DADQTOF-MS-MS/MS RP-HPLC-DADQTOF-MS-MS/MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS Prep. HPLC, XAD-4 resin CC, MS HPLC

[10]

[74]

[72]

[7]

[69]

[10]

[10]

Reference [7]

160 R. H. Mekky et al.

Sesaminol diglucoside

Sesaminol triglucoside

Sesaminol tetrahexoside

14

15

Sesaminol-20 -O-β-Dglucopyranoside

13

12

C44H58O27

C38H48O22

C32H38O17

C26H28O12

Japan Sweden Thailand Japan Egypt Sweden South Korea

Seeds Seeds Black sesame seeds cake Seeds Cv Giza 32 Seeds Nonfermented cake Cv Giza 32 Egypt

Greece

Thailand

Seeds Dehulled seeds

Japan

Seeds

Hydromethanolic hydroacetonic

Boiling with water

Hydromethanolic hydroacetonic Ethanol:water (80:20)

Methanol:water (80:20)

Methanol

Ethanol:water (80:20)

Methanol:water (80:20)

Methanol

Methanol

Methanol:water (80:20)

RP-HPLC-DADQTOF-MS-MS/MS

Prep. HPLC, XAD-4 resin CC, MS Silica gel CC, 1H, and 13 C NMR XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS Prep. HPLC, XAD-4 resin CC, MS LC-MS, TLC, silica CC, NMR Prep HPLC, 1H NMR, 13 C NMR Prep. HPLC, XAD-4 resin CC, MS RP-HPLC-DADQTOF-MS-MS/MS LC-MS, TLC, silica CC, NMR HPLC

(continued)

[10]

[74]

[77]

[10]

[72]

[76]

[75]

[72]

[69]

[73]

[72]

9 Bioactive Phytochemicals from Sesame Oil Processing By-products 161

20

19

Sesamolin

Sesamolinol-40 -O-β-Dglucoside

Hydroxysesamolin trihexoside Sesamolinol

17

18

Compound Episesaminol-6catechol

# 16

Table 1 (continued)

C20H18O7

C28H34O14

C20H20O7

C38H48O23

Molecular formula C19H18O7

Greece

China Thailand

Sesame cake Seeds

Greece

Dehulled seeds

Dehulled seeds

Egypt

Japan

Seeds Cv Giza 32

Greece

Egypt

Geographical origin Greece

Dehulled seeds

Cv Giza 32

Occurrence Dehulled perisperms

Hydro-ethanolic Methanol

Methanol

Hydromethanolic hydroacetonic Methanol

Methanol:water (80:20)

Hydromethanolic hydroacetonic Methanol

Extraction after defatting and/or oil pressing Methanol

Method of analysis XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS RP-HPLC-DADQTOF-MS-MS/MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS Prep. HPLC, XAD-4 resin CC, MS RP-HPLC-DADQTOF-MS-MS/MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS HPLC Silica gel CC, 1H and 13 C NMR

[35] [73]

[69]

[69]

[10]

[72]

[69]

[10]

Reference [7]

162 R. H. Mekky et al.

Disaminyl ether

22

24

50 -Methoxylariciresinol

Furano lignans 23 Lariciresinol

Sesamin

21

C21H26O7

C20H24O6

C26H26O9

C20H18O6

Dehulled perisperms

Dehulled perisperms Greece

Greece

Greece

Dehulled perisperms

China Thailand

Sesame cake Seeds Greece

Greece

Dehulled perisperms

Dehulled seeds

Greece

Dehulled seeds

Methanol

Methanol

Methanol

Methanol

Hydro-ethanolic Methanol

Methanol

Methanol

XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS

XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS HPLC Silica gel CC, 1H and 13C NMR XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS

(continued)

[7]

[7]

[7]

[69]

[35] [73]

[7]

[69]

9 Bioactive Phytochemicals from Sesame Oil Processing By-products 163

Episesaminone-9O-β-D-sophoroside

Acuminatin

26

27

7-Hydroxymatairesinol

C20H22O7

Dehulled perisperms

Greece

Greece

Greece

Greece

Greece

Greece

Geographical origin Greece

Methanol

Methanol

Methanol

Methanol

Methanol

Methanol

Extraction after defatting and/or oil pressing Methanol

XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS

XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS

Method of analysis XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS XAD-4 resin CC, 1D-2D NMR, HMQC, HMBC, NOSEY, MS

[7]

[7]

[7]

[7]

[7]

[7]

Reference [69]

RP reversed-phase, HPLC high-performance liquid chromatography, DAD diode array detector, QTOF quadrupole time of flight, MS mass spectrometry, MS/MS tandem mass, CC column chromatography, D dimensional, NMR nuclear magnetic resonance, HMQC heteronuclear multiple quantum coherence, HMBC heteronuclear multiple bond coherence, NOSEY nuclear overhauser effect spectroscopy, Prep, preparative

30

Dehulled perisperms

Dehulled perisperms

Dehulled perisperms

C21H24O9

C20H42O7

Dehulled perisperms

Dehulled perisperms

Occurrence Dehulled seeds

C32H38O17

Molecular formula C20H18O7

Dibenzylbutyrolactone lignans 29 Matairesinol C20H22O6

Dibenzylbutyrolactol lignans 28 Sesamolactol

Compound Episesaminone

# 25

Table 1 (continued)

164 R. H. Mekky et al.

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

165

9 (1)

(2)

R=H (3) R= trihexoside (4) R= malonyl trihexoside (5)

R1=R2=H (6) R1=glucoside, R2=H (7) R1=R2=hexose (8) R1=malonyl hexoside, R2=hexose (9)

R=H (10) R=dipentoside (11) R=glucoside (12) R=diglucoside (13) R=triglucoside (14) R=tetrahexoside (15)

(16)

(17)

R=H (18) R=glucoside (19)

(20)

(21)

(22)

R=H (23)

R=OCH3 (24)

R=H (25) R= β-D-sophoroside (26)

(27)

R=H (29) R=OH (30)

Fig. 1 Chemical structures of lignans described in sesame cakes

(28)

Flavanones 32 Naringenin 33 Pinocembrin Flavones 34 Apigenin 35 Apigenin di-C-pentoside 36 Apigenin C-pentoside C-hexoside 37 Luteolin 38 Luteolin 7-O-β-Dglucopyranoside 39 Luteolin C-hexoside 40 Luteolin Cdeoxyhexoside Chexoside

# Compound Flavan-3-ols 31 ()-Epicatechin

Cv Giza 32

C15H10O5 C25H26O13 C26H28O14

C21H20O11 C27H30O15

C15H10O6 C21H20O11

Cv Giza 32

Cv Giza 32

C15H14O6

C15H12O5 C15H12O4

Occurrence

Molecular formula

Table 2 Flavonoids described in the cakes of sesame

Egypt

Egypt

Egypt

Geographical origin

Hydromethanolic hydroacetonic

Hydromethanolic hydroacetonic

Hydromethanolic hydroacetonic

Extraction after defatting and/or oil pressing

RP-HPLC-DAD-QTOFMS-MS/MS

RP-HPLC-DAD-QTOFMS-MS/MS

RP-HPLC-DAD-QTOFMS-MS/MS

Method of analysis

[10]

[10]

[10]

Reference

166 R. H. Mekky et al.

C15H10O8

C27H30O16

C21H20O11

C21H20O12

C15H10O6 C16H12O6 C15H10O7 C21H20O12 Cv Giza 32

Egypt

Hydromethanolic hydroacetonic

RP-HPLC-DAD-QTOFMS-MS/MS

[10]

RP reversed-phase, HPLC high-performance liquid chromatography, DAD diode array detector, QTOF quadrupole time of flight, MS mass spectrometry, MS/MS tandem mass

Flavonols 41 Kaempferol 42 Kaempferide 43 Quercetin 44 Quercetin 3-O-β-Dglucopyranoside 45 Quercetin 3-O-β-Dgalactopyranoside 46 Quercetin 3-Orhamnopyranoside 47 Quercetin 3-O-rutinoside (rutin) 48 Myricetin

9 Bioactive Phytochemicals from Sesame Oil Processing By-products 167

168

R. H. Mekky et al.

R=OH (32) R=H (33)

(31)

R1=R2=H (34) R1=R2=pentoside (35) R1= hexoside R2= pentoside (36)

R1= R2= R3=H (37) R1= R2=H R3=glucoside (38) R1= R3=H R2=hexoside (39) R1=H R2=hexoside R3=deoxyhexoside (40)

R1=R2=R3=R4=H (41) R1=R2=R4=H R3=CH3 (42) R1=OH R2=R3=R4=H (43) R1=OH R2=R3=H R4=glucoside (44) R1=OH R2=R3=H R4=galactoside (45) R1=OH R2=R3=H R4=rhamnoside (46) R1=OH R2=R3=H R4=rutinoside (47) R1= R2=OH =R3= R4=H (48)

Fig. 2 Chemical structures of flavonoids described in sesame cake

2.3

Total Phenol Content, Total Flavonoid Contents, Total Lignans Content

The quantification of the total contents of phenols, flavonoids, and/or lignans of vegetal matrices is considered an indicator of their antioxidant activity impact on the well-being in general [82–84]. In this sense, a plethora of studies focused on quantifications of the aforementioned parameters of sesame cake. The TPC ranged from 0.8 to 1.9 mg GAE (gallic acid equivalent) g1 DW (dry weight defatted seed extract) and from 19.2 to 32.3 mg GAE g1 FW (fresh weight defatted seeds extract). In line with the total flavonoids content (TFC), it ranged from 0.4 to 0.88 mg QE (quercetin equivalent) g1 DW and from 11.2 to 13.9 mg CE (catechin equivalent) g1 FW (Table 5). As for total lignans content (TLC), Bodria et al. determined the TLC of the Argentinian defatted sesame seeds, and it was 21.6 mg SE (sesamin equivalent) g1 FW [86].

2.4

Comparison Between Sesame Seed Cake and Oil

An untargeted metabolic profiling employing RP-HPLC-DAD-QTOF-MS and tandem MS was performed for the sesame seed cake and oil of the Egyptian cultivar Giza 32 [10, 79]. A total number of 112 metabolites were observed in the cake and 86 metabolites in the oil. Among them, 72 metabolites were commonly detected in both the cake and the oil. This profiling presents an insight on the significance of the cake as an agri-food residue being a richer source of bioactive metabolites than the oil. Generally, the common metabolites between the cake and oil mainly belonged to phenolics with the presence of glutathione disulfide. The presence and transfer of such bioactive metabolites from the cake to the oil enhances the biological potential of the oil as well as its shelf life and oxidative stability [25, 85, 88, 89]. In this

Cv Giza 32

C7H6O4 C7H6O4 C8H8O4 C14H18O9 C19H26O13

Protocatechuic acid Gentisic acid Vanillic acid Vanillic acid hexoside Vanillic acid pentoside hexoside Gallic acid Syringic acid

51 52 53 54 55

Tetrahydrofurn followed by methanl: acetone:water (7:7:6) Hydromethanolic hydroacetonic

Canada Egypt

C15H18O8

Cv Giza 32

p-Coumaric acid hexoside

Hydromethanolic hydroacetonic

63

Tetrahydrofurn followed by methanl: acetone:water (7:7:6) Hydromethanolic hydroacetonic

Canada Egypt

Hydromethanolic hydroacetonic

Egypt

Egypt

Cv Giza 32

Tetrahydrofurn followed by methanl: acetone:water (7:7:6) Hydromethanolic hydroacetonic

Canada Egypt

Hydromethanolic hydroacetonic

Hydromethanolic hydroacetonic

Extraction after defatting and/or oil pressing

Egypt

Egypt

Geographical origin

C9H8O2 C9H8O3 C9H8O3

Cv Giza 32

C14H18O9 C15H20O10

58 Syringic acid pentoside 59 Syringic acid hexoside Hydroxycinnamic acid 60 Cinnamic acid 61 m-Coumaric acid 62 p-Coumaric acid

Cv Giza 32

Cv Giza 32

C7H6O3

p-Hydroxybenzoic acid

50

C7H6O5 C9H10O5

Cv Giza 32

C7H6O2

56 57

Occurrence

Molecular formula

# Compound Hydroxybenzoic acid 49 Benzoic acid

Table 3 Phenolic acid and coumarins described in the cakes of sesame

RP-HPLC-DADQTOF-MS-MS/MS

Esterification then GLC

RP-HPLC-DADQTOF-MS-MS/MS

RP-HPLC-DADQTOF-MS-MS/MS

RP-HPLC-DADQTOF-MS-MS/MS Esterification then GLC

RP-HPLC-DADQTOF-MS-MS/MS

RP-HPLC-DADQTOF-MS-MS/MS RP-HPLC-DADQTOF-MS-MS/MS Esterification then GLC

Method of analysis

Bioactive Phytochemicals from Sesame Oil Processing By-products (continued)

[10]

[80]

[10]

[10]

[80]

[10]

[10]

[80]

[10]

[10]

Reference

9 169

Caffeic acid hexoside deoxyhexoside Chlorogenic acid Ferulic acid

65

C9H6O3

C29H36O15 C29H36O15 C29H36O16

C15H18O8 C16H20O9 C22H30O14 C26H28O12 C11H12O5 C17H22O10 C23H32O14

Cv Giza 32

Cv Giza 32

Cv Giza 32

C21H28O13

C16H18O9 C10H10O4

Occurrence Cv Giza 32

Molecular formula C9H8O4

Egypt

Egypt

Canada

Hydromethanolic hydroacetonic

Tetrahydrofurn followed by methanl: acetone:water (7:7:6) Hydromethanolic hydroacetonic

Tetrahydrofurn followed by methanl: acetone:water (7:7:6) Hydromethanolic hydroacetonic

Canada Egypt

Extraction after defatting and/or oil pressing Hydromethanolic hydroacetonic

Geographical origin Egypt

RP-HPLC-DADQTOF-MS-MS/MS

RP-HPLC-DADQTOF-MS-MS/MS

Esterification then GLC

RP-HPLC-DADQTOF-MS-MS/MS

Method of analysis RP-HPLC-DADQTOF-MS-MS/MS Esterification then GLC

[10]

[10]

[80]

[10]

[80]

Reference [10]

RP reversed-phase, HPLC high-performance liquid chromatography, DAD diode array detector, QTOF quadrupole time of flight, MS mass spectrometry, MS/MS tandem mass GLC, gas-liquid chromatography

Ferulic acid pentoside Ferulic acid hexoside Ferulic acid dihexoside Diferuloyl hexoside Sinapic acid Sinapic acid hexoside Sinapic acid deoxyhexoside hexoside 75 Verbascoside 76 Isoverbascoside 77 β-Hydroxyverbascoside (campneoside II) Coumarin 78 7-Hydroxycoumarin (umbelliferone)

68 69 70 71 72 73 74

66 67

Compound Caffeic acid

# 64

Table 3 (continued)

170 R. H. Mekky et al.

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

171

R1=R2=R3=R4=R5=H (49) R1=R2= R4=R5=H R3=OH (50) R1=R4= R5=H R2= R3=OH (51) R1=R4= OH R2=R3=R5=H (52) R1=R4= R5=H R2=OCH3 R3=OH (53) R1=R4= R5=H R2=OCH3 R3=O-hexoside (54) R1=R4= R5=H R2=OCH3 R3=O-pentoside hexoside (55) R1= R5=H R2=R3=R4=OH (56) R1= R5=H R2=R4=OCH3 R3=OH (57) R1= R5=H R2=R4=OCH3 R3=O-pentoside (58) R1= R5=H R2=R4=OCH3 R3=O-hexoside (59)

R1=R2=R3=R4= H (60) R1= R3=R4= H R2=OH (61) R1=R2=R4= H R3=OH (62) R1=R2= R4= H R3=O-hexoside (63) R1= R4=H R2=R3=OH (64) R1= R4=H R2=R3=O-deoxyhexoside hexoside (65) R1= quinic acid R2=R3=OH R4=H (66) R1= R4=H R2=OCH3 R3=OH (67) R1= R4=H R2=OCH3 R3=O-pentoside (68) R1= R4=H R2=OCH3 R3=O-hexoside (69) R1= R4=H R2=OCH3 R3=O-dihexoside (70) R1= R4=H R2=OCH3 R3=O-ferulyl-hexoside (71) R1= H R2= R4=OCH3 R3=OH (72) R1=H R2= R4=OCH3 R3=O-hexoside (73) R1=H R2= R4=OCH3 R3=O-deoxyhexoside hexoside (74)

R=H (75) R=OH (77)

(76)

Fig. 3 Chemical structures of phenolic acid and coumarins described in sesame cake

context, Fig. 5 illustrates the base peak chromatograms (BPC) of both the oil (Fig. 5a1) and cake (Fig. 5a2) of the Egyptian cultivar Giza 32 and the observed metabolites classified concerning mass to charge (m/z), retention time (RT), and relative area for the oil (Fig. 5b1) and the cake (Fig. 5b2) [10, 79].

2.5

Proximate Composition of Sesame Cakes

Sesame cakes are considered a rich source of nutrients [29]. In this line, the proximate analysis of sesame cake indicates the composition of sesame cakes of nutrients. The protein contents ranged from 30.5% to 41%, and hence, it represents an undervalued source of protein. As for carbohydrate content, it varied from 14.4% to 56.4% (Table 6).

Organic acid and sugars Gluconic/galactonic C6H12O7 acid Citric acid C6H8O7 Malic acid C4H6O5 Citramalic acid C5H8O5 Isopropylmalic acid C5H6O4 Itaconic acid C7H8O5 ()-3C7H12O6 Dehydroshikimic acid Quinic acid C9H17NO5 Pantothenic acid (Vit C7H12O5 B5) Azelaic acid C9H16O4 Sesamose C24H42O21

Molecular Compound formula Amino acid and peptides Asparagine C4H8N2O3 Leucine/isoleucine C6H13NO2 Phenylalanine C9H11NO3 Tyrosine C9H11NO2 Glutathione disulfide C20H32N6O12S2 Tryptophan C26H30N2O10 derivative Nucleoside Succinyladenosine C14H17N5O8

Cv Giza 32

Cv Giza 32

Cv Giza 32

Occurrence

Egypt

Egypt

Egypt

Geographical origin

Hydromethanolic hydroacetonic

Hydromethanolic hydroacetonic

Hydromethanolic hydroacetonic

Extraction after defatting and/or oil pressing

RP-HPLC-DAD-QTOFMS-MS/MS

RP-HPLC-DAD-QTOFMS-MS/MS

RP-HPLC-DAD-QTOFMS-MS/MS

Method of analysis

[10]

[10]

[10]

Reference

RP reversed-phase, HPLC high-performance liquid chromatography, DAD diode array detector, QTOF quadrupole time of flight, MS mass spectrometry, MS/MS tandem mass

95 96

93 94

87 88 89 90 91 92

86

85

79 80 81 82 83 84

#

Table 4 Non-phenolic compounds in sesame cake

172 R. H. Mekky et al.

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

(79)

173

R=H (81) R=OH (82)

(80)

(83)

(85)

(86)

(87)

R=H (88) R=CH3 (89) R=isopropyl (90)

(91)

(92)

(93)

(94)

(95)

(96)

Fig. 4 Chemical structures of non-phenolic compounds described in sesame cake

3

Biological Activities

3.1

Antimutagenic Activity

Sesamolinol-40 -O-β-D-glucoside, sesamolinol, samine, sesaminol-2-O-β-Dglucopyranoside, sesamolin, episesaminone, xanthoxylol isolated from dehulled defatted sesame seeds exhibited antimutagenic activities in both hydrogen peroxide and benzo[a]pyrene models [69].

3.2

Antidepressant Activity

Liu et al. investigated the antidepressant effect of the alcoholic extract sesame cake (600 mg/kg/day) and sesamol (10 mg kg1 day1) in a chronic unpredictable mild stress (CUMS)-induced model of mice. Remarkably, both sesame cake and sesamol significantly increased serotonin levels and inhibited oxidative stress in brain tissues of depressed mice. Moreover, both prevented the associated memory loss by

Sudan Turkey Yemen

South Korea

Argentina

Geographical origin Egypt Egypt

Boiling with water, inoculated (1%, v/v L. plantarum P8, 24 h, 37
C) Methanol-UAE Methanol-UAE Methanol-UAE

Methanol 63.5% ethanol, 220
C 8 MPa

Extraction after defatting and/or oil pressing Hydromethanolic hydroacetonic Methanol:water

23.10  0.00b 22.32  0.00b 19.21  0.03b

1.48  0.001a

0.81  0.02a 32.3  2.96b

TPC (mg GAE g ) DWa or FWb 1.9  0.3a 1.94  0.02a

1

13.95  0.00b^ 11.20  0.00b^ 11.57  0.00b^

0.4  0.02a* 2.56  2.96b*

0.88  0.02a*

TFC (mg QE* or CE^ g1) DWa or FWb

21.6  0.12b

TLC (mg SE g1 FW)

[87] [87] [87]

[74]

[24] [86]

Reference [10] [85]

L. plantarum Lactobacillus plantarum, DW dry weight (a), FW fresh weight (b), GAE gallic acid equivalent, QE quercetin equivalent (*), CE catechin equivalent (^), SE sesamin equivalent

Defatted sesame seeds Fermented sesame cake Sesame cake Sesame cake Sesame cake

Sample Cv. Giza 32 Cv. Shandweel 3

Table 5 TPC, TFC, and TLC of different sesame cake

174 R. H. Mekky et al.

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

175

Fig. 5 Base peak chromatograms (BPC) of the Egyptian cultivar of sesame Giza 32 of the oil (a1) and the cake (a2) and the distribution and classification of the observed metabolites in the oil (b1) and the cake (b2). (Adapted from [10, 79]) Table 6 Proximate composition of different sesame cake Proximate composition (%) Moisture Protein Carbohydrate Fat Ash

[90] 10.1 40.9 32.3 10.4 6.10

[91] 8.1 35.0 14.4 11.2 8.6

[92] 0.25 31.0 56.4 0.40 11.8

[93] 9.2 34.0 30.4 9.3 8.9

[94] 7.92 30.5 28.1 27.8 5.27

increasing postsynaptic density protein 95 in mice hippocampus depression and cognitive impairments [35].

3.3

Hypoglycemic Activities

Defatted sesame seeds expressed hypoglycemic activity in genetically diabetic KKAy male mice. The mice were fed hot water extract of defatted sesame seeds (4%) and its water-eluent (1.4%) and methanol-eluent (0.7%) fractions. Remarkably, hot water extract and its methanol-eluent fractions lowered plasma and urine glucose levels that could be attributed to their effect on the delay of glucose absorption

176

R. H. Mekky et al.

[95]. In the same manner, Wikul et al. [73] isolated lignans from sesame cake viz., pinoresinol, sesamolin, sesamin, and sesaminol monoglucoside. The isolated lignans exhibited α-glucosidase inhibitory activity except for sesaminol monoglucoside, where the IC50 ranged from 200 to 492 μM, indicating the bioactivity of the furofuran lignan aglycones. Moreover, the methanol extract of defatted black sesame cake showed α-glucosidase inhibitory in a dose-dependent manner where the IC50 of α-glucosidase inhibition was 375 μg mL1 extract. Nevertheless, the extract showed milder α-amylase inhibitory activity with 18% inhibition at approximately 750 μg mL1 extract [92].

3.4

Antiaging Activity

Nantarat et al. [76] isolated sesaminol diglucoside from black sesame seed cake. It exerted collagenase inhibitory activity (IC50 0.26 mg mL1), which was greater than the standard ascorbic acid collagenase inhibitory activity (IC50 0.44 mg mL1), and hence, it has a preventive effect on collagen degradation and wrinkles formation and could be a potential component in cosmetics preparations.

3.5

Anti-inflammatory Activity

Jan et al. [96] studied the anti-inflammatory activity of sesaminol triglucoside that was isolated from defatted sesame seeds. In a model of Sprague-Dawley rats and upon the oral administration of sesaminol triglucoside, its concentration was higher in small intestines, colon, cecum, and rectum than in the heart, lungs, liver, and kidneys with low detectable presence in the brain. The intestinal flora metabolized sesaminol triglucoside into catechol metabolites absorbed and distributed to the cardiovascular system and other systems. Significantly, they decreased the production of inflammatory markers as TNF-α and IL-6, RAW264.7 murine macrophages stimulated with lipopolysaccharide. The isolated sesaminol diglucoside from defatted black sesame seeds showed an inhibitory effect on hyaluronidase using SDS-PAGE with an IC50 value of 0.70 mg mL1 at 48 h in a concentration-dependent manner [76].

3.6

Estrogenic Activity

The isolated sesaminol triglucoside from sesame cake was metabolized by intestinal flora to catechol metabolites that exhibited ligand-dependent transcriptional activation in estrogen receptors beyond sesaminol triglucoside itself [96].

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

3.7

177

Antimicrobial Activity

Das et al. [97] managed to prepare protein hydrolysate from defatted sesame meal in an enzymatic membrane reactor with sequential fractionation and filtration to obtain peptides. They were tested against the pathogens Pseudomonas aeruginosa and Bacillus subtilis. Significantly, sesame peptides with molecular weight less than 1 kDa showed bacteriostatic activity.

3.8

Antihypertensive Activity

Regarding the antihypertensive activity of sesame, Aondona et al. studied the potential of the protein isolates of defatted sesame protein meal against angiotensin-converting enzymes (ACE) and human recombinant renin. The less than 1 kDa peptide fraction exhibited inhibition of (81%) against ACE being the most active among other protein isolates, whereas the other peptides (>3–5 and 5–10 kDa) were the most effective against renin with inhibition of (75–85%) [98]. In this context, Nakanao et al. investigated the antihypertensive activity of sesame peptide powder against ACE where the peptides Leu-Val-Tyr, Leu-Gln-Pro, and Leu-Lys-Tyr efficiently inhibited ACE at respective Ki values of 0.92 M, 0.50 M, and 0.48 M. Besides, a reconstituted mixture of the peptides Leu-Ser-Ala, Leu-GlnPro, Leu-Lys-Tyr, Ile-Val-Tyr, Val-Ile-Tyr, Leu-Val-Tyr, and Met-Leu-Pro-Ala-Tyr exerted intense antihypertensive activity via a significant temporal decrease in the systolic blood pressure (SBP) in spontaneously hypertensive rats (SHRs) by a single administration (1 and 10 mg kg1). These findings necessitate further studies for the development of nutraceuticals of sesame protein isolates to prevent hypertension [99].

3.9

Hypocholesterolemic Activity

Visavadiya and Narasimhacharya explored the hypocholesterolemic activity of sesame where defatted sesame seeds powder was administered orally through the diet to normal and hypercholesterolemic males Wistar rats for 4 weeks period at 5% and 10% dose levels. The powder of defatted sesame seeds did not influence normal rats. Nevertheless, it exerted a significant decline in the serum and hepatic levels of the total lipids, cholesterol, and LDL-cholesterol with an increase in the levels of HDL-cholesterol. Also, there was an increase in the fecal excretion of cholesterol and bile acids accompanied by a significant increase in hepatic HMG-CoA reductase activity and bile acid content. In addition, the oral intake of defatted sesame powder significantly enhanced hepatic cellular antioxidant enzymes viz, catalase, and superoxide dismutase. The activity is mainly attributed to the sesame meal of fibers and lignans, among other phenolics [100].

178

3.10

R. H. Mekky et al.

Antioxidant Activity

Sesame cake showed strong antioxidant potential. However, the radical scavenging activity of a compound or a plant is dependent on the polarity of the extract and the type of assay. Therefore, it is advised to use several assays to figure out the antioxidant potential of a specific extract [24]. In this context, several studies addressed the antioxidant activity of different extracts of sesame cakes from different geographical origins employing 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicalscavenging activity, β-carotene/linoleic acid bleaching assay, trolox equivalent antioxidant capacity assay (TEAC), ferric ion reducing antioxidant power (FRAP), among other activities. Table 7 demonstrates the antioxidant activities of some sesame cakes from different geographical origins.

4

Valorization Strategies of Sesame Oil Processing By-products

4.1

The Preservative Potential of Sesame Bio-waste

Natural antioxidants have captured the interest as a preservative for food products as they are safer than synthetic ones [23]. Sesame oil is one of the most stable vegetable oils of high oxidation resistance, preserving its nutritional values for a longer shelflife [29]. Sesame oil stability was explained by many antioxidant compounds such as sesamol, sesamin, and sesamolin. The waste of sesame oil processing still contains the previously mentioned lignans and other antioxidant compounds such as phenolic acids and flavonoids [24]. Sesamol, sesamin, and sesamolin, which were isolated from sesame cake, showed higher antioxidant activities than synthetic butylated hydroxytoluene (BHT), which, for example, reach the double activity as for sesamol [22]. Sunflower oil was effectively stabilized by sesame cake methanolic extract at 200 ppm, comparable to those of BHT and butylated hydroxyanisole (BHA). The total phenolics and flavonoid contents were 0.81 mg gallic acid equivalent g1 dry weight and 0.4 mg quercetin equivalent g1 dry weight. Sesame cake methanolic extract was able to reduce the loss of polyunsaturated fatty acids as well as inhibited double bond conjugation and thermal deterioration of sunflower oil. Mohdaly et al. recommended the use of sesame cake as a potent source of preservative for foods, especially vegetable oils and/or nutraceutical industries [24]. Moreover, cake methanolic extract was tested for preserving sunflower and soybean oils qualities using three different antioxidant mechanisms that proved a higher activity of the extract at 200 ppm than BHT and BHA at their legal limit. The estimated total phenolic and flavonoid of the extract were 1.94 (mg gallic acid equivalent g1 dry weight) and 0.88 (mg quercetin equivalent g1 DW), respectively [23]. Nadeem et al. tested three different concentrations of ethanolic sesame cake extract (50, 100, 150 ppm for 3 months), which was incorporated into olein-based butter and compared with control, BHA, and BHT for their potentials as a natural food preservative. The lipid peroxidation inhibition of ethanolic extract at 150 ppm

Turkey

Yemen

Thailand

Sesame cake

Sesame cake

Sesaminol diglucoside isolated from black sesame seed cake

Methanol-UAE

Methanol-UAE

15.3 mgTEAC g1 FS 14.5 mgTEAC g1 FS 12.5 mgTEAC g1 FS

100% at 100 μg mL1

TEAC (ABTS) 2.65 μmol TE g1 extract 82% at 50 μg mL1

2.18 mM Fe (II)/g of extract

[76]

[87]

15.8 mg-TEAC g1 FS IC50 0.201 mg mL1

[87]

16.9 mg-TEAC g1 FS

[74]

[86]

[24]

[85]

Reference [10]

[87]

68% at 200 μg mL1 68% at 200 μg mL1

FRAP

18.4 mg-TEAC g1 FS

60% at 200 μg/ mL 48% at 200 μg/ mL 84% at 200 μg/ mL 80.5%

DPPH

β-Carotenelinoleic acid bleaching

Bioactive Phytochemicals from Sesame Oil Processing By-products

TE Trolox equivalent, FS fresh sample, UAE ultrasound-assisted extract

Sudan

South Korea

63.5% ethanol, 220
C 8 MPa Boiling with water, inoculated (1%, v/v Lp, 24 h, 37
C) Methanol-UAE

Methanol

Egypt

Argentina

Methanol:water

Extract type Hydromethanolic hydroacetonic

Egypt

Fermented cake with Lactobacillus plantarum P8 Sesame cake

Cv. Shandweel 3 defatted seeds Cv. Shandweel 3 defatted seeds Defatted sesame seeds

Sample Cv. Giza 32 defatted seeds

Geographical origin Egypt

Table 7 Antioxidant activity of sesame cakes from different sources in TEAC, DPPH, β-carotene/linoleic acid, and FRAP systems

9 179

180

R. H. Mekky et al.

was superior to those of control, BHA, and BHT. The oxidative stabilization potentials of ethanolic extract was explained by the presence of antioxidant phenolic compounds at 1.72 mg gallic acid equivalent g1 dry weight and higher extents of antioxidant substances such as sesamol, sesamin, and sesamolin. The preservative effect of ethanolic extract was better than (BHT) without affecting overall acceptability score which suggesting its long-term use as a preservative [25]. Hydroethanolic extracts 70% of coconut oil meal and sesame oil meal were able to improve oxidative stability and extend the microbial shelf life of the vanilla cake. The total phenolic contents of coconut meal and sesame meal extracts were 0.77 and 2.11 mg gallic acid equivalent g1 dry weight. Meals extracts were incorporated at 20 mg 100 g1 of margarine before mixing with other ingredients of vanilla cake. Over 90% of the antioxidant activity was retained indicating high thermal stability after heating for 2 h at 180
C [31]. Extraction is a crucial step that affects the yield of the recovered amount of antioxidant compounds from sesame waste. Furthermore, the solvent, extraction time, temperature, and technique are the main factors that should be harmonized to maximize the recovered amount [29]. It is found that methanol and ethanol are more efficient solvents than the less polar ones such as diethyl ether, hexane, and petroleum ether using overnight maceration in a shaker at room temperature [24]. New electricity-based extraction techniques of sesame cake, such as high voltage electrical discharges and pulsed electric fields, offer an industrial solution through the decreased amount of used solvent and temperature values than conventional extraction procedure and increased yield up to 4.40 (mg GAE g1 DW) [26]. Sesame waste as a source of these phytochemicals with high antioxidant potentials can serve as high added-value compounds in many ways, such as antioxidants of health benefits that can protect from damaging effects of free radicals, which can cause many diseases like cancer. Furthermore, sesame waste can be used as food additive for fat containing foods to prevent lipid oxidation as a potent natural preservative of edible plant origin [29].

4.2

Balancing of Food Product Contents and Its Health Impacts

Nutrient phytochemicals of sesame residue can improve and balance the nutritional value of some commercial food products. Beside non-nutrient phytochemical content, cold-pressed cake is rich in protein (16.9–45.9%), essential amino acids, crude fiber (3.28–22.7%), and minerals such iron (14.5–55.6 mg 100 g1), zinc (10.2–13.0 mg 100 g1), sodium (23.3–39 mg 100 g1), potassium (117–406 mg 100 g1), and calcium (153–560 mg 100 g1) [29, 32]. Sesame meal contains relatively the same contents of protein and crude fiber as cake. However, sesame protein concentrate contains about 59% of protein which can be a suitable alternative source of protein for food industries [33]. Many nutritional limitations of the extruded products based on wheat, such as high gluten content, are linked to celiac disease, relatively low protein content, and a high glycemic index. These problems could be overcome by the addition of nutrient-rich supplements such as sesame

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

181

protein concentrate which contributed to decrease of gluten and carbohydrate (lower glycemic index) and increase of protein contents, as well as tef flour and tomato powder contributed to improving antioxidant properties and fiber content. Therefore, sesame protein concentrate could help balance macronutrients of wheat-based extruded as a partial substitute by improving nutritional and functional properties. Formulas with 10% have higher scores for acceptability of the color [30]. Nutritional qualities of wheat crackers and corn crackers enriched with sesame oil cake (DSC) and sesame waste sieved from tahini processing (SSWPT) were enhanced by increased protein, fiber, and minerals contents, as well as the caloric value and was decreased by a reduction in carbohydrates contents. Additionally, the antioxidant phytochemical content of (DSC) and (SSWPT) explains the high antioxidant activity and low peroxide value, which positively impacts both cracker’s stabilities. As a result, the nutritional and functional qualities of both crackers were improved. Moreover, both crackers containing 20% sesame sieved waste were the highest-ranked for technological qualities and overall liking of panelists [27]. Prakash et al. observed an improvement of microbial stability and nutritional qualities of wheat flour biscuits fortified with defatted flour of white and black sesame up to 50% without affecting biscuits’ overall quality [28]. Nowadays, several trails for the development of valuable dietary products using sesame waste for decreasing hydrogenated fat content adverse effects on the health such as spreadable cocoa cream as well as enhancing functional and nutritional qualities of other traditional foods such as Jordanian Ma’amoul’s dessert or Indian Cook Curry Mix [101–103].

4.3

Prospects for Treatment of Certain Diseases

Wichitsranoi et al. observed a decrease in the blood pressure of prehypertensive patients after treating with 2.52 g/day black sesame meal capsules for 4 weeks in a double-blinded study. Sesamin, sesamolin, and total tocopherol contents were 1.17 mg g1 DW, 0.60 mg g1 DW, and 105 μg g1 DW, respectively. The hypotensive effect was suggested to the decreased oxidative stress. Therefore, Wichitsranoi et al. recommended regular daily ingestion of 2.52 g dietary black sesame meal for prehypertensive individuals to prevent the progress of hypertension and with hypertensive patients as a part of the treatment [104]. Moreover, a metaanalysis showed that the consumption of sesame could be helpful in the reduction of blood pressure after retrieving data from eight controlled trials of 843 patients who met the eligibility criteria [105]. Reactive oxygen species (ROS) have been implicated in the initiation of neuronal cell death, which is responsible for the progression of many neurodegenerative diseases, such as Alzheimer’s disease, Parkinson’s disease, and Huntington’s disease. Oxidative stress worsens these diseases through impairment of cognitive functions and memory deficits [106]. Sesame cake extract, hydrolysate, and bioactive peptides proved beneficial effect in treating these neurodegenerative diseases by reducing oxidative stress combined with different mechanisms, as shown in Table 8. Sesame by-products, as a cheap source of great benefits

182

R. H. Mekky et al.

Table 8 Sesame biowaste as a potential source for the development of nutraceuticals for neurodegenerative diseases Sesame by-product Sesame cake hydrolysates

Disease Impaired spatial learning and memory deficits of Alzheimer’s disease

Model organism Mice using the Morris water maze test

Sesame cake extract and sesamol

Chronic unpredictable mild stress (CUMS) induced memory deficits

Mice using Morris water maze and Y-maze

Sesame cake bioactive peptides

Alzheimer’s disease

Transgenic Alzheimer’s disease Caenorhabditis elegans model

Sesame cake bioactive peptides

Parkinson’s disease

Two transgenic C. elegans models (NL5901 and BZ555)

Biological Activity and suggested mechanism Medium dose (20 mg kg1 d1) enhanced learning and memory function than lower and higher doses, improving mRNA expression of hippocampal cyclic AMP-responsive element-binding protein and up-regulating N-methyl-D-aspartate receptor NR2A and NR2B along with reduced oxidative stress CUMS-induced memory loss was significantly prevented with oral doses of sesamol (10 mg kg1 d1) and cake extract (600 mg kg1 d1), enhancing serum and hippocampus serotonin levels and postsynaptic density protein 95 expression as well as oxidative stress inhibition Dietary supplementation reduces amyloid-β induced toxicity by blocking skn-1 downregulation and enhancing oxidative stress tolerance through upregulation of key antioxidant enzyme levels The results showed decreased α-synuclein aggregation in muscle cells, 1-methyl-4phenylpyridinium ion-induced dopaminergic neuron degeneration, and reduced the level of ROS

Reference [37]

[35]

[34]

[38]

(continued)

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

183

Table 8 (continued) Sesame by-product Sesame cake bioactive peptides

Disease Huntington’s disease

Model organism Two transgenic C. elegans models (AM140 and HA759)

Biological Activity and suggested mechanism Bioactive peptides decreased polyglutamine aggregation, which reduced behavioral dysfunction in ASH neurons and polyglutamine mediated neuronal death. Furthermore, peptides increased resistance to oxidative stress and restored mitochondrial functional parameters

Reference [36]

in combating these neurodegenerative diseases, made them potential candidates for the development of nutraceuticals to be a part of the treatment guidelines.

4.4

Animal Feedstuffs

Price fluctuations in the feedstuff market can affect the production cost of animal products such as meat and dairy products. Therefore, developing good quality feed, especially cheap oil by-products, offers an economical and environmentally sustainable solution [55]. Soybean meal is one of the most expensive ingredients in conventional ruminant diets, which can be replaced by cheap alternative and a good source of protein such as sesame oil meal, cake or hulls [51, 54, 55], as shown in Table 9. Sesame meal improved feed intake and digestibility in lambs without affecting their performance and carcass composition [32]. The fermentation process of sesame meal using Lactobacillus acidophilus, Saccharomyces cerevisiae, and a combination of them showed the improved nutrient value and decreased phytic acid content. Therefore, broiler performances were enhanced by incorporating fermented sesame meal better than the raw meal [57]. Additionally, a broiler diet supplemented with sesame meal bioactive peptides showed beneficial effects on performance and microbiota activity [56], as shown in Table 9. Since fishmeal represents about 65% of the production costs in aquaculture [52], sesame oil cake, whether fermented or not, can be a less expensive and more sustainable alternative source of protein in fish feed, as shown in Table 9. However, the cake can be bio-processed using solid-state fermentation to increase amino acids and decrease crude fiber and antinutritional factors contents [53].

184

R. H. Mekky et al.

Table 9 Beneficial impacts for using sesame by-products as a feedstuff ingredient Studied Animal Barki lambs of 5–6 months age

Sesame by-product used in feedstuff Sesame meal replacing 50% and 100% of soybean meal which represents 16% of the feed mixture

Lactating Awassi ewes’ lambs

Sesame meal replacing 50% and 100% of soybean meal which represents 15% of the feed mixture

Awassi lambs

25% of conventional feedstuff was replaced by a mixture of dry bread, carob pods, olive cakes, and sesame meal

Desert lambs of Sudan (Shugor ecotype)

Sesame cake up to 20% of feedstuff

Awassi lambs

25% of sesame hulls

Broiler chickens

Fermented sesame meal for 12 days incorporated at 15% and 25% of total feedstuff ingredients, which represent about 50% and 100% replacement of soybean meal, respectively Sesame meal bioactive peptides at 100 mg/kg

Broiler chickens

Rainbow trout (Oncorhynchus mykiss)

Up to 52% substitution of the fishmeal with sesame oil cake without amino acid supplementation

Gained benefits Feed cost for kilogram gain was decreased, and economic efficiency for half and total replacement was improved by 147.9% and 163.5% without affecting their performance, ruminal fermentation, and digestibility Milk yield for both formulas was increased with decreased cost for a kilogram of milk production without affecting the remaining nutrients digestibility Alternative diet successfully reduces the cost of production without any substantial change in lamb performance or meat quality Carcass yield and feedlot performance were satisfactory for sesame cake diet inclusion in comparison with groundnut cake Feed intake was improved with no significant effects on carcass characteristics or meat quality and lowered production cost by replacing soybean meal and barley grain with sesame hulls Crude protein and phosphorus digestibility were improved, and subsequently, broilers performance

The population of Lactobacilli was increased while Escherichia coli viable cell count in the caecum segment was decreased Voluntary feed intake was markedly improved, which may explain the significant enhancement of their growth rate

Reference [55]

[54]

[107]

[108]

[51]

[57]

[56]

[109]

(continued)

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

185

Table 9 (continued) Studied Animal Rohu fingerlings, (Labeo rohita)

4.5

Sesame by-product used in feedstuff Fermented sesame oil cake by a phytase-producing, Bacillus subtilis

Gained benefits 40% showed better weight gain and carcass composition

Reference [53]

Substrate for Production of Valuable Ingredients

Sesame waste is a good source of nitrogen carbon that offers an inexpensive alternative substrate for the microbial production of antibiotics, antioxidants, and enzymes which mostly used solid-state fermentation technique (SSF) (Table 10). Sesame oil cake was a good carbon source for the production of daunorubicin with HEPES (N-[2-Hydroxyethyl]piperazine-N0 -[2-ethanesulfonic acid]) or phosphate buffer, which effectively increase the yield 6.6 and 5.4 folds and reduce the cost of production to 4.26% and 0.26%, respectively, in comparison with standard media [39]. Bacitracin production was improved by incorporating inexpensive sesame oil cake with soybean meal compared to soybean meal as a single source of nitrogen [47]. However, using sesame oil cake as a single source of nitrogen showed enhanced productivity of neomycin 8834 mg kg1 compared to soybean meal 8245 mg kg1 and control 7455 mg kg1 [40]. In the same way, rifamycin production was enhanced by using sesame oil cake as a single source of nitrogen [44]. The extraction efficiency for sesaminol triglucoside and sesaminol diglucoside was 12.2 and 7.6 mg g1 DW in the fermented sesame oil cake and 6.8 and 3.4 mg g1 DW in the nonfermented, respectively, which represent about a twofold increase. Therefore, fermentation can be a valuable tool for sesaminol glucosides industrial production [41]. Sesame waste was used for increasing the parasporal protein production, and carbon and nitrogen sources replacing control medium with sesame oil cake extract which showed concentration increase from 0.23 to 0.34 mg mL1 [48]. Pullulan was produced at 54.50 g/kg of sesame oil cake substrate, significantly higher than other substrates [50]. Sesame oil cake can be used as a co-substrate to produce polyhydroxyalkanoate, a promising bioplastic substitute for petrochemical plastics [49]. Many enzymes of critical industrial applications can be produced using sesame oil cake as a substrate, such as Lipase, phytase, L-glutaminase, and protease (Table 10). Their production depends on optimizing parameters such as time of incubation, moisture, pH, and particle sizes of substrate [32]. Although substrates based on sesame oil cake were investigated in many research pieces to produce various valuable compounds, which proved a success from the economic and environmental point of view, further studies are needed to discover more potentials and valorization strategies for this valuable agro-industrial waste.

186

R. H. Mekky et al.

Table 10 Valuable ingredients production using sesame oil cake Compound and its class Daunorubicin (antitumor antibiotic)

Microorganism Streptomyces peucetius

Bacitracin (antibiotic)

Bacillus licheniformis DW2 Streptomyces marinensis NUV-5 Amycolatopsis mediterranei OVA5-E7 Bacillus circulans YUS-2

Substrate and fermentation method Liquid culture medium supplemented with 5% sesame oil cake for 8 days Medium of solid-state fermentation supplemented with 1% sesame oil cake Medium of solid-state fermentation supplemented with 10% sesame oil cake for 10 days Medium of solid-state fermentation supplemented with 10% sesame oil cake for 9 days Liquid culture medium supplemented with 10% sesame oil cake for 8 days

Bacillus thuringiensis LDC-501

Spizizen medium supplemented with 5% (v/v) of sesame oil cake extract

[48]

Aureobasidium pullulans KY767024 Bacillus megaterium Ti3

Optimum conditions were liquidsolid ratio of 1.7 v/w and temperature of 23
C in SSF 57.7 g L1 of ragi husk, 17.3 g L1 of sesame cake, and 0.39 g/L KH2PO4 as substrate to produce a 0.61 g/L of polyhydroxyalkanoates submerged fermentation Optimized temperature and substrate to moisture ratio 32.3
C and 1:3.23 g mL1, respectively, in SSF with 22.40 U/g substrate Wheat bran with sesame cake (1:1 ratio) with 60.5% initial moisture content and 1% inoculum concentration for 72 h at 30
C in SSF with 44.5 U g1 dry substrate 75% sesame oil cake and 25% coconut oil cake substrate and the optimum parameters were temperature of 28
C, pH 7.0 with 50% moisture content and 40% inoculum volume for 120 h in SSF with 496 U g1 dry substrate

[50]

Neomycin (antibiotic)

Rifamycin (antibiotic)

Sesaminol triglucoside and sesaminol diglucoside (antioxidant lignans) Parasporal toxin (selective cytotoxic protein for human colon cancer cells) Pullulan (polysaccharide as thickener, E-1204) Polyhydroxyalkanoates (bioplastic polymer)

Lipase

Candida rugosa NCIM 3462

Phytase

Mucor racemosus NRRL 1994

L-glutaminase

Aspergillus wentii MTCC 1901

Reference [39]

[47]

[40]

[44]

[41]

[49]

[43]

[42]

[45]

(continued)

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

187

Table 10 (continued) Compound and its class Protease

4.6

Microorganism Serratia marcescens RSPB11

Substrate and fermentation method Optimum conditions for sesame oil cake were 7.0 for initial pH, 1.0 mL of inoculum volume, incubation for 72 h at 30
C in SSF with 1035 U/gram dry substrate

Reference [46]

Agriculture Applications

Sesame oil cake can be valorized in many agricultural applications such as liquid fertilizer, seeds priming agent, and for biocontrol of fungi and nematodes infecting crop plants. Cucumber plant height, leaf number, and shoot fresh weight were significantly increased after 14 days of treatment with 1% aqueous extract of sesame oil extract as a liquid fertilizer [61]. Priming maize seeds with 5% of sesame oil cake extract for 12 h was an effective treatment before sowing and showed the maximum percent of germination, length in root and shoot, and vigor index [59]. Rahman et al. observed that 3% of sesame oil extract produced 42.5% and 50.1% inhibition of Fusarium oxysporum FOS-3 isolate, which was higher than cake extracts of soybean and coconut, which may contribute to the biocontrol of Fusarium root rot and wilt disease of soybean [60]. Amending sesame oil cake to the soil at 50 g kg1 showed a 98.1% reduction in galling of the root-knot nematode, Meloidogyne incognita infecting tomato [58].

4.7

Environmental Bioremediation

Soil and water contamination with lead is a serious threat to both human health and the environment. Govarthanan et al. suggested that 2% of sesame oil cake extract can be employed to immobilize lead in mine soil through the biostimulation of nonindigenous activity of Bacillus sp. SKK11 [62]. Moreover, sesame oil cake hydrochar showed 24.5 mg/g Pb(II) adsorption capacity, which represents 97.2 adsorption percent for Pb(II) removal from water [64]. Additionally, powder of ZnCl2-modified sesame cake was a promising remedy for eliminating Basic Blue 26 from water with 91.2 mg/g maximum uptake capacity [63]. Therefore, sesame waste can be used for the bioremediation of both water and soil.

4.8

Bioenergy

The energy contained in organic compounds of sesame biomass can be produced either thermally by pyrolysis or anaerobic digestion. Pyrolysis of sesame oil cake in a semi-batch reactor yield 58.5% of bio-oil has a calorific value of 25.5 MJ kg1

188

R. H. Mekky et al.

which can be used as a fuel, and the produced bio-char can be used as combustion additive or adsorbent [65]. Chang et al. suggested using sesame oil meal as an alternative fuel because of the high combustion efficiency with 5140 kcal kg1 calorific value and low chlorine and sulfur emissions [67]. Rajagopalan et al. observed that the highest concentrations of butanol and hydrogen were obtained after 7 days of fermentation using Clostridium strain BOH3 in a mixed medium containing rice bran and sesame oil cake 94.5 and 36.7 g L1, respectively [66].

5

Conclusion

The global production of sesame is around seven million tons, with nearly 70% agrifood residue as the cake counterpart produced after oil expression. Several studies focused on the phytochemical composition of the cake counterpart, expressing its richness in polyphenolic as lignans, flavonoids, phenolic acids, and biologically active peptides. Besides, the sesame cake possesses several biological activities, for example, antioxidant, antimutagenic, hypocholesterolemic, anti-inflammatory, and antihypertensive activities with a remarkable neurodegenerative protective potential. Furthermore, sesame cake phenolics enhance the stability and extend the shelf life of vegetable oils. Furthermore, being a reservoir of nutrients, sesame cake is used in fortifications of animal feedstuffs and as liquid fertilizers. In addition, the by-product of sesame seeds is efficiently utilized in the bioremediation of the environment and bioenergy production. The efficient utilization of such under-valued agri-food residues provides a new prospect for its significance in the sustainable development of several industries.

References 1. FAO-Statistics (2018) Productions, crops. Accessed 25th Oct 2021 2. Bedigian D, Harlan JR (1986) Evidence for cultivation of sesame in the ancient world. Econ Bot 40:137–154 3. Aboelsoud NH (2010) Herbal medicine in ancient Egypt. J Med Plant Res 4:082–086 4. Shyu Y-S, Hwang LS (2002) Antioxidative activity of the crude extract of lignan glycosides from unroasted Burma black sesame meal. Food Res Int 35:357–365 5. Dachtler M, van de Put FHM, v. Stijn F, Beindorff CM, Fritsche J (2003) On-line LC-NMRMS characterization of sesame oil extracts and assessment of their antioxidant activity. Eur J Lipid Sci Technol 105:488–496 6. Singh K, Garg SK, Kalla A, Bhatnagar A (2003) Oilcakes as protein sources in supplementary diets for the growth of Cirrhinus mrigala (Ham.) fingerlings: laboratory and field studies. Bioresour Technol 86:283–291 7. Grougnet R, Magiatis P, Mitaku S, Terzis A, Tillequin F, Skaltsounis A-L (2006) New Lignans from the Perisperm of Sesamum indicum. J Agric Food Chem 54:7570–7574

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

189

8. Silva ER, Martino HSD, Moreira AVB, Arriel NHC, Silva AC, Ribeiro SMR (2011) Antioxidant capacity and chemical composition of whole grains of cream and black sesame. Pesqui Agropecu Bras 46:736–742 9. Lim T (2012) Sesamum indicum. In: Edible medicinal and non-medicinal plants, vol 4. Springer, pp 187–219 10. Mekky RH, Abdel-Sattar E, Segura-Carretero A, Contreras MDM (2019) Phenolic compounds from sesame cake and antioxidant activity: a new insight for agri-food Residues’ significance for sustainable development. Foods 8:432 11. Mekky RH, Abdel-Sattar E, Segura-Carretero A, del Mar Contreras M (2020) Profiling of the oil of the Egyptian cultivar of sesame ‘Giza 32’ using LC-MS-based untargeted metabolomics. In: 1st international electronic conference on food science and functional foods, foods 2020. Foods, MDPI. https://doi.org/10.3390/foods_2020-07730 12. Chang L-W, Yen W-J, Huang SC, Duh P-D (2002) Antioxidant activity of sesame coat. Food Chem 78:347–354 13. Chen PR, Chien KL, Su TC, Chang CJ, Liu T-L, Cheng H et al (2005) Dietary sesame reduces serum cholesterol and enhances antioxidant capacity in hypercholesterolemia. Nutr Res 25: 559–567 14. Namiki M (2007) Nutraceutical functions of sesame: a review. Crit Rev Food Sci Nutr 47:651– 673 15. Ahmed T, Shittu LJL, Bankole MA, Shittu RK, Adesanya OA, Bankole MN et al (2009) Comparative studies of the crude extracts of sesame against some common pathogenic microorganisms. Sci Res Essays 4:584–589 16. Nasirullah JT, Rakshitha D (2009) Isolation and antioxidant efficacy of nutraceutical concentrates from sesame and flax seed oils. J Food Sci Technol 46:66–69 17. Vishwanath HS, Anilakumar KR, Harsha SN, Khanum F, Bawa AS (2012) In vitro antioxidant activity of Sesamum indicum seeds. Asian J Pharm Clin Res 5:56–60 18. Mekky RH, del Mar Contreras M, Segura-Carretero A, Abdel-Sattar E (2018) Metabolic profiling of the cake of the Egyptian cultivar of sesame ‘Giza 32’ and antioxidant activity: a new insight for agro-industrial by-products utilization for sustainable development. In: 1st conference on sustainable development in pharmaceutical sciences. Faculty of Pharmacy and Drug Technology, Heliopolis University 19. Majdalawieh AF, Mansour ZR (2019) Sesamol, a major lignan in sesame seeds (Sesamum indicum): anti-cancer properties and mechanisms of action. Eur J Pharmacol 855:75–89 20. Tassoni A, Tedeschi T, Zurlini C, Cigognini IM, Petrusan J-I, Rodríguez Ó et al (2020) Stateof-the-art production chains for peas, beans and chickpeas-valorization of agro-industrial residues and applications of derived extracts. Molecules 25:1383 21. Yasothai R (2014) Chemical composition of sesame oil cake-review. Int J Environ Sci Technol 3:827–835 22. Suja KP, Jayalekshmy A, Arumughan C (2005) In vitro studies on antioxidant activity of lignans isolated from sesame cake extract. J Sci Food Agric 85:1779–1783 23. Mohdaly AAA, Smetanska I, Ramadan MF, Sarhan MA, Mahmoud A (2011) Antioxidant potential of sesame (Sesamum indicum) cake extract in stabilization of sunflower and soybean oils. Ind Crop Prod 34:952–959 24. Mohdaly AAA, Hassanien MFR, Mahmoud A, Sarhan MA, Smetanska I (2013) Phenolics extracted from potato, sugar beet, and sesame processing by-products. Int J Food Prop 16: 1148–1168 25. Nadeem M, Situ C, Mahmud A, Khalique A, Imran M, Rahman F et al (2014) Antioxidant activity of sesame (Sesamum indicum L.) cake extract for the stabilization of olein based butter. J Am Oil Chem Soc 91:967–977 26. Sarkis JR, Boussetta N, Blouet C, Tessaro IC, Marczak LDF, Vorobiev E (2015) Effect of pulsed electric fields and high voltage electrical discharges on polyphenol and protein extraction from sesame cake. Innov Food Sci Emerg Technol 29:170–177

190

R. H. Mekky et al.

27. Hafez HH (2018) Utilization of sesame processing byproducts in preparing some functional bakery products. Egypt J Agric Res 96:1077–1092 28. Prakash K, Naik SN, Vadivel D, Hariprasad P, Gandhi D, Saravanadevi S (2018) Utilization of defatted sesame cake in enhancing the nutritional and functional characteristics of biscuits. J Food Process Preserv 42:1–10 29. Şahin S, Elhussein EAA (2018) Assessment of sesame (Sesamum indicum L.) cake as a source of high-added value substances: from waste to health. Phytochem Rev 17:691–700 30. Sisay MT, Emire SA, Ramaswamy HS, Workneh TS (2018) Effect of feed components on quality parameters of wheat-tef-sesame-tomato based extruded products. J Food Sci Technol 55:2649–2660 31. Senanayake CM, Algama CH, Wimalasekara RL, Weerakoon WNMTDN, Jayathilaka N, Seneviratne KN (2019) Improvement of oxidative stability and microbial shelf life of vanilla cake by coconut oil meal and sesame oil meal phenolic extracts. J Food Qual 2019:1–8 32. Ancut‚a P, Sonia A (2020) Oil press-cakes and meals valorization through circular economy approaches: a review. Appl Sci 10:7432 33. Grasso S (2020) Extruded snacks from industrial by-products: a review. Trends Food Sci Technol 99:284–294 34. Ma X, Cui X, Li J, Li C, Wang Z (2017) Peptides from sesame cake reduce oxidative stress and amyloid-β-induced toxicity by upregulation of SKN-1 in a transgenic Caenorhabditis elegans model of Alzheimer’s disease. J Funct Foods 39:287–298 35. Liu Z, Liu X, Luo S, Chu C, Wu D, Liu R et al (2018) Extract of sesame cake and sesamol alleviate chronic unpredictable mild stress-induced depressive-like behaviors and memory deficits. J Funct Foods 42:237–247 36. Ma X, Li J, Cui X, Li F, Wang Z (2019) Dietary supplementation with peptides from sesame cake protect Caenorhabditis elegans from polyglutamine-induced toxicity. J Funct Foods 54: 199–210 37. Shu Z, Liu L, Geng P, Liu J, Shen W, Tu M (2019) Sesame cake hydrolysates improved spatial learning and memory of mice. Food Biosci 31:100440 38. Ma X, Li J, Cui X, Li C, Wang Z (2020) Dietary supplementation with peptides from sesame cake alleviates Parkinson’s associated pathologies in Caenorhabditis elegans. J Funct Foods 65:103737 39. Arun D, Dharmalingam K (1999) Short note: Streptomyces peucetius converts anthracycline intermediates efficiently in culture media containing oil cake as carbon source. World J Microbiol Biotechnol 15:333–334 40. Adinarayana K, Ellaiah P, Srinivasulu B, Bhavani Devi R, Adinarayana G (2003) Response surface methodological approach to optimize the nutritional parameters for neomycin production by Streptomyces marinensis under solid-state fermentation. Process Biochem 38:1565– 1572 41. Ohtsuki T, Akiyama J, Shimoyama T, S-i Y, Ui S, Hirose Y et al (2003) Increased production of antioxidative sesaminol glucosides from sesame oil cake through fermentation by Bacillus circulans strain YUS-2. Biosci Biotechnol Biochem 67:2304–2306 42. Roopesh K, Ramachandran S, Nampoothiri KM, Szakacs G, Pandey A (2006) Comparison of phytase production on wheat bran and oilcakes in solid-state fermentation by Mucor racemosus. Bioresour Technol 97:506–511 43. Rajendran A, Thangavelu V (2013) Utilizing agricultural wastes as substrates for lipase production by Candida rugosa NCIM 3462 in solid-state fermentation: response surface optimization of fermentation parameters. Waste Biomass Valori 4:347–357 44. Nagavalli M, Ponamgi S, Girijashankar V, Venkateswar Rao L (2015) Solid state fermentation and production of rifamycin SV using a mycolatopsis mediterranei. Lett Appl Microbiol 60: 44–51 45. Sameera V, Raju KJ (2015) Optimization of process parameters for the production of L-glutaminase with mixed substrate by solid state fermentation using Aspergillus wentii MTCC 1901. Int J Eng Res Techno 4:328–333

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

191

46. Bhargavi PL, Prakasham RS (2017) Agro-industrial wastes utilization for the generation of fibrinolytic metalloprotease by Serratia marcescens RSPB11. Biocatal Agric Biotechnol 9: 201–208 47. Wang Q, Zheng H, Wan X, Huang H, Li J, Nomura CT et al (2017) Optimization of inexpensive agricultural by-products as raw materials for bacitracin production in Bacillus licheniformis DW2. Appl Biochem Biotechnol 183:1146–1157 48. Grace JJ, Ramani G, Shenbagarathai R (2020) Enhancement of purified human colon cancerspecific parasporal toxin from Bacillus thuringiensis-LDC-501. Curr Microbiol 77:104–114 49. Israni N, Shivakumar S (2020) Polyhydroxyalkanoate (PHA) biosynthesis from directly valorized ragi husk and sesame oil cake by Bacillus megaterium strain Ti3: statistical optimization and characterization. Int J Biol Macromol 148:20–30 50. Mirzaee H, Khodaiyan F, Kennedy JF, Hosseini SS (2020) Production, optimization and characterization of pullulan from sesame seed oil cake as a new substrate by Aureobasidium pullulans. Carbohydr Polym Tech Appl 1:100004 51. Obeidat B, Aloqaily B (2010) Using sesame hulls in Awassi lambs diets: its effect on growth performance and carcass characteristics and meat quality. Small Rumin Res 91:225–230 52. Jahanbakhshi A, Imanpoor MR, Taghizadeh V, Shabani A (2013) Hematological and serum biochemical indices changes induced by replacing fish meal with plant protein (sesame oil cake and corn gluten) in the great sturgeon (Huso huso). Comp Clin Path 22:1087–1092 53. Das P, Ghosh K (2015) Improvement of nutritive value of sesame oil cake in formulated diets for rohu, Labeo rohita (Hamilton) after bio-processing through solid state fermentation by a phytase-producing fish gut bacterium. Int J Aquat Biol 3:89–101 54. Obeidat BS, Kridli RT, Mahmoud KZ, Obeidat MD, Haddad SG, Subih HS et al (2019) Replacing soybean meal with sesame meal in the diets of lactating Awassi ewes suckling single lambs: nutrient digestibility, milk production, and lamb growth. Animals 9:157 55. Omer HAA, Ahmed SM, Abdel-Magid SS, Bakry BA, El-Karamany MF, El-Sabaawy EH (2019) Nutritional impact of partial or complete replacement of soybean meal by sesame (Sesamum indicum) meal in lambs rations. Bull Natl Res Cent 43:98 56. Salavati ME, Rezaeipour V, Abdullahpour R, Mousavi N (2020) Effects of graded inclusion of bioactive peptides derived from sesame meal on the growth performance, internal organs, gut microbiota and intestinal morphology of broiler chickens. Int J Pept Res Ther 26,1541–1548 57. Hajimohammadi A, Mottaghitalab M, Hashemi M (2020) Influence of microbial fermentation processing of sesame meal and enzyme supplementation on broiler performances. Ital J Anim Sci 19:712–722 58. Radwan M, El-Maadawy E, Kassem S, Abu-Elamayem M (2009) Oil cakes soil amendment effects on Meloidogyne incognita, root-knot nematode infecting tomato. Arch Phytopathol Pflanzenschutz 42:58–64 59. Viji R, Manonmani V (2018) Influence of seed priming with oil cake extracts on quality parameters of maize seeds. Madras Agric J 105:243–246 60. Rahman MT, Rubayet MT, Khan AA, Bhuiyan M (2020) Integrated management of fusarium root rot and wilt disease of soybean caused by Fusarium oxysporum. Int J Biosci 17:83–96 61. Jang SJ, Park HH, Kuk YI (2021) Application of various extracts enhances the growth and yield of cucumber (Cucumis sativus L.) without compromising the biochemical content. Agronomy 11:505 62. Govarthanan M, Park S-H, Park Y-J, Myung H, Krishnamurthy RR, Lee S-H et al (2015) Lead biotransformation potential of allochthonous Bacillus sp. SKK11 with sesame oil cake extract in mine soil. RSC Adv 5:54564–54570 63. Jain SN, Garud VB, Dawange SD, Sonawane DD, Shaikh ER (2020) Sesame (Sesamum indicum) oil cake-industrial waste biomass for sequestration of Basic Blue 26 from aqueous media. Biomass Convers Biorefin 64. Khan MA, Alqadami AA, Wabaidur SM, Siddiqui MR, Jeon BH, Alshareef SA et al (2020) Oil industry waste based non-magnetic and magnetic hydrochar to sequester potentially toxic post-transition metal ions from water. J Hazard Mater 400:123247

192

R. H. Mekky et al.

65. Volli V, Singh R (2012) Production of bio-oil from de-oiled cakes by thermal pyrolysis. Fuel 96:579–585 66. Rajagopalan G, He J, Yang K-L (2016) One-pot fermentation of agricultural residues to produce butanol and hydrogen by Clostridium strain BOH3. Renew Energy 85:1127–1134 67. Chang F-C, Tsai M-J, Ko C-H (2018) Agricultural waste derived fuel from oil meal and waste cooking oil. Environ Sci Pollut Res 25:5223–5230 68. Ammar S, Contreras MM, Gargouri B, Segura-Carretero A, Bouaziz M (2017) RP-HPLCDAD-ESI-QTOF-MS based metabolic profiling of the potential Olea europaea by-product “wood” and its comparison with leaf counterpart. Phytochem Anal 28:217–229 69. Grougnet R, Magiatis P, Laborie H, Lazarou D, Papadopoulos A, Skaltsounis A-L (2011) Sesamolinol glucoside, disaminyl ether, and other lignans from sesame seeds. J Agric Food Chem 60:108–111 70. Schmidt TJ, Hemmati S, Fuss E, Alfermann AW (2006) A combined HPLC-UV and HPLCMS method for the identification of lignans and its application to the lignans of Linum usitatissimum L. and L. bienne Mill. Phytochem Anal 17:299–311 71. Guo H, Liu A-H, Ye M, Yang M, Guo D-A (2007) Characterization of phenolic compounds in the fruits of Forsythia suspensa by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry. Rapid Commun Mass Spectrom 21:715– 729 72. Katsuzaki H, Kawakishi S, Osawa T (1994) Sesaminol glucosides in sesame seeds. Phytochemistry 35:773–776 73. Wikul A, Damsud T, Kataoka K, Phuwapraisirisan P (2012) (+)-Pinoresinol is a putative hypoglycemic agent in defatted sesame (Sesamum indicum) seeds though inhibiting alphaglucosidase. Bioorg Med Chem Lett 22:5215–5217 74. Bae JJ, Yeon SJ, Park WJ, Hong GE, Lee CH (2016) Production of sesaminol and antioxidative activity of fermented sesame with Lactobacillus plantarum P8, Lactobacillus acidophilus ATCC 4356, Streptococcus thermophilus S10. Food Sci Biotechnol 25:199–204 75. Moazzami AA, Andersson RE, Kamal-Eldin A (2006) Characterization and analysis of sesamolinol diglucoside in sesame seeds. Biosci Biotechnol Biochem 70:1478–1481 76. Nantarat N, Mueller M, Lin W-C, Lue S-C, Viernstein H, Chansakaow S et al (2020) Sesaminol diglucoside isolated from black sesame seed cake and its antioxidant, anticollagenase and anti-hyaluronidase activities. Food Biosci 36:100628 77. Moazzami AA, Andersson RE, Kamal-Eldin A (2006) HPLC analysis of sesaminol glucosides in sesame seeds. J Agric Food Chem 54:633–638 78. Materska M (2015) Flavone C-glycosides from Capsicum annuum L.: relationships between antioxidant activity and lipophilicity. Eur Food Res Technol 240:549–557 79. Mekky RH, Abdel-Sattar E, Segura-Carretero A, Contreras MM (2021) Metabolic profiling of the oil of sesame of the Egyptian cultivar ‘Giza 32’ employing LC-MS and tandem MS-based untargeted method. Foods 10:298 80. Dabrowski KJ, Sosulski FW (1984) Composition of free and hydrolyzable phenolic acids in defatted flours of ten oilseeds. J Agric Food Chem 32:128–130 81. Mekky RH, del Mar CM, El-Gindi MR, Abdel-Monem AR, Abdel-Sattar E, Segura-Carretero A (2015) Profiling of phenolic and other compounds from Egyptian cultivars of chickpea (Cicer arietinum L.) and antioxidant activity: a comparative study. RSC Adv 5:17751–17767 82. Mekky RH, Thabet MM, Rodríguez-Pérez C, Elnaggar DMY, Mahrous EA, Segura-Carretero A et al (2020) Comparative metabolite profiling and antioxidant potentials of seeds and sprouts of three Egyptian cultivars of Vicia faba L. Food Res Int 136:109537 83. Mohdaly AAA, Sarhan MA, Smetanska I, Mahmoud A (2010) Antioxidant properties of various solvent extracts of potato peel, sugar beet pulp and sesame cake. J Sci Food Agric 90: 218–226 84. Morales-Soto A, García-Salas P, Rodríguez-Pérez C, Jiménez-Sánchez C, Cádiz-Gurrea ML, Segura-Carretero A et al (2014) Antioxidant capacity of 44 cultivars of fruits and vegetables grown in Andalusia (Spain). Food Res Int 58:35–46

9

Bioactive Phytochemicals from Sesame Oil Processing By-products

193

85. Abdelazim AA, Mahmoud A, Ramadan-Hassanien MF (2013) Oxidative stability of vegetable oils as affected by sesame extracts during accelerated oxidative storage. J Food Sci Technol 50: 868–878 86. Bodoira R, Velez A, Andreatta AE, Martinez M, Maestri D (2017) Extraction of bioactive compounds from sesame (Sesamum indicum L.) defatted seeds using water and ethanol under sub-critical conditions. Food Chem 237:114–120 87. Elhussein EAA, Şahin S (2019) Cleaner production of micronutrients from sesame seed pressed cake: a comparative study. Biomass Convers Biorefin 88. Konsoula Z, Liakopoulou-Kyriakides M (2010) Effect of endogenous antioxidants of sesame seeds and sesame oil to the thermal stability of edible vegetable oils. LWT 43:1379–1386 89. Wu S, Wang L, Shu F, Cao W, Chen F, Wang X (2013) Effect of refining on the lignan content and oxidative stability of oil pressed from roasted sesame seed. Int J Food Sci Technol 48: 1187–1192 90. Elsorady ME (2020) Characterization and functional properties of proteins isolated from flaxseed cake and sesame cake. Croat J Food Sci Technol 12:77–83 91. Nascimento EMGC, Carvalho CWP, Takeiti CY, Freitas DDGC, Ascheri JLR (2012) Use of sesame oil cake (Sesamum indicum L.) on corn expanded extrudates. Food Res Int 45:434–443 92. Reshma MV, Namitha LK, Sundaresan A, Ravi Kiran C (2013) Total phenol content, antioxidant activities and α-glucosidase inhibition of sesame cake extracts. J Food Biochem 37:723– 731 93. Sunil L, Appaiah P, Prasanth Kumar PK, Gopala Krishna AG (2015) Preparation of food supplements from oilseed cakes. J Food Sci Technol 52:2998–3005 94. Esmaeilzadeh Kenari R, Mohsenzadeh F, Amiri ZR (2014) Antioxidant activity and total phenolic compounds of Dezful sesame cake extracts obtained by classical and ultrasoundassisted extraction methods. Food Sci Nutr 2:426–435 95. Takeuchi H, Mooi LY, Inagaki Y, He P (2001) Hypoglycemic effect of a hot-water extract from defatted sesame (Sesamum indicum L.) seed on the blood glucose level in genetically diabetic KK-Ay mice. Biosci Biotechnol Biochem 65:2318–2321 96. Jan K-C, Ku K-L, Chu Y-H, Hwang LS, Ho C-T (2010) Tissue distribution and elimination of estrogenic and anti-inflammatory catechol metabolites from sesaminol triglucoside in rats. J Agric Food Chem 58:7693–7700 97. Das R, Dutta A, Bhattacharjee C (2012) Preparation of sesame peptide and evaluation of antibacterial activity on typical pathogens. Food Chem 131:1504–1509 98. Aondona MM, Ikya JK, Ukeyima MT, Gborigo T-wJA, Aluko RE, Girgih AT (2021) In vitro antioxidant and antihypertensive properties of sesame seed enzymatic protein hydrolysate and ultrafiltration peptide fractions. J Food Biochem 45:e13587 99. Nakano D, Ogura K, Miyakoshi M, Ishii F, Kawanishi H, Kurumazuka D et al (2006) Antihypertensive effect of angiotensin I-converting enzyme inhibitory peptides from a sesame protein hydrolysate in spontaneously hypertensive rats. Biosci Biotechnol Biochem 70:1118– 1126 100. Visavadiya NP, Narasimhacharya AVRL (2008) Sesame as a hypocholesteraemic and antioxidant dietary component. Food Chem Toxicol 46:1889–1895 101. Saleh M, Akash M, Al-Dabbas M, Al-Ismail K (2014) Sesame-oil-cake (SOC) impacted consumer liking of a traditional Jordanian dessert; a mixture response surface model approach. Life Sci J 11:38–44 102. Guzmán R, Gómez J, Chocrón S (2020) Potential use of Sesame (Sesamum indicum L.) oil and sesame oil cake in the development of spreadable cocoa cream. Am J Food Sci Nutr 2:1–11 103. Mummaleti G, Prasaram N, Busani N, Badugu MR, Satyanarayana CV (2020) Sesame meal and Moringa oleifera leaves ready to cook curry mix: an ethnic food of Godavari districts in Andhra Pradesh. India Eur J Nutr Food Saf:64–75 104. Wichitsranoi J, Weerapreeyakul N, Boonsiri P, Settasatian C, Settasatian N, Komanasin N et al (2011) Antihypertensive and antioxidant effects of dietary black sesame meal in pre-hypertensive humans. Nutr J 10:1–7

194

R. H. Mekky et al.

105. Khosravi-Boroujeni H, Nikbakht E, Natanelov E, Khalesi S (2017) Can sesame consumption improve blood pressure? A systematic review and meta-analysis of controlled trials. J Sci Food Agric 97:3087–3094 106. Barnham KJ, Masters CL, Bush AI (2004) Neurodegenerative diseases and oxidative stress. Nat Rev Drug Discov 3:205–214 107. Awawdeh MS, Dager HK, Obeidat BS (2019) Effects of alternative feedstuffs on growth performance, carcass characteristics, and meat quality of growing Awassi lambs. Ital J Anim Sci 18:777 108. Hassan H, Elamin K, Elhashmi Y, Eldar A, Elbushra M (2013) Effects of feeding different levels of sesame oil cake (Sesamum indicum L.) on performance and carcass characteristics of Sudan Desert sheep. J Anim Sci Adv 3:91 109. Nang Thu TT, Bodin N, De Saeger S, Larondelle Y, Rollin X (2011) Substitution of fish meal by sesame oil cake (Sesamum indicum L.) in the diet of rainbow trout (Oncorhynchus mykiss W.). Aquac Nutr 17:80–89

Part III Phytochemicals from Fruit Oil Processing By-products

Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products

10

Ame´lia Delgado, Nadia Chammem, Manel Issaoui, and Emna Ammar

Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 Most Common Processes for Olive Oil Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Most Common Processes for Table Olives Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Chemical Composition of Olive Processing By-products and Bioactive Compounds . . . . 2.1 Composition of Wastes and By-products from Olive Oil Extraction . . . . . . . . . . . . . . . . 2.2 Table Olives’ Wastewaters Composition and By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Bioactive Compounds from Olive Processing By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Extraction Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Applications and Health Benefits of Olive By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Valorization of Olive Processing By-products for Agricultural Applications . . . . . . . . . . . . . 5 Valorization of Olive By-products for Bioenergy and Other Purposes . . . . . . . . . . . . . . . . . . . . 6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

199 202 204 207 207 212 216 216 219 222 224 225 227

A. Delgado (*) Mediterranean Institute for Agriculture, Environment and Development (MED), University of Algarve Edf 8, Faro, Portugal e-mail: [email protected] N. Chammem Laboratoire d’Ecologie et de Technologie Microbienne, University of Carthage, Institut National des Sciences Appliquées et de Technologie (INSAT), Tunis, Tunisia e-mail: [email protected] M. Issaoui Lab-NAFS ‘Nutrition – Functional Food & Vascular Health’, Faculty of Medicine, University of Monastir, Monastir, Tunisia E. Ammar Laboratory of Environmental Sciences and Sustainable Development (LASED), University of Sfax, National Engineering School of Sfax, Sfax, Tunisia © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_10

197

198

A. Delgado et al.

Abstract

The olive sector is key in the Mediterranean countries and comprises olive oil extraction and table olive production, carried out by companies of different typologies and technological development. Due to increased awareness of the Food-Health-Environment Nexus, the popularity of olive oil has been steadily increasing worldwide, and consequently, more biowastes are produced (e.g., olive pomace and wastewaters). Comparatively to the olive oil industry, the table olives’ processing may generate highly variable amounts of wastewaters of different types, from close to zero waste, when olives are just dehydrated, as in Greek-style, to the serious environmental issues posed by the preparation of oxidized black olives (e.g., Californian-style). Most common industrial processes for olive oil and table olive obtainment generate biowastes that are pollutant and costly to treat. Such biowastes can be viewed as an environmental burden or a source for highly demanded chemicals, mainly due to their high content in phenolic compounds, which are highly valued by pharma and food industries, Therefore a growing number of publications and patents highlight the relevance of a circular economy approach in allowing increased profits through some innovation and process optimization. It is noteworthy that the circular approach aims at optimizing the resources (by re-using them and tackling waste) while minimizing the environmental impact of manufacturing operations (eco-economic decoupling). The current chapter focuses on olive by-products, presenting their compositions, highlighting the presence of certain bioactive compounds. We discuss herein prospective ways to valorize olive processing by-products in compliance with the 2030 agenda and with strict legislation on environmental protection. We believe that the information and proposed strategies are relevant to many stakeholders including smallholders in developing countries. Keywords

Biowaste valorization · Circular economy · Hydroxytyrosol · Olive oil · Olive pomace · Polyphenols · Table olive · Tocols · Tyrosol · Wastewater Abbreviations

ADF BOD COD EC EF-FEOX EVOO GRAS IP MUFA NDF

Acid detergent fiber Biological oxygen demand Chemical oxygen demand Electrical conductivity Electro fenton-fenton oxidation Extra virgin olive oil Generally recognized as safe Intellectual property Mono-unsaturated fatty acid Neutral detergent fiber

10

Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products

OMW OSW TOW PUFA DF SME SWOT VOO WIPO

1

199

Olive mill wastewater Olive solid waste Table olives’ wastewater Poly-unsaturated fatty acid Dietary fiber Small and medium size enterprise Strengths, weakness, opportunities, and threats Virgin olive oil World Intellectual Property Organization

Introduction

Olive oil is being consumed since antiquity because of its easy extraction from mature fruits, and it has been the main dietary source of fats in the Mediterranean, home to ancient civilizations that coined the western culture. Olive oil and table olives are also deeply rooted in the Mediterranean diet, becoming popular worldwide [1–3]. At least partly due to such a close relationship, the olive oil demand continues to follow a reasonable rising trend with figures of less than two orders of magnitude below those for the palm oil trade [4]. While olive oil keeps a reputable image, palm oil has been associated with severe environmental damage [5–7], and many food industries have removed it from food formulations in response to consumer demands. A Eurobarometer survey found that 91% of citizens from EC stated that climate change is a serious problem, and over three-fourths believe changes in the way we consume, produce, and trade are needed [8]. The pioneer EC climate law strongly encourages optimizing manufacturing processes, waste reduction, and the safe use of by-products and recycled materials [9]. On the other hand, many consumers from different parts of the world are also adopting more responsible and sustainable behaviors regarding food options. Recently, a survey conducted by the European Institute of Innovation and Technology [10] in 18 European countries revealed that awareness of consumers on healthy and sustainable food choices is increasing, despite possible gaps between intention and action. Another broad observational study with over 10,000 participants from 13 countries of different continents delivered similar results, highlighting that consumers seem to prefer food that have been produced and packed in sustainable ways [11]. Regarding sustainable and healthy consumer choices, as mentioned above, olive oil and table olives are pillars of the Mediterranean diet, recognized as healthy and sustainable outside the Mediterranean basin, namely in the relatively new oliveproducing countries such as the USA, Australia, Brazil, and Chile. Thus, according to the International Olive Oil Council, IOC [12], the main olive oil and table olives producer and consumer countries are in the Mediterranean area, notably Spain, Portugal, Greece, Italy, and Tunisia. However, Australia and the USA have been enforcing their presence both as producers and consumers. It is noteworthy that table olives can also be of high importance for the local economy in Mediterranean

200

A. Delgado et al.

countries as Spain, Italy, Greece, Turkey, Tunisia, and Morocco [13, 14]. Traditional olive oil production and table olives’ preparation are indeed at the reach of many small family businesses and can even be easily produced for auto-consumption thus tackling food security. Regarding table olives, generally in the Mediterranean countries, almost 50% of the supply is ensured by the informal sector, even in southern European countries, and its relevance for local economies in terms of wealth, health, and tradition should be noted. The adopted table olives manufacturing processes involve know-how on ancestral practices and agri-biodiversity valorization (choosing the best match of preparation style, fruit cultivar, and fruit ripeness stage). However, producers may lack basic knowledge of hygiene practices and wastewaters management. As for the olive oil, and when well processed, table olives constitute an interesting, rich source of flavors and beneficial compounds [15, 16]. In the current climate change scenario, a brighter future for the olive oil industry, involving so many smallholders, may depend on the capacity of these companies to implement actions toward a circular economic model. In practice, it means increasing process yields and efficiency while simultaneously decreasing waste and valorizing by-products, based on “reduce, reuse, recycle, recover, redesign, and remanufacturing” [17]. D’Adamo et al. [18] have shown that small-family businesses actively develop the circular economy, namely through savings (reducing inputs and reusing resources). SWOT analyzes show that the European model (which framework is the European climate law) creates opportunities for additional income such as energy recovery from biomass (from olive groves’ pruning, virgin olive oil pomace, or table olive’s pits), as well as from the recovery of added-valued compounds from wastewaters, allowing their reuse as secondary raw materials (e.g., in cosmetics or agriculture) [18, 19]. Estimations of the IOC indicate that world olive oil production for the 2020/2021 season could increase by 2.5%, and consumption would increase by 0.4%. Moreover, a glimpse of statistical data shows that the olive sector is gaining importance outside the Mediterranean area [20]. Since this chapter concerns the olive sector’s by-products valorization, we started with an overview of the most common processes used to obtain olive oil and table olives to clarify better what wastes or by-products accumulate, and how they can be handled and valorized. Figure 1 summarizes the most common processes, and hence the main sources of wastes from the olive sector. The Olea europaea leaves can also be an exciting source of valuable compounds, but since it is a waste mainly generated when trees are pruned and not when the fruit is processed, it is out of the scope of this chapter. As shown in Fig. 1, Olea europaea’s olive fruit can be processed as olive oil (mainly virgin olive oil) or as table olives. In both cases, liquid effluents and solid wastes are generated. Common compounds of commercial interest are found in these different wastes since the raw material is the same. In other words, the composition of such wastes is somewhat determined by their common raw material – the olive fruit, notably in respect to hydroxytyrosol, one of the most valued compounds. On

a

Wastewater (94% water + 1% oil) = 1000–1200Kg

Solid waste (50% 500–600 water + 4% oil) = 500-600Kg

OOSW

OOSW humid

OOSW

Solid + water waste (60% water + 3% oil) = 800-950 Kg

OMWW

Fig. 1 Olive processing into olive oil (a) and table olives (b)

Solid waste (25% water + 6% oil) = 400Kg

Wastewater (88% water + solids and oil) = 600Kg

Energy: 40–63 kWh

OMWW

Energy 90–117 kWh

OOSW

OOSW

Oil

Energy < 90117kWh

OMWW

1 ton

Water to polish the impure oil: 10L Fresh water for decanter : 0.5-1m3

Oil OMWW

H2O0.1–0.12 m3

1 ton

H2O 0.1–0.12 m3

Fruit processed as olive oil

Washing water 0.1–0.12

Washing Wastewater 0.5-2.0 m3 /ton TO

wastewater (lye) 0.5 m3 /ton TO

COD (g O2/l): 10-45

Spanish style green olives

0.5 m3 /ton TO

Fermentation wastewater

Washing Wastewater

Fermentation wastewater

b

0.5 -0.25 m3 /ton TO 0.5-3.0 m3 /ton TO 0.5 m3 /ton TO

wastewater (lye)

COD (g O2/l) : 2..5-35

Californian style black-ripe olives

Preparation stage : Reception, sorting, Fruits washings

Fruit processed as table olives (TO)

10 Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products 201

202

A. Delgado et al.

the other hand, observed differences are due to the chosen processes. As can be seen in Fig. 1, such differences and similarities can be regarded from different angles – from the final product point of view (olive oil and table olives) as well as within each process: for example, differences in volume and composition of waste are noted between olive oil extraction methods or between table olive preparation methods, when inspecting the left side (a) and right side (b) of Fig. 1.

1.1

Most Common Processes for Olive Oil Extraction

The olive oil is obtained by applying pressure to the drupes (fruit type) from Olea europaea, where oil represents 17–30% of the fresh olive weight, mainly in the pulp (mesocarp and in the epicarp), with the stone containing about 1% [21–24]. When considering olive oil extraction, the most valued fractions are of virgin olive oil, which can be graded as “extra-virgin olive oil” (EVOO) or just “virgin olive oil” (VOO), according to the quality (stability/low free acidity) and the sensorial assessment. Although some industries focus their business on optimizing the quality of the most valued oil types (EVOO and VOO), other companies proceed with the extraction of further oil fractions, still valued, despite their lower quality. Such oil fractions are obtained by the use of high temperatures and solvents as well as refining steps. In this case, a diversified range of products/brands is commercialized, eventually with increased profit, while the effluents usually contain less-valued compounds and may be harder and expensive to treat than in the case of VOO extraction only. Further details on oil extraction and refining can be found elsewhere [20, 25–28]. For the purpose of the present work and for practical reasons, we will not deal herein with solvent-containing and other effluents of complex composition, but we will rather focus on the process’ types that offer easy migration to a circular economic model presenting more gains and less obstacles in the short term. Among producers with whom “the organic logo” is gaining adherents, as in Europe and in the USA, the olive mills are generally located nearby the olive groves. Harvesting is mostly made by hand, despite some growers use light machinery. In intensive cultivation mode, fruits are carefully transported and quickly processed to ensure the best olive oil quality by avoiding physical damage of fruits, which enhances microbial contamination and lipid peroxidation. The most valued type, EVOO, is the fresh juice of the olive, obtained after a few physical unit operations at ambient or mild temperatures (T < 30
C). Besides pickling, storage, and processing, other factors contributing to the fruit’s quality include agronomic practices, weather conditions during ripening and harvesting seasons, the fruit variety and ripeness, and soil conditions [29–31]. Advances in technology now enable us to crush and press fruits, just like the ancient way, ensuring the best quality of the final product while maximizing the process yield and minimizing waste. Most recent research aims to improve these processes further, reducing waste, and decreasing energy and water consumption. In what respects the current processes, there are three main kinds of olive oil extraction

10

Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products

203

procedures generating different types and quantities of wastes, discontinuous, continuous two-phase decanter, and continuous three-phase decanter. Discontinuous processes with different optimization levels can be found all over the Mediterranean, especially in small mills and/or familiar businesses, because of its simplicity, generally allowing the production of high-quality olive oil and manageable amounts of waste (Fig. 1). Traditionally, stone olive mills, which have been around for many centuries, still grind the fruits. The stone cylinders turn around in a round tray whose floor is also in stone. Thanks to the slow and non-violent crushing action, good dough preparation is achieved, and the obtained oils are generally harmonious and balanced, from a sensorial perspective and thus of high-quality (EVOO). In this discontinuous process, a wet pomace is obtained after pressing the dough between mats by applying about 100 kg cm2 to squeeze out the oil, and wastewater (closely related to the fruit composition) is transposed into tanks, where natural decantation occurs to separate the aqueous from the oil phase. According to the process, this wastewater, of variable composition, is herein designated as olive mill wastewater (OMW) and contains nothing else but nutrients and other compounds originally present in the fruit [21, 24, 30]. Whatever the process, continuous or discontinuous, a critical step in olive oil extraction is the malaxation, which aims to facilitate the oil droplets’ coalescence into larger drops, avoiding emulsions and facilitating oil and water separation. Malaxer may also work as a heat exchanger in the continuous processes, being critical in olive oil extraction. The technological parameters of mixing (time and temperature) are essential for the yield, and as longer the homogenization time (usually from 45 to 60 min), the higher the yield and the lower the oil proportion lost in OMW. However, long exposures to air and water increase the oil-oxidation risk and may thus affect the olive oil quality and stability. After the malaxation step, the dough is injected (by a pump) into a centrifuge with a horizontal axis which acts as a horizontal decanter (of 2 or 3-phase). Inside the decanter, the olive dough, containing both added water and oil, may remain until the oil is separated from the water phase and the remaining solids, as happens in a settling tank, but more quickly [21, 25, 32]. In short, current automated processes consist of: 1. Crushing the fruits to break down the cells and release the so-called first pressure oil 2. Water addition and malaxation, consisting of slowly stirring and compressing the olive dough, in order to drain out the maximum of oil 3. Water–oil phase separation, by decanting/centrifugation, where the volumes of solid and liquid wastes differ between the two-phase and the three-phase centrifugal extraction system, herein designated as two-phase or three-phase decanter When comparing the three types of extraction systems described above (Fig. 1), it could be noticed that the discontinuous system requires less energy than the continuous system. On the other hand, the three-phase decanter uses more energy and water in the continuous system and produces the highest volumes of waste. In

204

A. Delgado et al.

general, the yield and the oil quality produced by the two-phase decanter continuous system are the highest, thus the most sustainable process to date [25, 30, 33]. The energy consumption in olive mills is mainly electric power to operate equipment, and only a small part is used to warm up water, for washing the oil at a temperature not exceeding 28
C. It is noteworthy that this water can be heated in a boiler fed with biomass (solid) waste, as the fruit stone accounts for a quarter of its weight), representing a circular approach saving in the electricity bill while reducing generated waste.

1.2

Most Common Processes for Table Olives Production

Besides producing olive oil, the fruits from diverse cultivars of Olea europaea L. can also be used for table olives manufacture, for which a myriad of traditional recipes exist, but only a few of them were scaled up for industrial production. Indeed, olives directly harvested are not edible because of flesh astringency and bitterness and their appropriate processing is required to get edible and good-tasting table olives. Processing styles are multiple and depend on the fruit maturation stage (green, turning color, or black) and variety, which in turn define physicochemical characteristics leading to specific final products. Such table olives’ processing mainly includes the debittering step and the preparation steps [34, 35]. Actually, before processing, olives undergo successive operations such as: (i) The picking: during this operation, olives intended for confectionery are handpicked regardless of their ripening stage for the same reasons mentioned above for olive oil. (ii) Transportation is generally ensured in perforated plastic crates to guarantee aeration and limit moisture loss from the olives. Once at the factory, the olives cannot be stored for more than 48 h because of rapid wilting. This period is further reduced to 24 h for mature fruits. (iii) Sorting and calibration: The sorting operation removes pitted, stained, injured and overripe olives, leaves, twigs, and peduncle. As for sizing, it represents a decisive step in the olive processing using lye. This step must imperatively precede the olives’ debittering treatment to allow the uniform penetration of the alkaline solution. Sizing is also used for the commercial classification of the final products. The present work focus on the most consumed products worldwide, specifically the pickled green olives (Spanish-style), the natural black olives in brine, and the olives darkened by oxidation (Californian-style) as presented in Fig. 2. The “Spanish-style” process can be summarized in an alkaline pretreatment, ensuring the fruits’ debittering and then a setting in brine, enhancing the lactic acid fermentation. The debittering step involves the olives’ treatment with lye or a potash solution to remove the excess of oleuropein, a glucoside responsible for the olive’s bitter taste.

10

Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products

205

Olive reception

Storage

Calibration

Sorting

Washing WTO Alkaline treatment

Sprinkling TODO

NTO

Alkaline treatment PTO

Washing

Washing

Oxidation in air

Fermentation

Packaging

NTO: Natural table olives PTO: Pickled table olives WTO: Wrinkled table olives TODO: Table olives darkened by oxidation

Fig. 2 Table olives processing steps according to different elaboration styles [35, 36]

An alkaline hydrolyzis occurs (Eq. 1), and the released glucose is an important carbon source in the initial steps of fermentation: Oleuropein ! Oleanolic acid þ Hydroxytyrosol þ Glucose

ð1Þ

The desired results are achieved within 8–12 h. The NaOH diffusion in the pulp hydrolyzes pectins softening the olive pulp [35]. The same reaction above (1) can be held enzymatically with glucosidases and esterases.

206

A. Delgado et al.

The alkaline solution’s concentration, immersion time, and penetration degree vary with the fruit variety, degree of maturity, and temperature. The concentrations of lye solutions used vary from 1.3 to 2.6% (w/v) [36]. During this process, washes are preceded by rinsing that should be carried out immediately after draining the alkaline solution to stop the debittering as quickly as possible avoiding the olives’ blackening phenomenon. The washes are also a fairly important step for good fermentation progress. Once washed, the olives are placed in barrels or fermentation tanks where they will be housed in brine to undergo the typical lactic fermentation. In general, sodium chloride is added to reach a concentration of 9 to 10% (w/v). However, the salt content should not exceed 5–6% during the fermentation step to avoid inhibiting lactic acid bacteria, particularly Lactobacillus sp., known as a dominant genus, particularly in the “Spanish-style” process. The fermentation step lasts from 3 to 6 months, depending on various factors, including the ambient temperature [37]. In obtaining black olives in brine (or natural black olives), the excess of bitter compounds is eliminated from the ripe fruits through several washes (debittering). As soon as the olives are received in the factory, they are placed in water for 2 or 3 days with several water renewals. Alternatively, the debittering stage may consist of a shorter washing period (not exceeding 18 h) with acidified water (pH 4.5). Debittered olives are then introduced into fermentors generally previously filled to one-third with a brine solution containing 8–10% NaCl and acidified to pH 4.5. A spontaneous fermentation process occurs thanks to an indigenous microflora consisting mainly of yeasts and lactic acid bacteria. By the end of the fermentation, herbs, lemon, orange peel, garlic, and other condiments, as well as olive oil, may be added for flavoring and preservation purposes. Regarding the olives darkened by oxidation (Californinan-style), two operations are key to this process: immersion in a lye solution and aeration. The darkening process of fruits begins with the first immersion of fruits in an alkaline solution (1–1.5% NaOH). This solution is then removed to expose the olives directly to the open air, promoting the oxidation of the bitter phenolic compounds. Once the epidermis is blackened in a uniform manner, the oxidation of the rest of the pulp involves successive immersions in NaOH solutions of decreasing concentration, from 1.5 to 0.5% for 2–24 h, interspersed by periods of exposure to the open air (dry) or insufflation of compressed air. Once completed, this oxidation treatment is then followed by washing for 5–7 days. The washing water is renewed on average twice a day to optimize the elimination of the residual lye. For a more intense blackening, the olives may also be treated with 0.1% of an iron gluconate solution. The fruits are then placed in a diluted brine to compensate for the NaCl losses caused by the alkaline treatments and the numerous washes. Calibration, color classification, and packaging are finally carried out. There are other commercial preparations of secondary importance because of the quantities of fruits processed or because of a delicate elaboration. The best known are:

10

Bioactive Phytochemicals from Olive (Olea europaea) Processing By-products

207

Black olives in dry salt: Fruits are picked when fully ripe, washed, and placed in alternating layers with dry salt (15% of the weight of the olives). The finished product is black with a subdued bitterness, a wrinkled appearance, and a tender pulp. As a result, the generated volumes of wastewaters are much smaller than with the above-mentioned processes. Greek-style olives: Also picked when ripe, the fruits are treated with a diluted alkaline solution. Then, they will be sprinkled with salt in barrels. The finished product is packed in dry, and it is more or less bitter, with the flesh of a wrinkled appearance. As above, this process generates reduced amounts of wastewaters. In short, the main commercial types of table olives are the Spanish-style green olives (50% of total production), Californian-style, black olives (25% of total production), and naturally black olives in brine (25% of total production) [35, 36, 38]. These processes are also those that generate larger amounts of wastewater, and they are the focus of the information and discussions herein presented when concerning table olives.

2

Chemical Composition of Olive Processing By-products and Bioactive Compounds

When approaching olive processing from the circular economy perspective, the opportunities for cost savings should be revealed as they enclose encouraging short-term gains [17]. An illustrative example regards water savings and subsequent reduction in the water footprint of the product. Thus, before any processing step, either oil extraction or table olives’ production, the fruits are first washed with fresh running water to clean them and separate leaves, small branches, and other solid impurities. As noted in Table 1, this water is suitable for other uses in the olive mill, such as equipment washing. It should be noted, however, that such reuse of resources may require layout planning and slight adjustments, which investment is likely to be quickly recovered and will undoubtedly bring important benefits in the long run, given the water scarcity that is already experienced in the Mediterranean [24, 39– 41].

2.1

Composition of Wastes and By-products from Olive Oil Extraction

Two main types of waste are generated from VOO extraction: olive mill solid waste (OSW), called pomace, and olive mill wastewater (OMW). The OMW, also called vegetable water, is a dark aqueous liquid, which quantity and quality depend on the extraction system, the fruit type, etc. A thin oil phase and a water/oil emulsion interphase are present on top of the dominant water phase [21, 30, 42–44]. Table 1 summarizes the main olive oil extraction processes, described in 1.1, from the perspective of the final product’s yield and volumes of waste. The values

0.5 m3 OMW

350 kg wet OSW

Pressure green leafy cover > tree leaf > skins > kernels. Nevertheless, the ascendancy of each acid in the goods varied upon its site in the samples [5]. Among the recognized phenolic acids, p-coumaric acid was most plentiful in hazelnut kernel, green leafy cover, and tree leaf, while gallic acid was most copious in hazelnut skin and hard shell, perhaps suggesting the existence and possibly the

25

Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products

565

supremacy of tannins in the latter sections. Qualitative and quantifiable variations occurred among nuts in the phenolic acids represented, with gallic acid prevalent except pine nut, almond, and hazelnut (filbert) [17]. A total of 8 phenolic acids were quarantined and named among 8 nuts (acids of p-hydroxybenzoic, p-hydroxyphenyl acetic, vanillic, protocatechuic, syringic, gallic, caffeic, and ferulic). Protocatechuic acid has been registered as the main phenolic acid in hazelnut skin with a concentration of 0.36 μg g
1. This phenolic acid was not found in previous studies [5, 6]. It was stated that caffeic, sinapic, ferulic, and p-coumaric acids are superior antioxidants than syringic, vanillic, and protocatechuic acids [18]. The MeOH wrest of hazelnut shells was probed for the phenolic content. These were categorized as a different diarylheptanoid, giffonin V, along with 15 known phenolic mixes going to diarylheptanoid, neolignan, phenylpropanoid, and flavonoids [19]. The quantifiable findings highlighted that essential compound appeared in the extract in intensity varying from 6.4 to 83 (mg/100 g). Pilot optimization indicated that a high-level revival of phenolics could be attained with less than 0.5 mm shell particle size when mined with acetone at 50  C. RSM tests revealed that a 10 g/l liquid to solid ratio, 58% acetone, and 12 h extraction time produced the greatest amount of phenolics. A 27 phenolic compound was found in hazelnut shells by mass spectrometry. Coumaroylquinic acid, epicatechin gallate, quercetin, and 6 other phenolics were found in hazelnut shells for the first time. The most plentiful phenolics in hazelnut shells were catechin, epicatechin gallate, and gallic acid [20]. The major polyphenolic subclass consists of monomeric and oligomeric flavan-3-ols, reported for more than 95% of total polyphenols. Flavonols and dihydrochalcones were 3.5%, while phenolic acids were fewer than 1% of the total identified phenolics [21]. A 6 phenolic aglycon, involving gallic acid, p-hydroxybenzoic acid, epicatechin and/or caffeic acid, sinapic acid, and quercetin, was divorced and shyly labeled in Turkish and American hazelnut extracts [22], demonstrating the excessive impacts of the array and extraction solvents on the concentration and irregularity of phenolic acids. For example, Amaral, Ferreres [23] discovered and measured 4 phenolic acids, namely, p-coumaroyltartaric acid, 5-caffeoylquinic acid, caffeoyl tartaric acid, and 3-caffeoylquinic acid in hazelnut leaves from 10 different cultivars cultivated in Portugal. Waste hazelnut shells (which account for about 50% of the nut weight) are potential raw materials to produce added-value goods. Hydrothermal pretreatment lets the hemicelluloses solubilization, while cellulose and lignin stay in the solid phase almost intact, letting their following processing for a vital valorization of the feedstock. The data included provide the basis for evaluating the large-scale fabrication of replaced oligosaccharides with bound phenolics as bioactive components of functional use in food, cosmetics, or pharmaceuticals [24]. Supercritical carbon dioxide extraction was found as an appropriate technique to regain the oil and other minor lipid bioactive compounds of the cake by-product, with a possible application in foods and nutraceuticals [25]. Figure 2 summarizes the main bioactive components of hazelnut oil-processing by-products. Table 1 also concludes the whole components of hazelnut oil-processing by-products either major or minor ones.

566

A. Nawaz and I. Khalifa

p-coumaric acid

Gallic acid

Protocatechuic acid

p-Coumaroylquinic acid

Fig. 2 Main bioactive components of hazelnut oil-processing by-products, drawn by Chem 3D ver. 19.1

5

Health-Promoting Effects of Hazelnut Oil Processing By-products

The key bioactive particles in hazelnut by-products are phenolic compounds. They consist of phenolic acids, stilbenes, lignans, and flavonoids. A comprehensive study on hazelnut by-products showed their antioxidant activity by various examinations, exposing as they could be deemed an exceptional supplier of raw antioxidants [26]. Hazelnut shells have a prospective source of antioxidant combinations with industrial interest in the cosmetic, pharmaceutical, and food industries. Antioxidants from hazelnut shells can be solubilized in autohydrolysis actions and recovered using resins. The data supplied could be more helpful to build and use phenolic compounds from hazelnut shells as a cause of pure antioxidants [28]. The total antioxidant activities of hazelnut extracts varied from 29 to 148 μmol of Trolox equivalent per g of EtOH extract, lowest in hazelnut kernel and greatest in hazelnut tree leaf. The antioxidant values of hazelnut by-product extracts were almost fourfivefold than those of hazelnut kernel at the same extract concentration. Similar

25

Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products

567

Table 1 Tocopherols (mg kg
1), polar phenolic compounds (mg kg
1), antioxidant activity (mmol kg
1), and pigments (mg kg
1) in different varieties of hazelnut nuts, their oils, and residual cakes. (Data source [27]) Hazelnut α-Ta γ-T α-Ta γ-T α-Ta γ-T Total polar phenolsb

DPPHc

ORACd

Pigments (cakes)

Nut Oil Cake Nut Oil Cake Nut Oil Cake Nut Oil Cake Chlor. Carot.

Negret 194.0 2.0 321.0 5.5 41.0 0.9 1720.0 12.1 4179.0 5.8 0.05 13.9 77.1 1.81 179.7 15.6 7.5

Pauetet 200.0 0.8 310.0 6.0 42.0 1.2 1324.0 10.4 3439.0 4.0 0.05 10.3 58.6 1.17 158.7 13.7 6.6

Tonda 235.0 1.0 378.0 3.2 49.0 1.8 1086.0 11.3 2261.0 2.9 0.09 8.1 56.5 2.17 122.5 10.9 7.9

Quantified using α-tocopherol as standard Quantified by Folin using gallic acid as standard c Quantified by radical 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl (DPPH) using Trolox as standard d Quantified by oxygen radical absorbance capacity (ORAC) using Trolox as standard. Chlor., chlorophylls; carot., carotenoids; α-T, α-tocopherol; γ-T, γ-tocopherol a

b

results were attained by Siriwardhana and Shahidi [15], who evaluated the total antioxidant activities of almond and its by-product extracts and understood that the 80% EtOH extracts at the same extract concentration were in the order of brown skin > green shell cover > whole seed. The total antioxidant values of brown skin and green shell cover extracts were 12.6- and 9.8-fold compared to whole seed extract, respectively. Alasalvar, Karamać [6] noted that extracts obtained from 80% EtOH were described as having significantly reduced antioxidants linked to extracts taken from 80% acetone. Wu, Beecher [29] evaluated the lipophilic and hydrophilic antioxidants of pooled foods in US marketplaces and derived that hazelnut had the third top value (96.4 μmol of Trolox equivalent per g) among 10 nuts that were examined, with pecan and walnut getting the best. The importance of defatted hazelnut and hazelnut makes the measurable comparison between the two findings difficult. Results revealed greater ideals when included tannins were analyzed, supported by the crude extract. Both 80% acetone and MeOH were adept at obtaining phenolics, but 80% acetone was a more efficient solvent for removing compressed tannins. These findings indicate that hazelnut skin can be deemed as a value-added by-product for use as dietary antioxidants [30]. The antioxidant activity of all the secluded compounds assessed indicated as flavonoid derivatives displayed

568

A. Nawaz and I. Khalifa

a greater free radical scavenging activity. Moreover, the cytotoxicity of each compound was analyzed against the cancer cell lines A549 and Hela and against human skin fibroblasts HaCat. None of the verified compounds, in a range of concentrations between 12.5 and 100 μM, cause a substantial decrease in the cell number [19]. The antioxidant values of the skins ranged between 0.6 and 2.2 mol of reduced iron/kg of the sample, which is about 3 times the antioxidant values of whole walnuts, 7– 8 times that of dark chocolate, 10 times that of espresso coffee, and 25 times that of blackberries [21]. Roasted hazelnut skins developed in proanthocyanidins with antioxidant activity and antifungal estates against Candida albicans without cytotoxic effect on HEKa and HDFa lines [31]. The metabolite reporting of roasted hazelnut skins was done, comprising oligomeric proanthocyanidins primarily formed by B-type oligomers of (epi)-catechin. Also, (epi)-gallocatechin and gallate derivatives were known as monomer units, and A-type PAs were detected as slight compounds [31]. Concerning antioxidants, the highest DPPH-scavenging effect value was achieved with 80% (v/v) aqueous acetone for 24 h with an active concentration equal to 1.12 mg/mL. When other nuts – walnuts, almonds, pine nuts, and peanuts – were detached under this condition, only walnut extract presented settled phenol content (268 mg GAE/g extract), antioxidant activity as unhurried by reducing power (EC50 ¼ 0.091 mg/mL), and free radical scavenging capacity than hazelnut extract [3]. Among the analyzed samples, the skin of whole roasted hazelnuts presented incredibly high extraction yields (about 30%) and extracts with the richest phenolic content (up to 502 mg/g, stated as gallic acid equivalents). The extracts from the skin of whole roasted hazelnuts documented the solidest antioxidant activity, similar or larger to butylated hydroxyanisole, butylated hydroxytoluene, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, and α-tocopherol, at equal concentrations, because they are rich in tannins [32]. Hazelnut skin and hazelnut green leafy shelter extracts at 50 ppm concentration proficiently kept copper-induced oxidation of human LDL cholesterol (99 and 93%, respectively) equated to hazelnut kernel (42%), hazelnut hard shell (56%), and hazelnut tree leaf (61%) extracts, which touched the same level of efficiency (99%) at 100 ppm. It is worth noting that at the 50-ppm level, all hazelnut extracts, except hazelnut kernel, were far more effective in impeding human LDL oxidation than catechin (53%) used as a standard. At 100 ppm, catechin showed 99% shyness, which was demonstrated by all hazelnut extracts. Like this study, Wijeratne, AbouZaid [33] found that the brown skin of almond exerted the highest preventative effect against LDL oxidation linked to those of whole almond and its green shell (leafy) cover. At 200 ppm, all extracts used the same effects. Dietary antioxidants, including those from hazelnut extracts, may thus reduce risk factors that have engaged in CHD. It was said that oxidation of human LDL by free radicals occurring from lipid oxidation products might be implicated in the pathogenesis of atherosclerosis, and transition metal ions could promote oxidative modification through binding with hydroperoxides [34]. The effect of hazelnut extracts on DNA single-strand breaks caused by Fenton reagent was analyzed [26]. Hazelnut skin extract proved the biggest inhibition, whereas hazelnut kernel extracts showed the lowest effect at

25

Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products

569

4 concentrations tested (5, 10, 25, and 50 ppm). Extracts from by-products (skin, hard shell, green leafy cover, and tree leaf) indicated stronger reserve than hazelnut kernel extract (except between tree leaf and hazelnut kernel extracts at the 25 ppm dose, which was either better than or like catechin in activity against OH-radical). Although plant-derived phenolic compounds could act as prooxidants and destroy biomolecules [35], all hazelnut extracts tested showed protective effects even up to a level of 50 ppm. The inhibitory effects of hazelnut extracts may be attributed to their capability to scavenge OH-radical. Thus, hazelnut products may also enroll in cancer prevention. Wijeratne, Abou-Zaid [33] explored the modesty of peroxyl and OH radical-produced DNA scission of whole almond seed, brown skin, and green shell (leafy) cover extracts between 2 and 100 ppm levels. Green shell cover extract at 50 ppm level completely captured peroxyl radical-induced DNA scission, but 100 ppm of brown skin and whole seed extracts was vital for equal yields. The common activity of hazelnut extracts was unique and may vary on the type of specific phenolics that appear in each extract, their relation activities, and possible synergistic and antagonistic effects taken about by various links among the mixtures involved. The advanced glycation end products (AGEs) arise from nonenzymatic results of sugar with protein side chains, some of which are oxidoreductase in the environment. Improved production of AGEs performs a crucial role in the pathogenesis of diabetic impediments and natural aging, renal failure, oxidative stress, and chronic inflammation. The antiglycation effects of polyphenols obtained by hazelnut skin that signifies an example of polyphenols-rich food industry by-product on AGEs creation were studied. AGEs derived from the cultivation of bovine serum albumin (BSA) and methylglyoxal (MGO) were described by fluorescence. The phenolics identification and total polyphenol content in hazelnut skin extracts were examined by HPLC-MS and the Folin-Ciocalteu method. Antioxidant efficacy was assessed by checking total antioxidant activity to evaluate samples’ ABTS radical scavenging activity by TEAC assay and oxygen radical absorbance capacity (ORAC) assay, conveyed as millimoles of Trolox equivalents per gram of sample. It was suggested that phenolic compounds in hazelnut skin have a repressing effect on the BSA-AGEs model in vitro, and this effect is concentration dependent. The putative role of the hazelnut skin antioxidative assets for hindering AGEs formation is also debated. Because of AGEs donation to the pathogenesis of several chronic diseases, foods, or inserts, including natural bioactive particles, able to impede their creation could be an exciting new tactic for supportive therapeutic attempts with a positive effect on human health [36].

6

Edible Applications of Hazelnut Oil-Processing By-products

Hazelnut, a vital supply of nutrition, is valuable for hazelnut milk making. Hazelnut cake, a by-result from hazelnut oil fabrication by cold media extraction technique, does not include any chemical excess and can be utilized for hazelnut beverage

570

A. Nawaz and I. Khalifa

manufacturing. Atalar, Gul [37] explored the effects of thermosonication on the quality factors of hazelnut milk and matched the findings found with the traditional thermal procedure. Various thermosonication situations at different amplitude stages (40 and 60% amplitudes for 5, 10, 15, 20, and 25 min and 80% amplitude for 3, 5, 10, and 15 min) were calculated for physicochemical and rheological goods, as well as microbial deactivation and bioactive compounds of hazelnut milk shaped from the cold pushed hazelnut cake as a by-product of oil production. Usually, the sonication process significantly improved the total phenolic compounds, antioxidant activity, appearance, and structural properties like syneresis, sedimentation, viscosity, and stability of samples. The use of thermosonication at 60% amplitude for 25 min and 80% amplitude for 15 min achieved full deactivation of microorganisms (total aerobic mesophilic bacteria and yeast mold). The full deactivation of microorganisms was also achieved by pasteurization at 85  C, but this action altered some discarded alterations like fails of bioactive compounds and the decline of structural assets. The findings suggested that thermosonication can be used for mechanized conduct of hazelnut milk with improved quality. This technique allows the assembly of hazelnut milk in safety and quality standards more healthy than the average product. On the other hand, Gul, Atalar [38] noticed that the impact of homogenization pressure was greatest on hazelnut milk properties charted by hazelnut cake concentration and homogenization temperature within the trial area. The adjusted trial conditions for the homogenization of hazelnut milk were 1,140 bar for homogenization pressure, 38.1  C for homogenization temperature, and 12.9% for hazelnut cake concentration. Recently, Acan, Toker [2] found that using 43.5% sugar, 7.18% MOP, and 7.25% hazelnut cake produced the optimum chocolate spread with the greatest desirability (1.00) without unnecessary variations in the quality properties. Thus, the hazelnut cake as an industrial by-product could be used in chocolate spread to grow bioactive compounds and reduce product costs by reducing sugar, milk, and whey powder of the final product. Spagnuolo, Della Posta [39] analyzed the antiglycation effects of polyphenols extracted by hazelnut skin that signifies an example of phenolics-rich food industry by-product on advanced glycation end products formation. It was suggested that polyphenols in hazelnut skin have an inhibitory effect on the advanced glycation end products model in vitro, and this effect is concentration dependent. The putative role of the hazelnut skin’s antioxidative properties for hindering advanced glycation end products formation is also debated. Because of advanced glycation end products’ input to the pathogenesis of several chronic diseases, foods enriched or supplements covering natural bioactive molecules able to inhibit their production could be an exciting strategy for backup therapeutic lines with a beneficial effect on human health. Bursa, Toker [40] valorized hazelnut cake in compound chocolate (HCC) as a partial replacer of sugar and milk-derived powders (MOP: skimmed milk and whey powder in equal amounts). D-optimal mixture design was utilized to optimize HCC formulation. The optimal sugar, MOP, and HC amounts were chosen as 25.0–40.0, 6.0–21.0, and 0.0–15.0 g/100 g, respectively. Furthermore, particle sizes and water activity were defined between 25.67 and 78.20 μm and 0.31–0.38, respectively. Total phenolic content in HCC samples, their digestibility, and bioaccessibility ranged from

25

Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products

571

1389 to 3367, 2601–3955 mg GAE/kg, and 112–187%, respectively. The hardness and brittleness also varied between 7.85 and 11.55 N and 0.52–1.02 mm, respectively. The samples’ sensorial characteristics, flow actions, and physicochemical properties indicated that HC might be a healthful and low-cost ingredient in HCC design to replace sugar and MOP partly. Likewise, Acan, Toker [2] evaluated the impact of hazelnut cake as a partial replacer for sugar, milk, and whey powders on the chocolate spread by measuring their physicochemical properties and in vitro digestion of total phenolic compound before and after digestion and its bioaccessibility. The optimization of the variables suggested that using 43.562% sugar, 7.186% MOP, and 7.252% HC produced the optimum chocolate spread with the highest desirability (1.00) without unwanted variations in the quality properties. The HC as an industrial by-product could be used in chocolate spread to increase bioactive compounds and decrease production costs by decreasing the final product’s sugar, milk, and whey powder. All physicochemical properties investigated significantly differed except turbidity and viscosity. Sensory evaluation revealed that the overall acceptability of the formulations was comparable to each other and that the panelists preferred both [41]. Producing of bioactive pullulan-based films is loaded with polyphenolic-rich extracts from roasted hazelnut skins (RHS, Corylus avellana L.). The hydroalcoholic extracts obtained from RHS by-products were separately combined (1%, 5%, and 10% w/w) with the filmogenic pullulan (PL) exopolysaccharide to fabricate flexible and bioactive films via a simple solvent-casting technique. The films present thermal stability up to 200  C, good mechanical performance with young’s modulus values higher than 2.6 GPa, and UV-light barrier properties. Furthermore, these flexible PL-based films exhibit a minimum antioxidant activity of ca. 94% (DPPH scavenging activity) for the film composed of only 1% of hydroalcoholic extracts. Both sets of films were tested for antibacterial activity toward Staphylococcus aureus, and the results demonstrate antibacterial effectiveness with the increasing content of both hydroalcoholic extracts. All the data evidences the potential applicability of these PL-based films containing hydroalcoholic extracts from agri-food by-products to develop sustainable films for active food packaging [42]. Hazelnut is an essential nutritional source; it is reasonably expensive for the production of hazelnut milk. Moreover, hazelnut cake is a by-product from hazelnut oil production and should not be directly used for human consumption because it may contain some residual chemical solvent from the hazelnut oil extraction process. However, the cake from the cold press, a by-product of hazelnut oil production, does not contain any chemical residue and can be used for hazelnut beverages. Moreover, high pressure homogenization is generally used for eliminating sedimentation of solids and creaming problems.

7

Technical Concerns to Hazelnut Oil-Processing By-products

In this chapter, numerous benefits of HPB have been described. Although HPB can be introduced in human food, several concerns and challenges need to be addressed in the future. Most of the works associated with the hazelnut proteins so far

572

A. Nawaz and I. Khalifa

concentrated heavily on lessening food allergies [43–45]. Notably, the relative digestive permanence of hazelnut allergens was believed to be low as compared to peanut allergens [46]. Bioactive peptides may form during the processing or digestion of protein-containing foods [47]. Furthermore, using proteases, bioactive peptides can be produced by breaking down food proteins in vitro. Enzymatic preparation of bioactive peptides is highly advantageous since toxic chemicals and organic solvents can be avoided. The final products are suitable for use in food, cosmetics, and pharmaceutical products [48], while demonstrating various bioactivities, including antioxidative, anticarcinogenic, antimicrobial activities, and ACE-inhibition activities, can also be possible. Another concern is reducing allergenic effects during the enzymatic treatments, enhancing the chances of utilizing hazelnut peptides in food formulations. Thus, the fortification of hazelnuts in food must be described on the label for consumers’ information. Another technological problem with HPB is the process of extracting hazelnut oil, which will influence the resulting by-products. High shear and/or high-pressure homogenization procedures significantly impact the functional and physiochemical characteristics of suspensions. High-pressure heat treatment (HPHT), for example, has been shown to influence the functional and structural features of hazelnut meal protein suspensions [7]. According to the findings, HPHT concentrations higher than 70 MPa unfolded HM proteins and caused a slight decrease in band intensity. Because of the protein increase, functional properties of hazelnut meal protein suspensions such as solubility, emulsifying, and foaming improved with HPH treatment up to 100 MPa. Higher pressures than 100 MPa, on the other hand, may cause the protein to unfold further, resulting in the formation of hydrophobic and -SH residues as well as increased protein aggregation, leading to decreased solubility and emulsifying and foaming activities. Another major concern is the functional and emulsifying properties of HPB, including defatted hazelnut cake and hazelnut protein. Although protein after purification results in different functional properties as in the cake, there are other ingredients. For example, Tatar, Tunç [8] studied the functional properties of both abovementioned ingredients. More research is needed to clarify the stability and action mechanism of the nano-emulsions fully, as well as to optimize formulation (because the encapsulation process reduced the antioxidant activity of the extract) and dosages levels from various perspectives, such as cost (mainly if the nanoemulsions are intended to be used as a preserving additive for low-cost products) and scalability. The method of processing may have a significant impact on the allergenicity of tree nut oils. Chemical-free mechanically pressed tree nut oils, such as cold- or expeller-pressed oils, are normally minimally processed after being expressed. However, chemically refined oils that have undergone some processing steps contain more leftover peptides and proteins than oils obtained this way [49]. Refining removes not only free fatty acids, phosphatides, and other impurities but also decreases the amount of residual protein in oils, which could bind IgE. The roasted flavor of tree nut oils is achieved by heat treatment. Protein denaturation can occur during the roasting process, reducing allergen availability. The

25

Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products

573

majority of the studies have shown that using heat to reduce allergen levels has a negligible impact [50, 51]. Some tree nut allergens are present in storage proteins, which are often heat stable and are expected to be caused by roasting. During roasting, however, previously secret epitopes may become exposed because of a conformational change in protein structure, resulting in the production of new allergens. As a result, pretreatment, especially roasting, should be done with caution and consideration for the intended end use. The oxidative stability of tree nut oils is influenced by the degree of unsaturation and the amount of available antioxidative components, such as tocopherols and lipophilic phenolics. Heat-induced changes in hazelnuts can lead to oxidative instability of the oil and phenolic compound degradation. Therefore, the cold pressing method is often advocated.

8

Conclusions

Hazelnuts signify an exciting source of by-products, creating a significant amount of waste such as leafy covers, skins, and shells. Hazelnuts are usually used whole or used as an element in many treated foods. Lately, the study of their composition has earned interest intending to add economic value to waste from hazelnut treating. It is essential to conduct further research on the chemistry of the hazelnut residents and their absorption, metabolism, excretion, and execution in investigational models and humans. Additional research is also needed to identify and assess the composition of polyphenolic compounds, especially flavonoids and other phenolic acid elements (glycoside and ester-bound) in hazelnut kernel and hazelnut by-products. The healthpromoting effects of hazelnuts protein have been described, especially the essential amino acids, about 35% of total amino acids. This makes it a strong candidate for fortification. Besides this, the functional properties of hazelnut protein cake, such as solubility and hydration capacity (even at low pH), endorse its fortification in human food, especially in beverages. However, the extraction techniques are very important, for example, roasting hazelnuts will result in the denaturation of protein, which will ultimately affect the functional properties. Besides this, hazelnut allergy is a big concern that must be addressed. The sensorial characteristics of the new product fortified with hazelnut protein also lack in the literature. With all these recommendations, the introduction of HPB in human food will open a new window of protein alternatives and mainly plant-based protein sources. This will lead to zero waste generation and one step ahead toward safe, healthy, and nutritious food.

References 1. Sen D, Kahveci DJW, Valorization B (2020) Production of a protein concentrate from hazelnut meal obtained as a hazelnut oil industry by-product and its application in a functional beverage. Waste Biomass Valoriz 11(10):5099–5107 2. Acan BG et al (2021) Physicochemical properties of chocolate spread with hazelnut cake: comparative study and optimization. LWT 147:111548

574

A. Nawaz and I. Khalifa

3. Delgado T et al (2010) Hazelnut (Corylus avellana L.) kernels as a source of antioxidants and their potential in relation to other nuts. Ind Crop Prod 32(3):621–626 4. Xu YX, Hanna MA, Josiah SJ (2007) Hybrid hazelnut oil characteristics and its potential oleochemical application. Ind Crop Prod 26(1):69–76 5. Shahidi F et al (2007) Antioxidant phytochemicals in hazelnut kernel (Corylus avellana L.) and hazelnut byproducts. J Agric Food Chem 55(4):1212–1220 6. Alasalvar C et al (2006) Antioxidant and antiradical activities in extracts of hazelnut kernel (Corylus avellana L.) and hazelnut green leafy cover. J Agric Food Chem 54(13):4826–4832 7. Saricaoglu FT et al (2018) Effect of high pressure homogenization (HPH) on functional and rheological properties of hazelnut meal proteins obtained from hazelnut oil industry by-products. J Food Eng 233:98–108 8. Tatar F et al (2015) Turkish Tombul hazelnut (Corylus avellana L.) protein concentrates: functional and rheological properties. J Food Sci Technol 52(2):1024–1031 9. Aydemir LY et al (2014) Bioactive, functional and edible film-forming properties of isolated hazelnut (Corylus avellana L.) meal proteins. Food Hydrocoll 36:130–142 10. Sarkis JR et al (2014) Evaluation of the phenolic content and antioxidant activity of different seed and nut cakes from the edible oil industry. J Am Oil Chem Soc 91(10):1773–1782 11. Gorissen SHM et al (2018) Protein content and amino acid composition of commercially available plant-based protein isolates. Amino Acids 50(12):1685–1695 12. Kato H et al (2018) Nutritionally non-essential amino acids are dispensable for whole-body protein synthesis after exercise in endurance athletes with an adequate essential amino acid intake. Amino Acids 50(12):1679–1684 13. Gülseren İ, ÇAkir B (2019) Preliminary investigations in vitro ACE-inhibitory activities of tryptic peptides produced from cold press deoiled hazelnut meals. Gıda 44(2):309–317 14. Fleischer DM (2007) The natural history of peanut and tree nut allergy. Curr Allergy Asthma Rep 7(3):175–181 15. Siriwardhana SS, Shahidi F (2002) Antiradical activity of extracts of almond and its by-products. J Am Oil Chem Soc 79(9):903–908 16. Yu J, Ahmedna M, Goktepe I (2005) Effects of processing methods and extraction solvents on concentration and antioxidant activity of peanut skin phenolics. Food Chem 90(1–2):199–206 17. Senter S, Horvat R, Forbus WR (1983) Comparative GLC-MS analysis of phenolic acids of selected tree nuts. J Food Sci 48(3):798–799 18. Cuvelier M-E et al (1992) Comparison of the antioxidative activity of some acid-phenols: structure-activity relationship. Biosci Biotechnol Biochem 56(2):324–325 19. Masullo M et al (2017) LC-MS profiling highlights hazelnut (Nocciola di Giffoni PGI) shells as a byproduct rich in antioxidant phenolics. Food Res Int 101:180–187 20. Yuan B et al (2018) Extraction, identification, and quantification of antioxidant phenolics from hazelnut (Corylus avellana L.) shells. Food Chem 244:7–15 21. Del Rio D et al (2011) Polyphenolic composition of hazelnut skin. J Agric Food Chem 59(18): 9935–9941 22. Yurttas H, Schafer H, Warthesen JJ (2000) Antioxidant activity of nontocopherol hazelnut (Corylus spp.) phenolics. J Food Sci 65(2):276–280 23. Amaral JS et al (2005) Phenolic profile of hazelnut (Corylus avellana L.) leaves cultivars grown in Portugal. Nat Prod Res 19(2):157–163 24. Rivas S, Moure A, Parajó JC (2020) Pretreatment of hazelnut shells as a key strategy for the solubilization and valorization of hemicelluloses into bioactive compounds. Agronomy 10(6): 760 25. Vasquez WV et al (2021) Supercritical carbon dioxide extraction of oil and minor lipid compounds of cake byproduct from Brazil nut (Bertholletia excelsa) beverage production. J Supercrit Fluids 171:105188 26. Shahidi F, Alasalvar C, Liyana-Pathirana CM (2007) Antioxidant phytochemicals in hazelnut kernel (Corylus avellana L.) and hazelnut byproducts. J Agric Food Chem 55(4):1212–1220 27. Ojeda-Amador RM et al (2019) Chemical characterization of virgin almond and hazelnut oils and their by-products. Eur J Lipid Sci Technol 121(11):1900114

25

Bioactive Phytochemicals from Hazelnut (Corylus) Oil Processing By-products

575

28. Pérez-Armada L et al (2019) Extraction of phenolic compounds from hazelnut shells by green processes. J Food Eng 255:1–8 29. Wu X et al (2004) Lipophilic and hydrophilic antioxidant capacities of common foods in the United States. J Agric Food Chem 52(12):4026–4037 30. Alasalvar C et al (2009) Antioxidant activity of hazelnut skin phenolics. J Agric Food Chem 57(11):4645–4650 31. Piccinelli AL et al (2016) HRMS profile of a hazelnut skin proanthocyanidin-rich fraction with antioxidant and anti-Candida albicans activities. J Agric Food Chem 64(3):585–595 32. Contini M et al (2008) Extraction of natural antioxidants from hazelnut (Corylus avellana L.) shell and skin wastes by long maceration at room temperature. Food Chem 110(3):659–669 33. Wijeratne SS et al (2006) Antioxidant polyphenols in almond and its coproducts. J Agric Food Chem 54(2):312–318 34. Decker EA et al (2001) Inhibition of low-density lipoprotein oxidation by carnosine and histidine. J Agric Food Chem 49(1):511–516 35. Aruoma OI et al (1998) Effect of hydroxytyrosol found in extra virgin olive oil on oxidative DNA damage and on low-density lipoprotein oxidation. J Agric Food Chem 46(12):5181–5187 36. Spagnuolo L et al (2021) Antioxidant and antiglycation effects of polyphenol compounds extracted from hazelnut skin on advanced glycation end-products (ages) formation. Antioxidants 10(3):424 37. Atalar I et al (2019) Influence of thermosonication (TS) process on the quality parameters of high pressure homogenized hazelnut milk from hazelnut oil by-products. J Food Sci Technol 56(3):1405–1415 38. Gul O et al (2018) Effect of multi-pass high pressure homogenization on physicochemical properties of hazelnut milk from hazelnut cake: an investigation by response surface methodology. J Food Process Preserv 42(5):e13615 39. Spagnuolo L et al (2021) Antioxidant and antiglycation effects of polyphenol compounds extracted from hazelnut skin on advanced glycation end-products (AGEs). Formation 10(3):424 40. Bursa K et al (2021) Valorization of hazelnut cake in compound chocolate: the effect of formulation on rheological and physical properties. LWT 139:110609 41. Sen D, Kahveci D (2020) Production of a protein concentrate from hazelnut meal obtained as a hazelnut oil industry by-product and its application in a functional beverage. Waste Biomass Valoriz 11(10):5099–5107 42. Esposito T et al (2020) Valorisation of chestnut spiny burs and roasted hazelnut skins extracts as bioactive additives for packaging films. Ind Crop Prod 151:112491 43. Flinterman AE et al (2008) Hazelnut allergy: from pollen-associated mild allergy to severe anaphylactic reactions. Curr Opin Allergy Clin Immunol 8(3):261–265 44. Flinterman AE et al (2008) Lipid transfer protein–linked hazelnut allergy in children from a non-Mediterranean birch-endemic area. J Allergy Clin Immunol 121(2):423–428 45. Ortolani C et al (2000) Hazelnut allergy: a double-blind, placebo-controlled food challenge multicenter study. J Allergy Clin Immunol 105(3):577–581 46. Vieths S et al (1999) Digestibility of peanut and hazelnut allergens investigated by a simple in vitro procedure. Eur Food Res Technol 209(6):379–388 47. Dullius A, Goettert MI, de Souza CFV (2018) Whey protein hydrolysates as a source of bioactive peptides for functional foods–biotechnological facilitation of industrial scale-up. J Funct Foods 42:58–74 48. Agyei D, Danquah MK (2011) Industrial-scale manufacturing of pharmaceutical-grade bioactive peptides. Biotechnol Adv 29(3):272–277 49. Hidalgo FJ, Zamora R (2006) Peptides and proteins in edible oils: stability, allergenicity, and new processing trends. Trends Food Sci Technol 17(2):56–63 50. Masthoff LJ et al (2013) A systematic review of the effect of thermal processing on the allergenicity of tree nuts. Allergy 68(8):983–993 51. Vanga SK, Raghavan V (2017) Processing effects on tree nut allergens: a review. Crit Rev Food Sci Nutr 57(17):3794–3806

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil Processing By-products

26

Onur O¨zdikicierler and Burcu O¨ztu¨rk-Kerimoğlu

Contents 1 2 3 4 5

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Botanical and Morphological Characteristics of Pistachio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nutritional Features of Pistachio Including Phytochemical Compounds . . . . . . . . . . . . . . . . . Methods for Pistachio Oil Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pistachio Oil By-products with Regard to Their Potential Phytochemical Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Pistachio Flour . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Pistachio Hull . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Pistachio Shell and Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Assessment of Pistachio Originated By-products in Food Product Formulations: From Waste to Functional Ingredients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

578 579 580 581 583 584 588 589 590 592 592

Abstract

Nuts have been regular diet components for long years due to their excellent functional and nutritious properties. Pistachio (Pistachia vera L.) is one of the most popular and high-value tree nuts widely grown in various world regions. The unique chemical composition and favorable flavor make pistachio an attractive source to be used as a food ingredient or further processed into edible oil. Pistachio oil production starts with drying before the extraction that can be

“For everything in this world, for wealth, for the soul, for life, for success, the truest guide is science.” Mustafa Kemal Atatürk O. Özdikicierler (*) · B. Öztürk-Kerimoğlu Faculty of Engineering, Food Engineering Department, Ege University, Bornova/Izmir, Turkey e-mail: [email protected]; [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. F. Ramadan Hassanien (ed.), Bioactive Phytochemicals from Vegetable Oil and Oilseed Processing By-products, Reference Series in Phytochemistry, https://doi.org/10.1007/978-3-030-91381-6_27

577

O. O¨zdikicierler and B. O¨ztu¨rk-Kerimoğlu

578

applied by mechanical pressing or solvent extraction. Pistachio oil obtained using traditional solvent extraction needs to be refined to make it suitable for human consumption. Since refining operation has detrimental effects on vulnerable bioactive compounds, supercritical fluid extraction has become prominent since pistachio oil can be produced with high nutritive quality. The major by-products derived from pistachio oil production could be classified as flour, hull, and its extract, flour of pistachio skin, and shells. These by-products are known as rich in terpenoids (carotenoids and triterpenes), phenolic compounds (flavonoids, phenolic acids, and tannins), lipids, amino acids, and carbohydrates. Studies reveal that ground shells also have the potential as dye adsorbents and can be used in water treatment systems. This chapter provides insight into the main characteristics of pistachio, fundamentals of pistachio oil processing, classification of the by-products that arise from oil manufacture, and potential bioactive compounds derived from pistachio oil processing by-products. Keywords

Pistachio · Pistachio by-products · Pistachio flour · Pistachio hull · Pistachio oil · Pistachio shell

1

Introduction

Nuts are defined as fruits containing a hard shell covering an edible kernel [1]. The pistachio nut (Pistacia vera L.), known as “golden tree” or “green gold,” is a very popular crop nut that belongs to the cashew or sumac family (Anacardiaceae) [2]. Even though various species of the genus Pistacia are referred to as pistachio, only Pistacia vera fruits promote the possibility of being consumed as edible nuts [3]. Pistachio is broadly grown in hot-dry and saline regions of the Middle East, the Mediterranean, and America [4, 5]. The nut mainly has two centers of origin: (1) the Near East that comprises Anatolia, Caucasus Region, Iran, and Turkmenistan; and (2) Central Asia that comprises Northern India, Afghanistan, Tajikistan, and Pakistan. The initial cultivation area and, thereby, the main center of origin is the Southeastern Anatolia Region, where most of Turkey’s production is handled [2]. Since the pistachio tree has been spread mainly around many different areas worldwide, this has resulted in the development of different cultivars that could survive in the climatic conditions of their growing region [6]. According to the Food and Agriculture Organization Corporate Statistical Database (FAOSTAT) [7], annual worldwide production of pistachio has been increased from 837,888 tons in 2015 to 911,829 tons in 2019, indicating that the overall production has risen by almost 10% in the last years. Figure 1 depicts the world’s leading pistachio-producing countries according to their production volumes in 2019. As is seen in the figure, pistachio is mainly produced in the Islamic Republic of Iran, the USA, China, Turkey, and the Syrian Arab Republic. Apart from them, the

26

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil. . .

579

Fig. 1 Pistachio production percentages of countries worldwide in 2019. (Based on the source data from FAOSTAT, 2021)

largest producers of the European Union are Italy and Greece [1]. Due to the growing interest in mechanized production of crops in recent years, the knowledge of important physical characteristics such as shape, size, mass, bulk density, porosity, angle of repose has to be extended for contributing to supply the required standards and desired quality throughout harvesting and processing of pistachio [3, 4].

2

Botanical and Morphological Characteristics of Pistachio

The unique ecological features of pistachio are stated to lead the way in successful cultivation and relatedly the spread and development of this fruit [2]. The fruit has a well-known drought tolerance so that pistachios could survive in arid and semi-arid areas [8]. It grows better in hot, dry, and long summers, and thereby the pistachio tree could indicate a high yield in circumstances that are unfavorable for other fruit trees [1]. The pistachio tree is a single-trunk, perennial, deciduous, and dioic plant shaped like an open umbrella growing upwards and laterally up to 3–10 m with its strong roots and compound leaves [2]. The biomass from the harvesting of pistachios is made up of fruits, twigs, and leaves, and afterward, the fruits are separated from this biomass and then peeled [8]. The physical structure of the pistachio fruit is presented in Fig. 2. The fruit could be referred to as a semi-dry drupe that comprises a single edible seed named “kernel” which is encased by a thin and soft coat called “testa.” This structure is enclosed by a lignified shell called “endocarp.” In addition, the whole structure is covered by “mesocarp” (woody shell) and “epicarp” (hull) [8, 9]. As the nutmeat grows, it fills the shell, and after a specific growing, it cracks the shell open due to its growth exceeding the shell size. During this stage, the hull remains stable, thus protecting the nutmeat from insects and pathogens [10].

580

O. O¨zdikicierler and B. O¨ztu¨rk-Kerimoğlu

Fig. 2 The physical structure of the pistachio nut and representative images of roasted nuts and their fragments

3

Nutritional Features of Pistachio Including Phytochemical Compounds

Worldwide, leading health authorities recommend the regular consumption of nuts for a healthier diet [11] since nuts are well-associated with preventing cardiovascular diseases, hypertension, metabolic syndrome, diabetes, and total mortality [12]. The contribution of pistachio consumption to healthy eating is an indisputable fact. Pistachios have a high oil content comprised of a healthy fatty acid profile. The oil content of pistachios ranges between 50–62% in general; even some ecotypes may have an oil content of over 75% [1]. Salinas et al. [13] stated that lipids in the raw nut consist of 53% monounsaturated, 33% polyunsaturated, and 13% saturated fatty acids. The fatty acid profile of pistachio majorly consists of oleic acid (51–81%), linolenic acid (8–31%), and palmitic acid (7–15%) [6]. It is also a considerable source of proteins, with contents ranging between 19–31% [1, 13]. On the side, some proteins present in pistachio have been classified as allergens that could cause anaphylactic reactions [1]. Apart from proteins, pistachios are rich in dietary fibers beneficial for healthy gut microbiota [1]. Moreover, pistachio nut contains major proportions of minerals such as calcium, magnesium, zinc, iron, phosphorus, potassium, and vitamins such as Vitamin E, Vitamin A, Vitamin C, and Vitamin B complexes [1, 2, 13]. Pistachio nuts are natural sources that highly contain phenolic compounds. Since the fruit was ranked among the 50 foods with the highest antioxidant content, pistachio was considered a “unique functional food” [14]. Both the phenolic

26

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil. . .

581

compounds’ content and the pistachio hull’s antioxidant activity are higher than that of pistachio skin and kernel [15]. The main phenolic compounds in pistachio nuts are anthocyanins, flavan-3-ols, proanthocyanidins, flavonols, flavonoids, tocopherols, carotenoids, chlorophylls, isoflavones, flavanones, stilbenes, and phenolic acids [1, 14]. All those compounds are not only known for their high antioxidant activity but also are associated with chemopreventive, cardioprotective, and vasoprotective capacities [14]. Paterniti et al. [16] demonstrated that the polyphenols extracted from raw shelled pistachios and roasted-salted pistachio kernels exhibit antioxidant and anti-inflammatory properties at lower doses in vivo and in vitro. Considering all the aforementioned nutritious features of pistachio, Tekin et al. [2] have named the nut a “concentrated food pill” and mentioned the quality improvement impacts of pistachio when incorporated into a food product formulation. Pistachio nuts are mostly consumed as a snack food, either raw or roasted, while they are also used as an ingredient in ice cream, pudding, bread, sauces, and meat products [14]. Moreover, the kernels could obtain various products such as pistachio spread and pistachio milk [1]. However, in recent years edible oil production from pistachios has been of great interest in elaborating non-traditional oils [13]. The following section will deal with the main applications in the production of edible oil from pistachio nuts.

4

Methods for Pistachio Oil Production

Prior to edible pistachio oil extraction, a drying operation should be applied to reduce the moisture content of nuts down to 5–8%. Especially for the pressing methods, the moisture content is advised to remain below 5% to avoid microbial growth and obtain considerable efficiency from extraction [1]. Contrary to this, pistachio nuts were moisturized to 10% moisture (wet basis) before screw-pressing in a previous study, and the researcher indicated that moisturization was applied to optimize oil extraction [17]. There are two ways to dry pistachios; keeping under direct sunlight or at room temperature and using forced hot air circulation in a drier [18]. The elevated drying temperatures reduce drying time. Although drying application increases the extraction efficiency, excessive drying may cause oxidative rancidity for extracted pistachio oil. On the other hand, drying operation provides a certain degree of sterilization by blocking the growth or spread of fungi, such as Aspergillus flavus, and prevents aflatoxin accumulation [1, 19]. Sun-drying may reduce some nutritive compound levels in pistachio oil, but drying equipment may increase the amount of total phenolic compounds. Roasting is another pre-extraction technique worth mentioning where applied temperatures are higher than drying. Roasting is generally applied to enhance the sensory characteristics of the pistachio that will be consumed as a snack. However, in some cases, drying or roasting processes exceeding 70  C temperature can be advised to improve the sensory characteristics of pistachio oil at the expense of bioactive properties [1].

O. O¨zdikicierler and B. O¨ztu¨rk-Kerimoğlu

582

There are three different oil extraction methods to mention in this regard: (1) extraction of pistachio oil using organic solvents, (2) extraction using supercritical fluids, and (3) extraction using presses and other pressure systems [1]. Many different solvents, such as n-hexane, petroleum ether, dichloromethane, or ethyl acetate, can be mentioned for oil extraction [20]. Although solvent extraction is a standard method for seed oil production, there are several drawbacks to using organic solvents in pistachio oil extraction using oil quality. First, pistachio oil extracted using solvents cannot be identified as virgin since chemicals are used. Second, organic solvents cause a bad odor, and pistachio oil should be refined before human consumption. Third, refining operation harms bioactive compounds and reduces the nutritive quality of the oil. According to their phase diagrams, supercritical fluid extraction is a technique (Fig. 3) where solvents are used at a temperature-pressure combination at supercritical conditions. Carbon dioxide (CO2) is the most used solvent in supercritical extraction processes since it is safe and easy to remove from the oil obtained. The supercritical extraction system contains a fluid reservoir, compressor, heat exchanger, extractor, expansion valve, separator, and condensation cell [21]. Since supercritical fluids have lower viscosity when compared with traditional liquid organic solvents, extraction at supercritical conditions occurs rapidly. Moreover, selective extraction is possible by adjusting the temperature and pressure combinations of supercritical extraction [1]. In general, pressure systems that use a screw and hydraulic presses are considered easy methods with fair extraction yields. The oil obtained with pressing can be considered virgin since the extraction method relies on mechanical and physical forces. Recovery of pistachio oil ranges around 30% in hydraulic presses and 40% in screw presses, highly dependent on extraction temperature. The temperature increases during

Expansion valve

n Separato

Fluid Reservoir (CO2)

Extracted pistachio oil

Compressor

Heat

Fig. 3 Supercritical extraction system for pistachio oil production

cell

26

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil. . .

583

pressing due to friction should be expected. However, excessive temperature increases that reach 40–50  C may lead to adverse effects on the quality of pistachio oil. In a previous study, temperature regulation was carried out using electrical wiring and maintaining a constant temperature at 25  C [17]. In some studies, pressed pistachio oils were defined as “cold-pressed pistachio oil” as well [22, 23]. However, any application of roasting operation reaching 160  C prior to pressing prevents using the “cold pressing” definition for the product [23]. Because, as determined in Codex Alimentarius, “cold pressing” defines the oil obtained only by mechanical procedures or pressing without applying any heat. Therefore, the pressing and all procedures before and after pressing should be applied at low temperatures [24]. After oil extraction, a solid paste is collected. This paste is a by-product and can be utilized in the human diet as an additive or condiment in the catering industry or used in animal feed or agriculture as a nutritional supplement after grinding and homogenization [1, 18].

5

Pistachio Oil By-products with Regard to Their Potential Phytochemical Compounds

Processing plant food could result in the accumulation of various by-products, which could be referred to as considerable sources of natural antioxidants and bioactive compounds [10]. The term “phytochemical” is a broad expression that refers to plant (phyto) chemicals covering a wide variety of compounds naturally present in plant sources [25]. In general, phytochemicals are classified into six major categories as follows: 1. Carbohydrates: Monosaccharide, disaccharide, polysaccharide, oligosaccharide, and sugar alcohols. 2. Lipids: Monounsaturated fat, polyunsaturated fat, saturated fat, and fatty acids. 3. Terpenoids: Carotenoids, monoterpenoids, diterpenoids, triterpenes, triterpenoid saponins, sesquiterpenoids, sesquiterpene lactones, and polyterpenoids. 4. Phenolic acids: Flavonoids, phenolic acids, stilbenoids, tannins, lignans, xanthones, quinones, coumarins, phenylpropanoids, and benzofurans. 5. Alkaloids and other nitrogen-containing metabolites: Glucosinolates, amaryllidaceae, betalain, diterpenoid, indole, isoquinoline, lycopodium, peptide, pyrrolidine, piperidine, pyrrolizidine, quinoline, quinolizidine, steroidal, tropane, amino acids, amine, cyanogenic glycoside, purine, pyrimidines, proteins, and peptides [25]. Pistachio oil processing by-products are agri-industrial by-products that carry a great potential concerning phytochemical content (Fig. 4). According to the classification above, those by-products contain terpenoids (carotenoids and triterpenes), phenolic acids (flavonoids, phenolic acids, and tannins), and lipids amino acids and carbohydrates. The fundamental phytochemicals present in the three major

O. O¨zdikicierler and B. O¨ztu¨rk-Kerimoğlu

584

Fig. 4 Pistachio oil by-products and their major phytochemicals

by-products of the production of pistachio oil (flour, hull, and shell) are described hereunder.

6

Pistachio Flour

The pressing process applied throughout the production of pistachio oil generates a partially or totally defatted residual cake. This by-product is known as “pistachio flour” or “pistachio cake,” which is commonly wasted [12, 17, 26]. Salinas et al. [13] stated that the growing interest in pistachio oil consumption might increase its production, which may naturally increase by-products, including pistachio flour. The utilization of the pressed cake of pistachio as a functional ingredient in the formulation of various novel foods is of high interest since the flour contains considerable amounts of bioactive compounds. Therefore, this by-product was emphasized to be utilized as a natural source of phytochemicals for dietary supplements, and due to its nutritional advantages, the flour has an excellent potential to be further incorporated into functional food formulations [13, 17, 26]. Pistachio flour

26

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil. . .

585

could be in the form of either partially defatted or totally defatted: Ling et al. [26] separated the oil phase from crushed kernels using a hydraulic press at 60 kg/cm2 for 15 min without application of fat, and the residual cake contained approximately 22% of fat on the dry basis which was assigned as partially defatted flour. The second type, totally defatted flour, was obtained by defatting the residual cake in a Soxhlet apparatus using petroleum ether at a boing point ranging from 38.2 to 54.3  C for 24 h. The residual fat content of the residual cake was below 1%. As seen, a considerable difference is present between the two types of cakes in terms of fat amount. Here, it should be borne in mind that the temperatures applied for extracting fat might influence the sensible components resulting in decomposition and affecting functional properties of the proteins in the flour. Table 1 summarizes the studies carried out on the determination of phytochemicals present in different pistachio flours. Ojeda-Amador et al. [12] characterized the phenolic compounds present in residual cakes of pistachio virgin oils obtained from eight different cultivars. They reported that concentrations of phenolic compounds of the residual cakes ranged between 8600–15,000 mg kg 1 gallic acid equivalents, while the corresponding antioxidant activities were relatively high (12–46 and 155–496 mmol kg 1 for DPPH and ORAC, respectively) that demonstrated the potential application of pistachio flour as a functional ingredient. Furthermore, due to the remarkable amount of fat still present in the cake after the screw press extraction procedure (20–25%), the remaining cake could also be regarded as a source of γ-tocopherol. γ-Tocopherol concentrations of different pistachio cakes were between 125–208 mg kg 1 [12]. In a similar study that evaluated the chemical and nutritional profile of pistachio flours derived from Argentinian pistachios, it was found that the total phenolic content was 7.1 mg g 1, the antioxidant activity determined by FRAP was 8139 μg Trolox g 1. In contrast, the pistachio flour amount required to receive a 50% radical inhibition (EC50) was 41.8 mg mL 1 [13]. Besides, Stevens-Barrón [27] recorded that defatted pistachio flours had a substantial amount of hydrophilic phenolic compounds (2530 mg gallic acid equivalent 100 g 1 raw sample), while the flour contained 557 mg of catechin equivalent total flavonoids and 328 mg of catechin-equivalent condensed tannins. In addition, the researchers underlined that most of the antioxidants were released under oral and gastric conditions; however, bioaccessibility under intestinal conditions was also important for some antioxidants such as hydrophilic phenolic compounds. Therefore, further research should be carried out to determine the mechanisms of chemical interactions between the bioactive phytochemicals and macromolecules present in nut matrix and gastrointestinal biomolecules. Ling et al. [26] detected phenolic content of pistachio flours and the amino acid composition. They recorded that defatted pistachio kernel flour yielded considerably higher total phenolic (552–792 mg gallic acid equivalent 100 g 1 flour, d.b.) and flavonoid (124–280 mg RE 100 g 1 flour, d.b.) contents as well as antioxidant capacities. Moreover, it was detected that the essential amino acids of partially defatted unroasted flour formed 36.6% of the total amino acid content, and most of the amino acids were at higher levels than those listed in the FAO/WHO except

O. O¨zdikicierler and B. O¨ztu¨rk-Kerimoğlu

586

Table 1 Studies on determination and characterization of the phytochemicals present in pistachio oil by-products Type of the by-product Pistachio hull

Source of the by-product Fresh raw un-hulled pistachios from California

Raw pistachio hulls obtained from pistachio orchards in Iran

Four major pistachio varieties obtained by direct harvesting from orchards Pistachio hulls of Uzun and Ohadi varieties obtained from a pistachio processing plant

Target in brief Determination of pistachio hull composition by a comprehensive phytochemical screening of its components

Extraction of watersoluble polysaccharides of pistachio hulls and investigation as a prebiotic agent Investigation of uses of dried hull extracts as an antioxidant source and as raw material for biodiesel production Investigation and characterization of the phenolic and volatile composition of waste pistachio hulls

Pistachio nuts harvested from orchard

Microwave-assisted extraction of phenolic compounds and antioxidative activity of the extract

Pistachio hulls obtained from a pistachio production plant, dried and grounded

Extraction of phenolic compounds, microencapsulation using spray drying, and utilization of

Highlighted phytochemicals Anacardic acids, fatty acids, and phytosterols were the major components. Carotenoids, chlorophylls, tocopherols, and three triterpene acids (mangiferolic, isomangiferolic, and mangiferonic acids) were detected. Polysaccharides (investigated as a whole phase)

Reference [10]

[34]

Fatty acid profile (majors were C12:0, C14:0, C16:0, C18: 1, C18:2, and C18: 3)

[30]

Phenolic profile (gallic acid, catechin and 6 Eriodictyol-7-Oglucoside) and volatile composition of pistachio hulls Phenolic composition (gallic acid, p-hydroxybenzoic acid, protocatechuic acid, ( )epicatechin, syringic acid, p-coumaric acid, quercetin, caffeic acid) and β-carotene Phenolic compounds (total content)

[15]

[29]

[32]

(continued)

26

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil. . .

587

Table 1 (continued) Type of the by-product

Source of the by-product

Pistachio skin

Pistachio nuts were obtained from retail store, and liquid nitrogen used the remove skins

Pistachio flour (cake)

Eight different cultivars of pistachio (Aegina, Avdat, Kastel, Kerman, Larnaka, Mateur, Napoletana, and Sirora) Argentinian natural, roasted, and salted-roasted pistachios

Partially defatted unroasted and roasted, or totally defatted and roasted pistachios Different tree nuts including pistachio, pecan, oak acorn, almond, and walnuts

Target in brief pistachio hull powder in ice-cream formula Evaluation of the skin extract as a bioactive component source

Characterization of pistachio virgin oils and their partially defatted cakes in terms of antioxidant and bioactive properties Determination of the chemical and nutritional profile of pistachio oil and flour and the influence of roasting and salting-roasting processes during oil manufacture Evaluation of the nutritional value, functional features, bioactivity, and microstructure of flours Researching the chemical composition and in vitro bio-accessibility of phenolic compounds, tocopherols, and tocotrienols

Highlighted phytochemicals

Reference

Gallic acid, catechin, epicatechin, eriodictyol-7-Oglucoside, naringenin-7-Oneohesperidoside, eriodictyol, quercetin, luteolin, naringenin, kaempferol, cyanidin-3-Ogalactoside, and cyanidin-3-Oglucoside Phenolic compounds (total content) and γ-tocopherol

[14]

(+)-catechin, gallic acid, procyanidin dimer, eriodictyol, and ( )-epicatechin

[17]

Phenolic compounds (total content), flavonoids, essential and non-essential amino acids Phenolic compounds (total content), flavonoids, and condensed tannins

[26]

[12]

[27]

O. O¨zdikicierler and B. O¨ztu¨rk-Kerimoğlu

588

sulfur amino acid. Total non-essential amino acid content was 65.8% of the total amino acids, where the most abundant ones were Glu, Pro, Arg, and Asp. In another work, Martínez et al. [17] evaluated the phenolic profile of flours obtained from Argentinian natural, roasted, and salted-roasted pistachios. They reported that total phenolic and flavonoid concentrations were not modified by roasting; however, significant decrements were recorded in free radical scavenging (DPPH radical) and antioxidant power. In addition, the flours obtained from salted and roasted pistachios yielded decreased phenolic and flavonoid amounts. The researchers’ findings indicated that the processing conditions of pistachios have an unignorable influence on the bioactive compound profile of the by-product. The major phenolic compounds identified in pistachio flours were (+)-catechin (38–65.6 μg g 1 PF d.w.), gallic acid (23–36 μg g 1 PF d.w.), procyanidin dimer (10–15 μg g 1 PF d.w.), and eriodictyol (9–13 μg g 1 PF d.w.). Rest of the phenolic compounds comprised ( )-epicatechin, quercetin-O-hexoside, isoquercetrin, luteolin, and naringenin. The treatments applied during processing also affected the phenolic constituents of pistachio flour, where the roasting process of pistachios resulted in a significant reduction of some phenolics (gallic acid and (+)-catechin) in pistachio flours. In contrast, it increased others such as naringenin and luteolin.

7

Pistachio Hull

Pistachio hulls came forward as significant by-products which are good sources of natural phenolics and antioxidants. Therefore, these nutritional ingredients have attracted the food industry’s interest in valorizing pistachio hulls and skin as new bioactive sources. When the production disposal volumes of pistachio production wastes have been considered, a significant amount of hull can be obtained in the post-harvest de-hulling processes and considered the main agricultural waste of pistachio production [15]. Due to synthetic antioxidants’ toxicological and carcinogenic findings, natural antioxidants have become more popular as antimicrobial agents. With this regard, the pistachio hull came forward as a significant source of bioactive constituents, especially phenolic compounds. The use of pistachio hull as a source for bioactive compounds can extend pistachios to new levels [9]. The extraction method of the bioactive component-rich phase is a significant step to obtain functional components from the pistachio hull and skin with minimal damage. Since the hull is fleshy and contains significant moisture, drying (in an oven or under sunlight) and grinding are two main pre-extraction steps. Solvent extraction, with polar solvents, is the most used system for extracting the phenolic phase. Besides, microwave-assisted, enzymatic, and ultrasound-assisted extraction are other side applications for extracting phenolic components from pistachio hulls. The extraction system and the solvents used generally differ according to the targeted bioactive component [9]. Several studies have applied different extraction techniques to the pistachio hull to extract rich in phenolic compounds. Generally, drying and grinding are the common pre-extraction steps for pistachio hull [9, 28– 31]. Pre-extraction operations and extraction steps should be optimized to preserve

26

Bioactive Phytochemicals from Pistachio (Pistachia vera L.) Oil. . .

589

the phenolic compounds from possible degradation. Some studies are detailed below to present the common approach to obtain valuable pistachio hull extract. Pistachio hull extracts are significant sources of bioactive compounds that have antioxidant activity. Pistachio hulls were freeze-dried and ground before extracting ethanol: water mixtures in a previous study. The best extract yield was obtained at a 50:50 mixture ratio of ethanol to water. The highest total phenolic compound was measured at extracts obtained using 40:60 (ethanol: water) mixture as 40 mg GAE g 1 extract where also the highest antioxidant activity was measured [29]. Similar extraction was performed by Hamed et al. [31], where hot water (90  C) was used to extract the phenolic component-rich phase from pistachio hulls. Extraction was finalized by precipitation of polysaccharides using ethanol (90% v/v). Cold air-dried and grounded (