Food Lipids: Sources, Health Implications, and Future Trends 0128233710, 9780128233719

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Food Lipids

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­Food Lipids Sources, Health Implications, and Future Trends Edited by

José M. Lorenzo Head of Research, Centro Tecnológico de la Carne de Galicia (CTC); Associate Professor, University of Vigo, Ourense, Spain

Paulo Eduardo Sichetti Munekata Postdoctoral Researcher, Centro Tecnológico de la Carne de Galicia (CTC), Ourense, Spain

Mirian Pateiro Researcher, Centro Tecnológico de la Carne de Galicia (CTC), Ourense, Spain

Francisco J. Barba Doctor and Professor, University of Valencia, Valencia, Spain

Rubén Domínguez Researcher, Centro Tecnológico de la Carne de Galicia (CTC), Ourense, Spain

Academic Press is an imprint of Elsevier 125 London Wall, London EC2Y 5AS, United Kingdom 525 B Street, Suite 1650, San Diego, CA 92101, United States 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom Copyright © 2022 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN 978-0-12-823371-9 For information on all Academic Press publications visit our website at https://www.elsevier.com/books-and-journals

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Contents Contributors.............................................................................................................. xv Editors’ biographies.................................................................................................xix

CHAPTER 1 Introduction and classification of lipids.........................1 Rubén Domínguez, Mirian Pateiro, Laura Purriños, Paulo Eduardo Sichetti Munekata, Noemí Echegaray, and José M. Lorenzo 1 Introduction...................................................................................... 1 2 Classification of lipids..................................................................... 3 2.1 Fatty acids............................................................................... 4 2.2 Steroids................................................................................... 5 2.3 Isoprenoids.............................................................................. 7 2.4 Acylglycerols.......................................................................... 8 2.5 Waxes.................................................................................... 10 2.6 Phospholipids........................................................................ 11 2.7 Glycolipids............................................................................ 11 3 Conclusions.................................................................................... 14 Acknowledgments................................................................................. 14 References............................................................................................. 14

PART 1  Lipid sources and their chemical composition CHAPTER 2 Animal source: Meat, subcutaneous fat, milk, and dairy products............................................................19 Paulo Eduardo Sichetti Munekata, Rubén Domínguez, Mirian Pateiro, Noemí Echegaray, and José M. Lorenzo 1 Introduction.................................................................................... 19 2 Lipids in meat................................................................................ 20 3 Lipids in subcutaneous fat............................................................. 20 4 Lipids in milk................................................................................. 37 5 Lipids in dairy products................................................................. 37 6 Conclusion..................................................................................... 42 Acknowledgment.................................................................................. 44 References............................................................................................. 44

CHAPTER 3 Marine sources: Fish, shellfish, and algae..................51

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Mirian Pateiro, Rubén Domínguez, Paulo Eduardo Sichetti Munekata, Noemí Echegaray, Rubén Agregán, and José M. Lorenzo Introduction.................................................................................... 51 Lipid composition of fish............................................................... 52

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Algae: Potential sources of nutritionally important lipids............. 55 3.1 Microalgae............................................................................ 56 3.2 Macroalgae........................................................................... 57 4 Lipid composition and fatty acids of shellfish............................... 59 4.1 Crustaceans........................................................................... 59 4.2 Molluscs................................................................................ 61 5 Conclusions.................................................................................... 62 Acknowledgments................................................................................. 62 References............................................................................................. 63

CHAPTER 4 Plant source: Vegetable oils...........................................69 Gema Nieto and José M. Lorenzo 1 Introduction.................................................................................... 69 2 Lipid sources and their chemical composition.............................. 70 3 What are vegetable oils?................................................................ 70 4 Oils of plant origin......................................................................... 71 5 Fruit pulp oils................................................................................. 76 6 Olive oil......................................................................................... 76 7 Palm oil.......................................................................................... 78 8 Coconut oil..................................................................................... 80 9 Conclusions.................................................................................... 80 Acknowledgment.................................................................................. 80 References............................................................................................. 81

PART 2  Oxidative degradation CHAPTER 5 Lipid oxidation of animal fat...........................................89

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Sol Zamuz, Benjamin M. Bohrer, Paulo Cezar Bastianello Campagnol, Rubén Domínguez, Mirian Pateiro, Eva M. Santos, and José M. Lorenzo Lipid oxidation: Definition, mechanism, and implications........... 89 1.1 Autoxidation......................................................................... 90 1.2 Enzymatic oxidation............................................................. 91 1.3 Photooxidation...................................................................... 92 Intrinsic factors influencing development of lipid oxidation of animal-derived lipids................................................................. 94 2.1 Lipid composition................................................................. 94 2.2 Presence of prooxidants........................................................ 96 2.3 Presence of antioxidants....................................................... 96 Extrinsic factors influencing the development of lipid oxidation of animal-derived lipids................................................. 98

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4 Volatile compounds derived from oxidized fatty acids.................. 99 5 Key findings................................................................................. 101 Acknowledgments............................................................................... 101 References........................................................................................... 102

CHAPTER 6 Lipid oxidation of marine oils....................................... 105 Rubén Agregán, Noemí Echegaray, Mirian Pateiro, Alfredo Teixeira, José Ángel Pérez-Álvarez, Rubén Domínguez, Gonzalo Aleu, and José M. Lorenzo 1 Introduction.................................................................................. 105 2 Lipids in the marine environment: Composition and sources used by human beings.................................................................. 107 3 Marine oils in the food industry................................................... 110 4 Lipid stability of omega 3 (n-3) polyunsaturated fatty acid (PUFA)-rich fish oils................................................................... 111 5 Compounds resulting from lipid peroxidation of omega-3 (n-3) polyunsaturated fatty acids (PUFAs)................... 113 6 Protection of marine oils against oxidation................................. 116 7 Conclusion................................................................................... 119 Acknowledgments............................................................................... 119 References........................................................................................... 120

CHAPTER 7 Lipid oxidation of vegetable oils.................................. 127

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Noemí Echegaray, Mirian Pateiro, Gema Nieto, Marcelo R. Rosmini, Paulo Eduardo Sichetti Munekata, María Elena Sosa-Morales, and José M. Lorenzo Introduction.................................................................................. 128 Reaction mechanisms of lipid oxidation in vegetable oils............................................................................... 129 2.1 Lipid autoxidation of vegetable oils................................... 129 2.2 Photooxidation of vegetable oils......................................... 130 2.3 Enzymatic oxidation of vegetable oils................................ 130 2.4 Thermal oxidation of vegetable oils................................... 131 Origination of secondary products of lipid oxidation in vegetable oils........................................................................... 131 Factors influencing the lipid oxidation of vegetable oils............. 133 4.1 Lipid composition of vegetable oils.................................... 133 4.2 Presence of free fatty acid and mono- and diacylglycerols.................................................................... 134 4.3 Presence of phospholipids.................................................. 134 4.4 Presence of moisture........................................................... 136

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4.5 Presence of chlorophylls..................................................... 136 4.6 Presence of lipoxygenase.................................................... 136 4.7 Presence of metals.............................................................. 136 4.8 Presence of antioxidants compounds.................................. 137 4.9 Vegetable oil processing..................................................... 137 4.10 Oxygen exposure................................................................ 138 4.11 Light exposure.................................................................... 139 4.12 Temperature........................................................................ 139 5 Implications and importance of lipid oxidation in vegetable oils............................................................................... 139 5.1 Loss in sensory quality....................................................... 140 5.2 Loss in nutritional quality and formation of toxicological compounds.................................................... 140 6 Determination of the lipid oxidation of vegetable oils................ 141 6.1 Determination of peroxide value........................................ 141 6.2 Determination of p-anisidine value..................................... 142 6.3 Determination of Totox value............................................. 142 6.4 Determination of individually secondary products by chromatographic techniques............................................... 142 6.5 Determination of oxidation by sensory evaluations............ 143 7 Determination of oxidative stability of vegetable oils................. 143 8 Protection and improvements against lipid oxidation in vegetable oils........................................................................... 144 8.1 Protection during the processing of vegetable oils............. 144 8.2 Protection during storage of vegetable oils......................... 145 8.3 Improvement of vegetable oils stability by antioxidants addition........................................................... 145 8.4 Improvement of oxidative stability through the change of fatty acids....................................................................... 146 8.5 Improvement of oxidative stability by encapsulation techniques........................................................................... 147 9 Conclusions.................................................................................. 147 Acknowledgments............................................................................... 148 References........................................................................................... 148

PART 3  Lipid analysis in food CHAPTER 8 Fat and fatty acids.......................................................... 155

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Sol Zamuz, Mirian Pateiro, Carlos A. Conte-Junior, Ruben Dominguez, Asad Nawaz, Noman Walayat, and José M. Lorenzo Fat and fatty acids analysis in food.............................................. 155

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Extraction methods...................................................................... 156 Derivatization methods................................................................ 161 Separation methods: Gas chromatography and other chromatographic techniques........................................................ 162 5 Detection methods....................................................................... 167 5.1 GC detectors....................................................................... 167 5.2 HPLC detectors................................................................... 168 5.3 TLC detectors..................................................................... 169 5.4 SFC detectors...................................................................... 170 6 Key findings................................................................................. 170 Acknowledgments............................................................................... 170 References........................................................................................... 170

CHAPTER 9 Cholesterol and cholesterol oxidation products (COPs)............................................................... 173 Dorota Derewiaka 1 Cholesterol—Characteristics and functions................................ 173 2 Cholesterol occurrence in food products..................................... 176 3 Cholesterol oxidation—Mechanisms and products..................... 177 4 Impact of cholesterol oxidation products on the human organism....................................................................................... 180 5 Occurrence of cholesterol oxidation products in food products...... 182 6 Determination of cholesterol and cholesterol oxidation products in food products............................................................ 187 6.1 Gas and liquid chromatography.......................................... 187 6.2 Other methods for cholesterol quantification..................... 196 7 Summary...................................................................................... 197 References........................................................................................... 198

CHAPTER 10 Fat-soluble vitamins (A, E, D, and K)........................... 207 1 2

Carolina Nebot, Alejandra Cardelle-Cobas, Alberto Cepeda, and Beatriz Vázquez Introduction.................................................................................. 207 Sample preparation. Extraction techniques for vitamers of fat-soluble vitamins present in different food matrices........... 209 2.1 Saponification..................................................................... 209 2.2 Enzymatic hydrolysis.......................................................... 210 2.3 Matrix solid-phase dispersion (MSPD).............................. 211 2.4 Microwave extraction (MW).............................................. 211 2.5 Ultrasound-assisted extraction (UAE)................................ 212 2.6 Pressurized liquid extraction (PLE).................................... 212 2.7 Supercritical fluid extraction (SFE).................................... 212

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2.8 Enzyme-assisted extraction (EAE)..................................... 213 2.9 Dispersive liquid-liquid microextraction (DLLME)........... 213 3 Techniques of analysis for vitamers of fat-soluble vitamins present in different food matrices................................................ 213 3.1 Liquid chromatography (LC).............................................. 214 3.2 Gas chromatography (GC).................................................. 220 3.3 Thin layer chromatography (TLC)..................................... 220 3.4 Supercritical fluid chromatography (SFC)......................... 221 References........................................................................................... 221

CHAPTER 11 Lipid-derived oxidation products.................................. 231 Eliana Jerónimo and Susana P. Alves 1 Introduction.................................................................................. 231 2 Conventional methods................................................................. 233 2.1 Primary oxidation compounds............................................ 233 2.2 Secondary oxidation products............................................. 239 3 Alternative methodologies........................................................... 244 Acknowledgments............................................................................... 245 References........................................................................................... 246

PART 4  Lipids in human health CHAPTER 12 Fatty acids........................................................................ 257 Rubén Agregán, Teodora Popova, María López-Pedrouso, Jesús Cantalapiedra, José M. Lorenzo, and Daniel Franco 1 Introduction.................................................................................. 257 2 Fatty acids present in nature........................................................ 259 2.1 Chemical structure and differentiation of different fatty acids............................................................................ 259 2.2 Natural sources of fatty acids.............................................259 3 Relationship between saturated fatty acid (SFA) intake and health status........................................................................... 262 4 The role of unsaturated fatty acids (UFAs) in health................... 266 4.1 Monounsaturated fatty acids (MUFAs).............................. 266 4.2 Polyunsaturated fatty acids (PUFAs).................................. 268 5 The trans fatty acids (TFAs) and their health effects................... 273 6 Conclusions.................................................................................. 276 References........................................................................................... 276

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CHAPTER 13 Lipids in human health: Importance of n-3 long-chain and CLA......................................................... 287 Teodora Popova, José M. Lorenzo, Daniel Franco, and María López-Pedrouso 1 The n-3 long-chain polyunsaturated fatty acids (LC-PUFA).................................................................................. 287 1.1 Synthesis and storage in the body....................................... 287 1.2 Dietary sources and intake of n-3 LC-PUFA...................... 290 1.3 The n-3 LC-PUFA and human health................................. 292 2 Conjugated linoleic acid (CLA)................................................... 299 2.1 Synthesis and storage in the body....................................... 299 2.2 Dietary sources and intake of CLA....................................301 2.3 CLA and human health....................................................... 304 References........................................................................................... 308

CHAPTER 14 Sterols and fat-soluble vitamins................................... 323 Jianjun Zhou, Min Wang, Noelia Pallarés, Emilia Ferrer, Houda Berrada, and Francisco J. Barba 1 Introduction.................................................................................. 323 2 Sterols.......................................................................................... 324 2.1 Cholesterol.......................................................................... 324 2.2 Phytosterols......................................................................... 326 2.3 Fungal sterols...................................................................... 329 2.4 Other sterols........................................................................ 330 3 Fat-soluble vitamins and human health....................................... 332 3.1 Vitamin A............................................................................ 332 3.2 Vitamin D............................................................................ 333 3.3 Vitamin E............................................................................ 335 3.4 Vitamin K............................................................................ 338 4 Conclusions.................................................................................. 339 References........................................................................................... 340

CHAPTER 15 Dietary oxidized lipids................................................... 349 1 2

Min Wang, Jianjun Zhou, Noelia Pallarés, Emilia Ferrer, Houda Berrada, and Francisco J. Barba Introduction.................................................................................. 350 Oxidative types of dietary lipids.................................................. 352 2.1 Autooxidation..................................................................... 354 2.2 Photooxidation.................................................................... 355

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2.3 Enzymatic oxidation........................................................... 355 2.4 Decomposition and polymerization of hydroperoxides...... 356 3 Lipid oxidation of different dietary sources................................ 356 3.1 Meat and aquatic products.................................................. 356 3.2 Plant products..................................................................... 357 3.3 Emulsion products.............................................................. 358 4 Hazard of oxidation products....................................................... 359 4.1 Acrolein.............................................................................. 359 4.2 Crotonaldehyde................................................................... 359 4.3 4-Hydroxynonenal.............................................................. 360 4.4 Malondialdehyde................................................................ 360 5 Evaluation of lipid oxidation....................................................... 360 5.1 Primary oxidation products................................................. 361 5.2 Secondary oxidation products............................................. 362 5.3 Other methods..................................................................... 363 6 Reduced lipid oxidation............................................................... 364 6.1 Antioxidants........................................................................ 364 6.2 Packaged form.................................................................... 366 7 Conclusions.................................................................................. 367 References........................................................................................... 367

PART 5  Future trends CHAPTER 16 Application of emerging technologies to obtain valuable lipids from food byproducts.......................... 383 1 2

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Pablo G. del Río, Gil Garrote, Gonzalo Astray, Diana Oliveira, Patricia Costa, and Beatriz Gullón Introduction.................................................................................. 384 Ultrasound-assisted extraction for the extraction of lipid from fish byproducts.................................................................... 385 2.1 General aspects of ultrasound-assisted extraction process................................................................................ 385 2.2 Use of ultrasound-assisted extraction technology in fish byproducts...............................................................387 Microwave-assisted extraction for the extraction lipids from fish byproducts.................................................................... 389 3.1 General aspects of microwave-assisted extraction process................................................................................ 389 3.2 Use of microwave-assisted extraction technology in fish byproducts...............................................................389 Supercritical fluid extraction for the extraction of lipids from fish byproducts.................................................................... 390

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4.1 General aspects of supercritical fluid extraction process................................................................................ 390 4.2 Use of supercritical fluid extraction technology in fish byproducts........................................................................... 392 5 Contribution of polyunsaturated fatty acids to human health...... 395 5.1 Polyunsaturated fatty acids’s ratios and daily dosages....... 395 5.2 Health benefits of docosahexaenoic acid and eicosapentaenoic acid......................................................... 396 6 Conclusions.................................................................................. 403 Acknowledgments............................................................................... 403 References........................................................................................... 403

CHAPTER 17 Encapsulation techniques to increase lipid stability............................................................................. 413

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Aurora Cittadini, Paulo Eduardo Sichetti Munekata, Mirian Pateiro, María V. Sarriés, Rubén Domínguez, and José M. Lorenzo Introduction.................................................................................. 414 Measurements of effectiveness of encapsulation process............ 417 2.1 Encapsulation efficiency..................................................... 417 2.2 Payload...............................................................................418 2.3 Particle size......................................................................... 418 2.4 Stability............................................................................... 418 2.5 Encapsulation yield............................................................. 419 Technology for encapsulation of lipids........................................ 419 3.1 Emulsification..................................................................... 422 3.2 Spray-drying....................................................................... 423 3.3 Freeze-drying...................................................................... 425 3.4 Coacervation....................................................................... 425 3.5 Fluidized bed coating.......................................................... 427 3.6 Coaxial electrospray system............................................... 428 3.7 Ionic gelation...................................................................... 429 3.8 Supercritical fluid technology............................................. 430 3.9 Liposome entrapment......................................................... 431 Shell materials used for lipid encapsulation................................ 432 4.1 Carbohydrates..................................................................... 433 4.2 Proteins............................................................................... 434 4.3 Lipids.................................................................................. 435 4.4 Combination of different bio-based materials.................... 435 Applications of micro/nanoencapsulated oils.............................. 436 5.1 Cereals and bakery products............................................... 444 5.2 Dairy products.................................................................... 446 5.3 Meat products..................................................................... 447

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6 Conclusions.................................................................................. 450 Acknowledgments............................................................................... 451 References........................................................................................... 451

CHAPTER 18 Replacement of saturated fat by healthy oils to improve nutritional quality of meat products......... 461 Rosane Teresinha Heck, Bibiana Alves Dos Santos, José M. Lorenzo, Claudia Ruiz-Capillas, Alexandre José Cichoski, Cristiano Ragagnin de Menezes, and Paulo Cezar Bastianello Campagnol 1 2

Introduction.................................................................................. 462 Health benefits of reducing SFA and increasing PUFA intakes............................................................................... 464 3 Fatty acid profile of the main oils used in meat products............ 465 3.1 Oils rich in monounsaturated fatty acids (MUFA)............. 465 3.2 Oils rich in n-6 PUFA......................................................... 467 3.3 Oils rich in n-3 PUFA......................................................... 468 4 Approaches for the addition of healthy oils in meat products..... 469 4.1 Addition of liquid healthy oils to meat products................ 469 4.2 Addition of preemulsified healthy oils to meat products............................................................................... 471 4.3 Addition of healthy oils microencapsulated to meat products............................................................................... 474 4.4 Addition of gelled healthy oils to meat products................ 476 4.5 Addition of healthy oils enriched with bioactive compounds to meat products.............................................. 479 5 Final remarks............................................................................... 481 Acknowledgments............................................................................... 481 References........................................................................................... 482 Index....................................................................................................................... 489

Contributors Rubén Agregán Centro Tecnológico de la Carne de Galicia, Ourense, Spain Gonzalo Aleu Faculty of Agricultural Sciences, Catholic University of Córdoba, Córdoba, Argentina Susana P. Alves CIISA—Centre for Interdisciplinary Research in Animal Health, Faculty of Veterinary Medicine, University of Lisbon, Avenida da Universidade Técnica, Lisbon, Portugal Gonzalo Astray Department of Physical Chemistry, Faculty of Science, University of Vigo (Campus Ourense), Ourense, Spain Francisco J. Barba Preventive Medicine and Public Health, Food Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy, University of Valencia, Valencia, Spain Houda Berrada Preventive Medicine and Public Health, Food Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy, University of Valencia, Valencia, Spain Benjamin M. Bohrer Department of Animal Sciences, The Ohio State University, Columbus, OH, United States Paulo Cezar Bastianello Campagnol Federal University of Santa Maria, Santa Maria, Rio Grande do Sul, Brazil Jesús Cantalapiedra Servicio de Ganadería, Xunta de Galicia, Lugo, Spain Alejandra Cardelle-Cobas Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Veterinary Medicine, University of Santiago de Compostela, Lugo, Spain Alberto Cepeda Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Veterinary Medicine, University of Santiago de Compostela, Lugo, Spain Alexandre José Cichoski Federal University of Santa Maria, Santa Maria, Rio Grande do Sul, Brazil

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Aurora Cittadini Institute on Innovation and Sustainable Development in Food Chain (IS-FOOD), Public University of Navarre, Pamplona; Centro Tecnológico de la Carne de Galicia, Ourense, Spain Carlos A. Conte-Junior Programa de Pós-Graduação em Ciência de Alimentos, Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, Brazil Patricia Costa Catholic University of Portugal, Centre of Biotechnology and Fine Chemistry (CBQF), Laboratorio Associado, Escola Superior de Biotecnologia, Porto, Portugal Cristiano Ragagnin de Menezes Federal University of Santa Maria, Santa Maria, Rio Grande do Sul, Brazil Pablo G. del Río Department of Chemical Engineering, Faculty of Science, University of Vigo (Campus Ourense), Ourense, Spain Dorota Derewiaka Warsaw University of Life Sciences, Institute of Food Sciences, Faculty of Food Technology, Department of Food Technology and Assessment, Division of Food Quality Assessment, Warsaw, Poland Rubén Domínguez Centro Tecnológico de la Carne de Galicia, Ourense, Spain Noemí Echegaray Centro Tecnológico de la Carne de Galicia, Ourense, Spain Emilia Ferrer Preventive Medicine and Public Health, Food Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy, University of Valencia, Valencia, Spain Daniel Franco Centro Tecnológico de la Carne de Galicia, Ourense, Spain Gil Garrote Department of Chemical Engineering, Faculty of Science, University of Vigo (Campus Ourense), Ourense, Spain Beatriz Gullón Department of Chemical Engineering, Faculty of Science, University of Vigo (Campus Ourense), Ourense, Spain Rosane Teresinha Heck Federal University of Santa Maria, Santa Maria, Rio Grande do Sul, Brazil Eliana Jerónimo Alentejo Biotechnology Center for Agriculture and Agro-Food (CEBAL)/ Polytechnic Institute of Beja (IPBeja); MED—Mediterranean Institute for Agriculture, Environment and Development, CEBAL, Beja, Portugal

Contributors

María López-Pedrouso Departamento de Zooloxía, Xenética e Antropoloxía Física, Universidade de Santiago de Compostela, Santiago de Compostela, Spain José M. Lorenzo Centro Tecnológico de la Carne de Galicia; University of Vigo, Ourense, Spain Paulo Eduardo Sichetti Munekata Centro Tecnológico de la Carne de Galicia, Ourense, Spain Asad Nawaz Jiangsu Key Laboratory of Crop Genetics and Physiology, College of Agriculture, Yangzhou University, Yangzhou, People’s Republic of China Carolina Nebot Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Veterinary Medicine, University of Santiago de Compostela, Lugo, Spain Gema Nieto Department of Food Technology, Nutrition and Food Science, Veterinary Faculty, University of Murcia, Murcia, Spain Diana Oliveira Catholic University of Portugal, Centre of Biotechnology and Fine Chemistry (CBQF), Laboratorio Associado, Escola Superior de Biotecnologia, Porto, Portugal Noelia Pallarés Preventive Medicine and Public Health, Food Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy, University of Valencia, Valencia, Spain Mirian Pateiro Centro Tecnológico de la Carne de Galicia, Ourense, Spain José Ángel Pérez-Álvarez IPOA Research Group (UMH-1 and REVIV-Generalitat Valenciana), Agro-Food Technology Department, Escuela Politécnica Superior de Orihuela, Miguel Hernández University, Alicante, Spain Teodora Popova Institute of Animal Science-Kostinbrod, Kostinbrod, Bulgaria Laura Purriños Centro Tecnológico de la Carne de Galicia, Ourense, Spain Marcelo R. Rosmini Department of Public Health, Faculty of Veterinary Science, National University of the Littoral, Esperanza, Argentina Claudia Ruiz-Capillas Institute of Food Science, Technology and Nutrition (ICTA-CSIC), Madrid, Spain

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Bibiana Alves Dos Santos Federal University of Santa Maria, Santa Maria, Rio Grande do Sul, Brazil Eva M. Santos Universidad Autónoma del Estado De Hidalgo, Área Académica de Química, Mineral de la Reforma, Hidalgo, Mexico María V. Sarriés Institute on Innovation and Sustainable Development in Food Chain (IS-FOOD), Public University of Navarre, Pamplona, Spain María Elena Sosa-Morales Departamento de Alimentos, División de Ciencias de la Vida, Campus IrapuatoSalamanca, Universidad de Guanajuato, Guanajuato, Mexico Alfredo Teixeira Centro de Investigação de Montanha (CIMO), Polytechnic Institute of Bragança, Bragança, Portugal Beatriz Vázquez Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Veterinary Medicine, University of Santiago de Compostela, Lugo, Spain Noman Walayat Department of Food Science and Engineering, College of Ocean, Zhejiang University of Technology, Hangzhou, China Min Wang Preventive Medicine and Public Health, Food Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy, University of Valencia, Valencia, Spain Sol Zamuz Centro Tecnológico de la Carne de Galicia, Ourense, Spain Jianjun Zhou Preventive Medicine and Public Health, Food Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy, University of Valencia, Valencia, Spain

Editors’ biographies José M. Lorenzo is the Head of Research at the Centro Tecnológico de la Carne de Galicia, Ourense, Spain, and Associate Professor at the University of Vigo, Spain. He is the author of more than 640 scientific articles (h index: 57) and more than 280 communications to congresses, mostly international. He has edited 12 international books and has written 72 chapters in international and national books. Paulo Eduardo Sichetti Munekata is a postdoctoral researcher at the Centro Tecnológico de la Carne de Galicia (CTC), Ourense, Spain. He is the author of 145 scientific articles (h index: 31) in well-recognized peer-reviewed international journals, 31 book ­chapters, and more than 30 communications to national and international congresses. Mirian Pateiro is a researcher at the Centro Tecnológico de la Carne de Galicia, Ourense, Spain. Her scientific production includes 189 scientific articles (h index: 35) in high-impact peer-reviewed journals and 25 book chapters in the food science and biochemistry areas as well as 89 scientific communications to national and international meetings, congresses, and symposiums. Francisco J. Barba is Doctor and Professor at the University of Valencia, Valencia, Spain. He is a highly cited researcher in agricultural sciences (Clarivate Analytics, Web of Science) since 2019. He is the author of more than 350 peer-reviewed articles in high-impact factor journals (h index: 62 and 69 in SCOPUS and Google Scholar, respectively), 150 congress communications, and 60 book chapters and has edited more than 12 books in editorials of international repute. Rubén Domínguez is a researcher at the Centro Tecnológico de la Carne de Galicia (CTC), Ourense, Spain. He is the author of 163 scientific articles (h index: 32) in high-impact peer-­reviewed international journals, 27 book chapters, and more than 57 communications to congresses, mostly international.

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CHAPTER

Introduction and classification of lipids

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Rubén Domíngueza, Mirian Pateiroa, Laura Purriñosa, Paulo Eduardo Sichetti Munekataa, Noemí Echegaraya, and José M. Lorenzoa,b a

Centro Tecnológico de la Carne de Galicia, Ourense, Spain b University of Vigo, Ourense, Spain

­C hapter outline 1 Introduction...............................................................................................................1 2  Classification of lipids................................................................................................3 2.1  Fatty acids.............................................................................................. 4 2.2 Steroids.................................................................................................. 5 2.3 Isoprenoids............................................................................................. 7 2.4 Acylglycerols........................................................................................... 8 2.5 Waxes................................................................................................... 10 2.6 Phospholipids....................................................................................... 11 2.7 Glycolipids............................................................................................ 11 3 Conclusions............................................................................................................ 14 Acknowledgments....................................................................................................... 14 References................................................................................................................. 14

1 ­Introduction Currently, there is no unique definition for lipids. Therefore, several definitions were proposed by multiple authors (Valenzuela & Valenzuela, 2013). However, they could be defined as a heterogeneous group of water-insoluble natural compounds, soluble in nonpolar organic solvents, which are formed mainly by carbon, hydrogen, and oxygen atoms although many structures also contain other atoms such as phosphorus, nitrogen, and sulfur. All definitions highlight two main aspects: they are insoluble in water and they are compounds derived from living organisms. However, the definitions based on these two properties are imprecise, since short-chain lipids ( 30 mg/100 g) are found in seabream, seabass, mackerel, goatfish, and red mullet.

3 ­Algae: Potential sources of nutritionally important lipids The species, place of cultivation, water salinity, atmospheric conditions, and harvesting period significantly influences algae chemical composition (Peñalver et al., 2020). In this regard, many studies confirm a temporal variability in lipid composition (Nelson, Phleger, & Nichols, 2002). Phospholipids, glycolipids, and neutral lipids are the main lipids identified in algae (Pereira, 2018). Phosphatidylglycerol, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, and phosphatidic acid are the main phospholipids identified in algae. Among glycolipids, monogalactosyldiacylglycerol, sulfoquinovosyldiacylglycerol, digalactosyldiacylglycerol, and sulfolipid stand out. Finally, triacylglycerol is the most abundant in the group of neutral lipids (Kumari, Kumar, Reddy, & Jha, 2013) because of its ability to synthesize n-3 LCPUFAs that has increased their commercial value (Kumari, Kumar, et al., 2013). However, not all species show adequate content of DHA and DPA.

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CHAPTER 3  Marine sources: Fish, shellfish, and algae

3.1 ­Microalgae Several profiles are included in the composition of fatty acids microalgae (Jónasdóttir, 2019). In most microalgal species, the polar fraction of complex lipids (phospholipids and glycolipids) represents the most abundant group (41%–92% of total lipids) whose composition depends on the species and culture conditions (Ahmmed, Ahmmed, Tian, Carne, & Bekhit, 2020). This group is followed by the nonpolar glycerolipids, which represent 5%–51% of total lipids (Mimouni, Couzinet-Mossion, Ulmann, & WielgoszCollin, 2018). Sterols were also included in the lipid composition of microalgae. Long-chain fatty acids are the most common, especially those that contain C16–C18 chain lengths. Among these, palmitic (C16:0), stearic (C18:0), palmitoleic (C16:1n-7), oleic (C18:1n-9), LA, ALA, γ-linolenic (GLA, C18:3n-6), and stearidonic acid (SDA, C18:4n-3) acids stand out; also, very-long-chain fatty acids of C20-C22 can be accumulated in significant amounts. Notable within this group are EPA, DHA, and DPA. Regarding PUFA, these FAs represent 10%–70% of total FA. Inside the phylum Plantae, Chlorophytes contain a high amount of C18 PUFA, while Rhodophytes and Glaucophytes have higher amounts of C20 PUFA such as arachidonic acid (ARA, C20:4n-6) and EPA. Regarding Chromista phylum, the class Ochrophyta (Xanthophyceae, Eustigmatophyceae) represent a rich source of ARA and EPA, while Haptophytes, Dinophytes, and Cercozoa have high contents of EPA and DHA (Lang, Hodac, Friedl, & Feussner, 2011). In the omega-6 FA family, high variability is found in LA contents depending on the species. Significant amounts were identified in Cyanophyceae (Chamaesiphon polonicus—54.75%) and xantophyta (Heterococcus endolithicus—53.37%) (Lang et al., 2011). Chlorophyceae (Deasonia multinucleate—29.9%, Desmodesmus multiformis—28.5%) and Cyanobacteria (Spirulina maxima—24.8%) showed the highest percentages of GLA. Regarding the omega-3 FA family, the specie Crypthecodinium cohnii (Dinophytes) stands out by its DHA contents (about 40% of total FA). Another important fatty acid is docosapentaenoic acid (DPA, C22:5n-3). Although DPA is less frequent than DHA (C22:6n-3), notable contents are found in Pyrocystis lunula (41.08%) from dinophytes, and in Trachelomonas volvocina (23.66%) from Euglenophyceae (Lang et al., 2011). The highest EPA contents are found in Eustigmatophytes from Ochrophyta (Nannochloropsis salina—44.2% (Safafar, Hass, Møller, Holdt, & Jacobsen, 2016), Monodus subterraneus—37.1%), and in P. lunula (41.1%) from Dinophyceae (Lang et al., 2011; Safafar et al., 2016). Although at lower levels, diatoms (Phaeodactylum tricornutum—23.8%), chlorophyta (Chlamydomonas allensworthii—24.0%, Tetraselmis suecica—19.5%) also display interesting contents (Lang et  al., 2011; Nielsen et al., 2019). Along with these essential nutrients, unusual very-long-chain PUFAs can also be identified but in a much lower concentration ( 50%), are highly resistant to lipid oxidation and perform well at high temperatures. On the other hand, oils rich in MUFA (> 60%) such as hazelnut, macadamia nut, avocado, apricot kernel, chufa, and rapeseed oils are more oxidatively unstable. However, within this same group, it should be noted that oils such as olive oil have acceptable stability as a consequence of their low presence of linolenic acid, being ideal for industrial applications such as deep-fried. On the contrary, rapeseed oil, despite being within the same group as olive oil, has lower stability because it shows higher amounts of linolenic acid (18%–30%), which reduces its oxidative stability. Lastly, oils rich in PUFA (> 50%) such as sunflower, soybean, quinoa, safflower, cottonseed, and corn oils display the lowest oxidative stability due to their high degree of unsaturation (Dubois, Breton, Linder, Fanni, & Parmentier, 2007).

4.2 ­Presence of free fatty acid and mono- and diacylglycerols Free fatty acids are more susceptible to autoxidation than esterified fatty acids and increase the rate of diffusion of oxygen from the headspace into the oil to accelerate vegetable oil oxidation. In the same way, mono- and di-glycerol act as prooxidants, incrementing oxidation mechanisms due to the same reasons as free fatty acids (Choe & Min, 2006). Furthermore, these compounds are more accessible than triglycerides to oxidative enzymes such as lipoxygenase.

4.3 ­Presence of phospholipids Phospholipids, as phosphatidylethanolamine, phosphatidylcholine, phosphatidylinositol, phosphatidylserine, and phosphatidic acid, are a type of lipids that are mainly present in crude oils since the degumming process removes them during refining. These compounds act as antioxidants when they are found at concentrations below 60ppm and in the presence of metals. Concretely, these compounds exert their

Table 7.2  Fatty acid composition of different common edible vegetable oils. Oils rich in SFA

Oils rich in MUFA

Oils rich in PUFA

Fatty acid

Coconut

Palm kernel

Palm

Olive

Chufa

Rapeseed

Sunflower

Soybean

Corn

8:0 10:0 12:0 14:0 16:0 18:0 20:0 22:0 24:0 ∑ SFA 16:1 n-7 16:1 n-9 17:1 n-7 18:1 n-9 18:1 n-7 20:1 n-9 20:1 n-7 22:1 n-9 24:1 n-9 ∑ MUFA 18:2 n-6 18:3 n-3 18:3 n-6 18:4 n-3 20:2 n-6 20:3 n-6 20:4 n-6 20:5 n-3 22:2 n-6 22:4 n-6 ∑ PUFA

7.6 6.5 48.2 18.5 8.7 2.7 0.1 – – 92.6 – – – 6.0 – 0.1 – – – 6.1 1.8 0.1 – – – – – – – – 1.9

4.1 3.7 46.0 17.8 8.4 1.6 – – – 81.9 – – – 16.4 – – – – – 16.4 3.1 – – – – – – – – – 3.1

0.1 0.1 0.4 1.1 43.8 4.4 0.3 0.1 0.1 50.4 0.2 – – 39.1 – 0.1 – – – 39.4 10.2 0.3 – – – – – – – – 10.5

– – – 0.0 12.1 2.6 0.4 0.1 0.1 15.3 0.8 – 0.2 72.5 – 0.3 – – – 73.8 9.4 0.6 – – – – – – – – 10.0

– – – 0.2 13.8 3.2 0.4 – – 17.5 0.3 – – 72.6 – – – – – 72.9 8.9 0.4 – – – – – – – – 9.3

– – – 0.1 5.1 1.7 0.6 0.3 0.2 8.0 0.2 – – 60.1 – 1.4 – 0.4 0.3 62.4 21.5 9.9 – – 0.1 – – – – – 31.5

– – 0.5 0.1 6.4 4.5 0.3 0.8 0.2 12.8 0.1 – – 22.1 – 0.2 – 0.1 – 22.4 65.6 0.5 – – – – – – – – 66.0

– – – 0.1 10.8 3.9 0.3 0.2 0.3 15.7 0.2 – – 23.9 – 0.1 – – – 24.2 52.1 7.8 – – – – – – – – 59.8

– – – – 12.3 1.9 0.4 0.1 0.1 14.8 0.1 – – 27.7 – 0.3 – 0.0 – 28.1 56.1 1.0 – – – – – – – – 57.1

Dates extracted from Dubois, V., Breton, S., Linder, M., Fanni, J., & Parmentier, M. (2007). Fatty acid profiles of 80 vegetable oils with regard to their nutritional potential. European Journal of Lipid Science and Technology, 109(7), 710–732. https://doi.org/10.1002/ejlt.200700040.

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antioxidant activity by chelating metal substances that easily induce autoxidation. Furthermore, phospholipids improve the oxidative stability of oils by hindering the solubilization of oxygen from the headspace into the oil. Nevertheless, in the absence of metals, phospholipids have been shown to act as prooxidants. In addition, if their concentration is very high, they can also have negative effects on crude oils (Choe & Min, 2006).

4.4 ­Presence of moisture Vegetable oils contain small amounts of water that can range from 0.02% to 0.09%, depending on the degree of refining to which they have been subjected. Furthermore, the water content can also be increased in the oil because it is generated as a product in the oxidation of hydroperoxides (Budilarto & Kamal-Eldin, 2015). At low levels, it has been seen that water can act as an antioxidant, as it hydrates and dilutes catalytic metal oxides. However, if water concentration increases, its presence can have the opposite effect and acts as a prooxidant by solubilizing the metal oxide catalysis in the vegetable oil (Ghnimi, Budilarto, & Kamal-Eldin, 2017).

4.5 ­Presence of chlorophylls Chlorophyll is a plant pigment present in oils naturally. These compounds and those resulting from their degradation (pheophytins and pheophorbides) act as sensitizers to produce singlet oxygen that triggers photooxidation reactions in the presence of light and triplet oxygen (Matthäus, 2010). In this way, they strongly accelerate the oxidation of vegetable oils. On the contrary, in the absence of light, chlorophylls can act as antioxidants, donating hydrogen to the free radicals present in the oil (Gutiérrez-Rosales, Garrido-Fernández, Gallardo-Guerrero, Gandul-Rojas, & Minguez-Mosquera, 1992).

4.6 ­Presence of lipoxygenase The presence of lipoxygenase can favor the enzymatic oxidation of vegetable oils since this enzyme catalyzes the reaction between molecular oxygen and UFAs, which form hydroperoxides (Tayeb et al., 2017). Controlling this reaction is very important in the extraction of oils from raw materials rich in this enzyme. Thus, when obtaining oil from soybeans and rice, it must be considered that lipoxygenase can greatly accelerate enzymatic oxidation reactions as they are the two main plant sources of this enzyme (Madhujith & Sivakanthan, 2019).

4.7 ­Presence of metals Various metals such as copper, iron, manganese, and nickel appear in vegetable oils as trace elements because they are absorbed by plants during their growth. For this reason, in general, virgin oils tend to have higher amounts of these compounds. However, some of these metals can also reach the oil through processing and may also

4 ­ Factors influencing the lipid oxidation of vegetable oils

be present in refined oils, although in less concentrations (Madhujith & Sivakanthan, 2019). On this matter, metals increase the rate of oxidation of the vegetable on account of the reduction of the activation energy of the initiation step in autoxidation; the production of lipid alkyl radicals directly; the generation of singlet oxygen; the generation of hydroxyl radicals and hydrogen peroxide; the rapid decomposition of hydroperoxides; and the destruction of phenolic compounds that can act as antioxidants (Ahmed et al., 2016; Choe & Min, 2006; Ghnimi et al., 2017).

4.8 ­Presence of antioxidants compounds Antioxidant compounds are naturally present in vegetable oils. These substances are great determinants of the stability of the oil as they help reduce oxidation processes. This occurrence is clearly observed in virgin oils, which, despite not undergoing a refining process that removes prooxidant substances, generally have greater oxidative stability than their refined counterparts (Ayyildiz, Topkafa, Kara, & Sherazi, 2015; Gertz, Klostermann, & Kochhar, 2000). Specifically, antioxidants delay the start of the oxidation induction period or help slow down the speed of the reactions that take place in this process. This antioxidant activity is achieved through different mechanisms of action since antioxidants have the ability to capture free radicals (such as lipid alkyl and peroxyl radicals), chelate metals, quench singlet oxygen, and/ or inactivate sensitizers (Matthäus, 2010). On the other hand, the individual effect of antioxidant compounds can be modified in a multicomponent matrix such as vegetable oil. Thus, it has been shown that the synergy between different antioxidants is an important factor in the oxidative stability of vegetable oils. On the contrary, it should also be considered that antioxidants can have a negative effect on the stability of the oil if the conditions in which they are found are not suitable. Thus, too high concentrations of antioxidants or the presence of certain substances, make these biocompounds possible to convert them into prooxidant substances (Choe & Min, 2006).

4.9 ­Vegetable oil processing The presence or absence of prooxidant and oxidant compounds is directly conditioned by the processing degree of the vegetable oils. In this way, industrial techniques to obtain oil from oleaginous material largely determine the oxidative stability of vegetable oils due to the working conditions employed (high temperatures, presence of light, oxidants, enzymes, humidity) and the degree of the extraction of natural prooxidants and antioxidants achieved (Pignitter & Somoza, 2012). However, there are two different types of oil production (with and without refining), which affect oxidative stability differently. This is how we distinguish between refined oils and virgin oils. In the case of refined oils, the raw plant material is subjected to mechanical and then chemical extraction. Organic solvents (generally hexane) are used for chemical extraction, which allows very high extraction yields to be obtained. Nevertheless, in the extraction process, the quality of the resulting vegetable oil is damaged in terms of sensory evaluation, color, and

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oxidative stability. Therefore, it is essential to carry out a final oil refining (typically consisting of the neutralization, bleaching, winterization, and deodorization steps) to eliminate the undesirable compounds generated and make it suitable for use in the food industry (Matthäus, 2007). Although the final objective of refining is to eliminate impurities minimally damaging the oil, the steps used can lead to the loss of antioxidant compounds, which can reduce the oxidative stability of the vegetable oil (Gertz et al., 2000). On the other hand, virgin oils are only obtained through physical processes. Thus, the extraction is done by pressing and subsequent filtration, decanting, or centrifugation techniques. In this way, oils with high oxidative stability are obtained since although the prooxidant substances are not eliminated, for the most part, the oils contain high concentrations of bioactive compounds with antioxidant activity. In contrast, it should be considered that if the raw starting material does not have a good oxidation state, or the physical-extraction conditions and/or storage are not adequate, the virgin oil obtained may have worse oxidative stability than that obtained by refining techniques (Matthäus, 2010). For this reason, the raw materials employed to obtain virgin oils must be of excellent quality and the technological processing to which they are subjected must be strictly controlled to minimize oxidation reactions.

4.10 ­Oxygen exposure Oxygen is one of the most important extrinsic factors responsible for lipid oxidation in oils. This substance is the main component of oxidation because it is a source of reactive oxygen species (triplet and singlet oxygen) that can react with alkyl radicals and/or directly with fatty acids. Thus, both the type and the concentration of oxygen play a very important role in the stability of edible vegetable oils (Choe & Min, 2006). The oxygen concentration in the vegetable oil is conditioned by the oxygen partial pressure in the headspace of the oil (Madhujith & Sivakanthan, 2019). Concretely, high partial pressures of oxygen cause the proportion of dissolved oxygen in the oil to increase, triggering oxidation reactions more easily (Min & Wen, 1983). In this case, it is worth noting that the solubility of oxygen is higher in oils that have not undergone a refining process, which can make virgin oils more susceptible to oxidation in the presence of this gas (Aho & Wahlroos, 1967). Additionally, oxygen and vegetable oils can react more efficiently when there is a high surface/ volume ratio, which allows greater oxygen diffusion. However, the oxidation rate is dependent on the oxygen concentration only when it is low since it has been seen that at high oxygen concentrations the oxidation rate is independent of the oxygen concentration. Moreover, the presence of different prooxidants (light, high temperature, metals, sensitizers, etc.) can accelerate oxidation reactions with the oxygen (Choe & Min, 2006). On the other hand, the reaction rate between lipids and oxygen depends on the type of oxygen species available. In this sense, the reaction rate of singlet oxygen with lipids is much higher than that of triplet oxygen, because singlet oxygen can react directly with lipids while triplet oxygen reacts with the radical state of lipids (Rawls & Van Santen, 1970).

5 ­ Implications and importance of lipid oxidation in vegetable oils

4.11 ­Light exposure Light is a determining factor in the oxidation produced in photooxidation. Its importance resides in the fact that the presence of light can promote the initiation phase of photooxidation due to the formation of singlet oxygen, through the intervention of pigments such as chlorophyll and porphyrin that can react directly with the lipids of the oil. Moreover, light can also accelerate the oxidation of oils through the presence of certain compounds, such as riboflavin, which can transfer light energy to the substrate directly without the intervention of singlet oxygen (Matthäus, 2010). Specifically, the light of shorter wavelengths has more damaging effects on vegetable oils than longer wavelengths, ultraviolet light is more harmful than visible light (Choe & Min, 2006). Additionally, the effect of light on oil oxidation decreases as the temperature increases, so that at high temperatures, photooxidation is less important (Velasco, Andersen, & Skibsted, 2004).

4.12 ­Temperature Even though the use of high temperatures drastically decreases the solubility of oxygen in the oil, the autoxidation reactions are immensely accelerated when applying heat treatments. Thus, at temperatures above 150°C, the hydroperoxides that form are rapidly decomposed, continuously generating new primary oxidation products (Dobarganes, 1998). On the contrary, the temperature hardly influences the oxidation reactions that occur during photooxidation since singlet oxygen has low activation energy (Choe & Min, 2007). For this reason, as mentioned previously, at high temperatures this mechanism of oil degradation hardly becomes interesting (Velasco et al., 2004). Given the above facts, it should be noted that the deep-frying process, widely used in industrial and home cooking, accelerates the oxidation of oil and leads to the formation of primary and secondary oxidative products that are absorbed by fried foods. For this reason, the use of vegetable oils that have high oxidative stabilities is of special interest, in addition to minimizing the processes of repeating frying with the same oil (Momchilova et al., 2012). Thus, the ingestion of oxidation products that can be harmful to health is also reduced (Madhujith & Sivakanthan, 2019).

5 ­Implications and importance of lipid oxidation in vegetable oils The control of the oxidation of the edible vegetable oils acquires very important attention since oxidation reactions can originate off-flavor compounds that make the oil less acceptable or unacceptable to consumers or for industrial employ as a food ingredient (Choe & Min, 2006; Roselló-Soto et al., 2019). In addition to losses in sensory quality, oxidation reactions also lead to losses in nutritional value due to the destruction of essential fatty acids and bioactive compounds. Moreover, this chemical process causes the formation of primary and secondary oxidative compounds, which are harmful to human health (Madhujith & Sivakanthan, 2019).

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5.1 ­Loss in sensory quality The principal effect that becomes clear as a consequence of the oxidation of edible vegetable oils is a decrease in sensory quality since oxidation reactions cause changes in the odor, flavor, color, and texture (Gómez-Cortés et al., 2015). Specifically, within these changes, the modification in the aromatic profile of the oil is most important since it determines the acceptance of the consumer (Zamuz et al., 2020). In this way, the formation and accumulation of volatile products derived from lipid oxidation, such as alkanals, 2-alkenals, and trans, trans-2,4-alkadienals, are responsible for the common oxidized oil flavor on account of their low threshold values (Choe & Min, 2006). More concretely, of all the volatile compounds, aldehydes may be one of the most important flavor substances in vegetable oils (Zhang, Cao, & Liu, 2020), usually referred to as rancidity (Syed, 2016). Thus, specific substances such as pentanal, and hexanal have been proposed as indicators for the development of off-flavors in vegetable oils (Van Ruth, Roozen, & Jansen, 2000). Additionally, in vegetable oils, other compounds were also identified that generated a wide rejection in consumers due to their aroma. This is the case of 2,4,7-decatrienal, which produces a fishy off-flavor during storage or heat treatment. Similarly, 1-penten-3-one and 1-octen3-one ketones were associated with the “fishy” descriptor in oils (Matthäus, 2010). Contrary, other compounds derived from lipid oxidation have been identified with pleasant odors. Thus, for example, 2,4-decadienal is considered one of the most important contributors to the flavor of deep-fried foods. This occurrence has generated the problem that consumers associate the perception of this pleasant aroma with good quality oils, even though it is characteristic of oxidized edible vegetable oils (Matthäus, 2010). On the other hand, it is important to note that the loss of sensory quality is closely linked to the fatty acid composition of the oil. Thus, depending on this intrinsic factor the characteristics and perceptions of rancid odors can be very distinct (Syed, 2016). In this aspect, it should be noted that oils that present linolenic acid result in volatile secondary oxidation products are more damaging to the aroma, as would be the case of the aforementioned 2,4,7-decatrienal. Due to this reason, the use of certain vegetable oils (such as rapeseed or soybean oils) is rejected by the industry and by consumers for it is used in the deep-frying process (Matthäus, 2010).

5.2 ­Loss in nutritional quality and formation of toxicological compounds During the oxidation of the oils, there is a loss of UFAs, also reducing the content of essential fatty acids such as linolenic acid. Similarly, the bioactive compounds present in vegetable oils degrade because of their intervention in oxidation reactions. In this way, there are significant losses at the nutritional level since most of the edible vegetable oils consumed are supposed to be interesting sources of unsaturated fatty acids and of certain antioxidants with beneficial effects on human health. In addition to the loss of nutritional value, the oxidation of the oils can have toxicological implications. In this sense, several secondary products of lipid oxidation formed in oils are judged to be a risk factor for human health (Madhujith & Sivakanthan, 2019).

6 ­ Determination of the lipid oxidation of vegetable oils

Specifically, the formation of hydroxylated α,β-unsaturated aldehydes, such as 4-hydroxy-2-trans-nonenal (HNE) and 4-hydroxy-2-trans-hexenal (HHE), acquires special interest due to these nonvolatile compounds that are probably a cause of a large number of diseases enclosing atherogenesis, diabetes, Alzheimer’s disease, and even cancer (Ma et  al., 2020). These possible damages are on account of the high chemical reactivity of these molecules, which makes them easily interact with nucleophiles such as proteins, DNA, and phospholipids, causing structural damage and functional alterations in vivo (Ayala, Muñoz, & Argüelles, 2014; Long & Picklo, 2010; Schneider, Porter, & Brash, 2008; Sousa, Pitt, & Spickett, 2017). Along the same lines, malondialdehyde (MDA) and 2-propenal (acrolein), which appear frequently after the oxidation of certain fatty acids in oils, are also secondary oxidation compounds of special interest due to their potential toxicity in the organism. Thus, it has been observed that MDA is an in vivo mutagenic compound owing to its ability to react with the DNA base adduct guanine, at the same time it has been shown to exert cancer-initiating (Kanner, 2007; Vieira, Zhang, & Decker, 2017). For its part, acrolein exerts its damaging effect mainly on account of its strong electrophilic power that allows this substance to easily react with glutathione, a molecule that mediates oxidative stress (Grootveld, Percival, Leenders, & Wilson, 2020; Vieira et al., 2017).

6 ­Determination of the lipid oxidation of vegetable oils Due to the important implications of the oxidation of edible vegetable oils, the measurement of this parameter plays an important role in assessing the quality of this food ingredient. On this matter, different physicochemical and chromatographic methodologies and sensory evaluations have been proposed for the determination of primary and secondary lipid oxidation compounds that allow knowing the oxidation state of the oil (Matthäus, 2010).

6.1 ­Determination of peroxide value The peroxide value (PV) is one of the major methods used to determine the oxidation state of vegetable oils (Roselló-Soto et al., 2019). This index may be determined potentiometrically or colorimetrically by Fourier transform infrared spectroscopy, iodometrically, or by chromatographic separation using HPLC (Mortensen, Sørensen, & Stapelfeldt, 2002). Any of these techniques allows knowing the quantity of primary oxidation compounds and therefore provides information about the oxidation state of the oils. However, because primary oxidation products are highly unstable and react rapidly to produce secondary products, the measurement of peroxide value can result in falsely low levels if their rate of decomposition is faster than that of formation. This fact is very important because sometimes the measurement of peroxide value does not provide real information on the quality of the oil (Matthäus, 2010). In this way, this index may not be adequate for the analysis of oils that present an advanced oxidation state. Despite the restrictions regarding the determination of the oxidation state, knowing the value of peroxides is commercially interesting since it

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permits the edible vegetable oils to be classified into categories established by the European Commission (Zamuz et al., 2020). In addition, a maximum peroxide value has been proposed from which the oils are not considered acceptable for the sensory attributes, being this of 10meq O2/kg (Roselló-Soto et al., 2019).

6.2 ­Determination of p-anisidine value In relation to p-anisidine value (AV), this index reflects the formation of substances derived from the decomposition of hydroperoxides (Rossell & Pritchard, 1991). Concretely, p-anisidine value principally measures 2-alkenals and 2,4-alkadienals (Yang & Boyle, 2016). This parameter may be determined by several methods such as Fourier transform infrared spectroscopy and CDR FoodLab method (Matthäus, 2010). Whatever principle is chosen for determining p-anisidine value, all methods involve the determination of the second oxidation step. Thus, this technique is useful for determining oils in advanced oxidation states, while it does not provide information on the oxidation state of the oils in the first oxidation phase. Due to these characteristics, the p-anisidine value is a suitable parameter to determine the history of edible oils and the oxidative state during long-term storage (Yang & Boyle, 2016). In this way, a lower p-anisidine value means better quality of the oil (Roselló-Soto et al., 2019).

6.3 ­Determination of Totox value Because peroxide and p-anisidine value determinations focus on only one phase of oxidation reactions, their use can sometimes be limited. In this sense, the Totox parameter acquires a special interest since it considers both determinations to provide complete information about the oxidative state of the oil. Thus, through the Totox value, information is obtained about the current state of the oil (using the peroxide index) and its history (using the p-anisidine value). This index is obtained by the formula: 2PV+AV, therefore low values mean a higher quality of the oil (Roselló-Soto et al., 2019).

6.4 ­Determination of individually secondary products by chromatographic techniques Determination of the oxidative state of vegetable oils can also be performed by identifying individual compounds through chromatographic techniques, principally through high-performance liquid chromatography (HPLC) and gas chromatography (GC). In this sense, the determination and quantification of volatile compounds such as hexanal, 3-hexenal, propanal, pentenal, 2,4-heptadienal, 2,4-decadienal, or 2-nonenal play an important role because some of these substances have been related to the oxidation of certain fatty acids, in addition to being related to off odors (Wang et al., 2019). Thus, through its determination and quantification, the oxidative state of the oil can be known. Similarly, the identification and quantification of toxic compounds such as HNE and HNN are interesting, in addition to knowing the oxidative state of

7 ­ Determination of oxidative stability of vegetable oils

the oil, to know the possible presence of toxic compounds, since as mentioned previously these compounds are related to different toxicology effects (Ma et al., 2020).

6.5 ­Determination of oxidation by sensory evaluations The determination of lipid oxidation by means of the physicochemical and chromatographic techniques explained in this section can be difficult to correlate with the parameters of the real quality of the oil as sensory perceived. For this reason, the sensory evaluation of edible oils is of special interest in quality examination. In fact, various standards judge sensory evaluation as the main parameter for examining the quality of edible oils (Matthäus, 2010). On this matter, different attributes (such as fruity, bitter, and spicy) and various defects (rancid, moldy, wine, metallic and oxidized) must be considered. In addition, in these types of determinations, the suitability of conducting tastings by both a panel of trained experts and consumers must be considered, to know the real acceptance and purchase preferences (Zamuz et al., 2020).

7 ­Determination of oxidative stability of vegetable oils The determination of the oxidative stability of the vegetable oils makes it feasible to predict the possible behavior of the product during storage. Thus, the main difference it presents with the lipid oxidation determination techniques discussed in the previous point is that oxidative stability does not supply information on the current state of the oil. However, the information provided by the oxidative stability is very valuable for the industry since it permits predicting the shelf life oils (Matthäus, 2010). The general methodology of this parameter is the storage of the vegetable oils under certain conditions for a predetermined period (usually simulating the expected storage conditions) and the subsequent measurement of the oxidative state of the oil through the determination techniques already explained in the previous section. These simulations tend to be performed in an accelerated way because the usual storage periods (under ambient conditions) of the oils would be too long (Kerrihard et al., 2015; Li et  al., 2013). Some examples of oxidative stability determination methods are the Schaal Oven Test and the Active Oxygen Method (AOM). In the case of the Schaal Oven Test, it is a method that applies temperatures close to 60°C and lasts between 4 and 8weeks, until the rancidity is perceived by sensory evaluation or by measuring the peroxides value. On the other hand, the Active Oxygen Method permits to reduce the analysis time since it subjects the oil to constant aeration of the oil at 98°C until a peroxide value of 100meq O2/kg is reached. In addition, there are other techniques available that measure secondary oxidation products. This is the case of the Rancimat test and oxidative stability Instrument, which are automated versions of the active oxygen method in which the determination of peroxide value is replaced by the measure of secondary compounds of lipid oxidation. Both automated methods have been reported of higher accurate and reproducible than the traditional Schaal Oven Test and the Active Oxygen Method (Matthäus, 2010).

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8 ­Protection and improvements against lipid oxidation in vegetable oils Given the importance and the implications of the oxidation of vegetable oils, both at sensory and nutritionally levels, protection against this deterioration mechanism is essential in the food industry to reduce economic losses and produce healthier products that are free of toxic compounds. On this matter, to maintain the quality and storage stability of edible oils, the most important aspects are the control of the factors that affect the oil from the outside (oxygen, temperature, and light), without forgetting the operations prior to obtaining the oil (Pignitter & Somoza, 2012). Thus, the vegetable oil industry should try to monitor all the treatments by which the vegetable oil is obtained and the subsequent exposure to oxygen, light, and high temperatures during storage to implement the necessary improvements.

8.1 ­Protection during the processing of vegetable oils The most important factors to consider in the oil extraction process are the temperature employed in the different steps and the oxygen exposure. In this sense, working at temperatures as low as possible and minimizing times of exposition with strict oxygen control is essential to obtain oils with good oxidative stabilities. These actions are of particular importance in refining steps such as deodorization where it is convenient to deaerate the oil at a low temperature to reduce oxygen solubility and minimize oxidation reactions (Matthäus, 2010). Furthermore, in the processing of virgin oils, there is also a tendency to use temperatures as low as possible, to reduce the loss of antioxidants. Hence, techniques such as cold-pressing are a good way to improve oxidative stability (Madhujith & Sivakanthan, 2019). Another aspect to consider when processing oils is ensuring the removal of prooxidant agents which promote oxidation (free fatty acids, photosensitizers, metals, etc.). Therefore, although high temperatures favor oxidation, they cannot be excluded from the refining methodology because they are necessary to carry out this process correctly. Thus, despite using oxidative conditions, the stability of the extracted oil is improved because alkali refining removes free fatty acids, phospholipids, metal ions, and chlorophylls; bleaching minimizes chlorophylls, carotenoids, metal ions, and oxidation products; deodorization eliminates volatile substances and free fatty acids; and steam treatment extracts short-chain degradation products (Matthäus, 2010). However, in the case of metallic prooxidants their presence is not only linked to the naturally occurring concentrations in raw materials but also that these compounds can be transferred from certain metallic surfaces to the oil during processing. In this sense, the use of facilities made with stainless steel is a good measure to minimize the transfer of undesirable metals from the equipment to the oil (Matthäus, 2007). Regarding the exposure to light, this does not acquire very notable importance in the process of obtention of vegetable oils because the influence of the application of high temperatures and exposure to oxygen are elements that prevail over the light factor (Matthäus, 2010).

8 ­ Protection and improvements against lipid oxidation in vegetable oils

8.2 ­Protection during storage of vegetable oils The storage conditions of vegetable oils also determine the oxidative stability and shelf life of this product (Pignitter & Somoza, 2012). However, the only way to maintain the quality and stability of vegetable oils during storage is to control the factors that affect the oil from the outside, these being the oxygen (just at the time of packaging), temperature, and light (Madhujith & Sivakanthan, 2019; Pattnaik & Mishra, 2021). In this sense, to improve oxidative stability during storage, it has been found convenient to keep the oil in absence of oxygen, at refrigeration temperatures, and protected from light (Choe & Min, 2006; Rabadán, Álvarez-Ortí, Pardo, & Alvarruiz, 2018). Despite the above knowledge, the storage of vegetable oils does not always produce in optimal conditions due to various reasons (mainly economic and consumer acceptance). An example is the elimination of oxygen in the packaging which is not usually carried out because it is a slow process and of high economic cost. However, to minimize the effects of this occurrence, in the packaging of oils the headspace that is left is minimal, the air being also replaced by inert gases (Matthäus, 2010). Regarding the use of refrigeration temperatures during the oils storage, this is conditioned by the precipitation processes of the compounds with a higher melting point because this fact can affect the acceptance by the consumer when observing sediments in vegetable oils (Matthäus, 2007). In this sense, oils are usually kept at room temperature for sale to final consumers. Similarly, despite the suitability of keeping the oil protected from light, on many occasions these are stored in transparent containers because the consumer values seeing the coloring of vegetable oils. This occurrence contrasts with the ease of incorporating various dyes in the containers, which would satisfactorily improve the stability of the oil against photooxidation by absorbing UV light (Choe & Min, 2006). Despite the peculiarities of oil storage for final consumption, it should be noted that the use of oils to produce other products in the food industry is not conditioned by the final consumer so that the conditions of refrigeration and the absence of light can be easily applied to improve oxidative stability.

8.3 ­Improvement of vegetable oils stability by antioxidants addition As explained earlier in this chapter, the natural presence of antioxidant compounds in vegetable oils is a factor that greatly improves the oxidative stability of these foods. In this way, the deliberate addition of certain antioxidant substances can be an ideal tool in the prevention of oxidation (Choe & Min, 2006). In fact, the use of antioxidants to reduce lipid oxidation in foods is widely accepted (Fki, Allouche, & Sayadi, 2005; Venturi et  al., 2017). However, it must be taken into account that the antioxidants utilized must accomplish various requirements such as not presenting toxicity, being soluble in oil, being effective at low concentrations, not modifying the sensory perception of the oil, and being stable during the processing and storage period of the oil (Matthäus, 2010). Moreover, it is appropriate to know the mechanisms of action of antioxidants against lipid oxidation, since this allows proper use of these substances. An example of this importance can be found in the prevention of photooxidation

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­ ediated by chlorophylls and pheophytins (Type II photooxidation reactions) since m these mechanisms are not mediated by free radicals. Therefore, commonly used antioxidants, which base their mechanism of action on the capture of free radicals would not be useful in this type of oxidation. On the other hand, it is worth highlighting the existence of two groups of antioxidants (according to their origin), namely natural and synthetic. In this sense, synthetic antioxidants such as butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) are very effective compounds with a low production cost. Despite this, due to their toxicity and the rejection they generate in consumers, natural antioxidants are a very interesting replacement option in the food industry (Grosso, Riveros, Asensio, Grosso, & Nepote, 2020). Thus, antioxidants naturally present in certain foods and/or by-products such as tocopherols, tocotrienols, phenolic compounds, and lignan substances, could be used to combat oxidation in vegetable oils (Fki et al., 2005; Matthäus, 2010; Venturi et al., 2017). Additionally, the use of these antioxidant compounds in oils is usually done in combination to promote the synergy effect since it has been seen that their combination results in higher resistance to oxidation compared to their effects alone. For example, the joint use of metal chelators and free radical scavengers generates protections against oxidation greater than the sum of their effects individually (Choe & Min, 2006).

8.4 ­Improvement of oxidative stability through the change of fatty acids Modifying the fatty acid profile of vegetable oils is another way to improve oxidative stability. Specifically, the reduction of polyunsaturated acids such as linoleic and linolenic is the most satisfactory way to obtain improvements in protection against oxidation (Wilson, 2012). On this matter, the use in the food industry of partial or total hydrogenation processes of highly unsaturated oils such as sunflower, soybean, rapeseed, or peanut can successfully reduce their oxidative deterioration. However, this methodology may limit the applications of the oils obtained (Madhujith & Sivakanthan, 2019). In addition, this technique generates high amounts of trans fatty acids, which have been shown to be harmful to health (Hua et al., 2020). On the other hand, genetic and reproduction techniques can also be employed to modify the fatty acid profile of vegetable oils (Wilson, 2012). The modification in the content of saturated acids, oleic acid, and linolenic acid is usually the most common in oilseed plants. Thus, the main objectives are to obtain oils with a high or medium oleic acid content, which see their oxidative stability increased at high temperatures (Lee, Bilyeu, & Shannon, 2007). Due to these characteristics, the modification through genetic and reproduction techniques has a greater acceptance compared to hydrogenation techniques, since it does not increase saturated fatty acids or lead to the formation of trans fatty acids (Madhujith & Sivakanthan, 2019). Similarly, the blending of different oils allows the modification of the fatty acid content without the incorporation of trans fatty acids. Thus, the simple combination of different oils and the modification in their proportions can be varied to improve oxidative stability and minimize oxidation reactions (Abdel-Razek, El-Shami, El-Mallah, & Hassanien, 2011).

9 ­Conclusions

8.5 ­Improvement of oxidative stability by encapsulation techniques Microencapsulation has a promising role in the present and future of the food industry since this technology is a method that allows to increase the shelf life of certain compounds (Gómez et al., 2018). In this sense, microencapsulation can help improve the oxidative stability of vegetable oils rich in polyunsaturated fatty acids through different techniques such as extrusion, spray drying, and freeze drying (Mohammed, Tan, Manap, Muhialdin, & Hussin, 2020; Pattnaik & Mishra, 2021). This occurrence allows the food industry to use microencapsulated vegetable oils in the elaboration of new products, minimally affecting their final oxidative stability. Moreover, with this addition, it is possible to improve the lipid profile of different foods such as meat derivatives, which naturally have a lower content of polyunsaturated fatty acids (Vargas-Ramella et al., 2020). Thus, healthy functional products are obtained while diversifying the market. Nevertheless, although microencapsulation is a technique that improves the stability of the oils, it must be considered that the operations used to obtain the microencapsulates could damage the fatty acids. For this reason, it must be considered that this process must minimize the action of the factors that favor the oxidation reactions.

9 ­Conclusions At present, there are still decreases in the quality of vegetable oils due to lipid oxidation. However, this mechanism occurs through complex reactions that differ according to the conditions in which the vegetable oils are found, which makes its complete control very difficult. Thus, this process is modified by many factors both inherent to the oil and to the environment in which it is found. In this regard, the fatty acid composition of the oil, the processing to which it has been subjected (refined or virgin oil), and the existence of antioxidant compounds in its core, together with the presence of oxygen, light, and high temperatures are the factors that most affect the oxidation of vegetable oils during their production, handling, and storage. Hence, the industrial operations carried out to obtain the oil and to use it as an ingredient, as well as to store it, must be very strict to minimize oxidation processes. On the other hand, the reaction products generated during lipid oxidation are responsible for off-flavor and the loss of nutritional quality as a consequence of the deterioration of essential fatty acids and the appearance of toxic compounds such as HHE and HNE. These negative modifications determine the oxidative state and oxidative stability of the oil necessary to guarantee the consumption of good quality oils and ensure the suitability of the product throughout its shelf life. In this sense, various techniques for determining lipid oxidation have been proposed, including sensory evaluations, as well as techniques that allow predicting oxidative stability. However, if the oxidation state of the oil is to be known exactly, these techniques must be combined to obtain adequate information. Finally, to these annotations, the need to improve the oxidative stability of the vegetable oils must be added, to avoid economic losses in the food industry and guarantee a nutritious food without toxic compounds to the consumer. In this

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regard, the study and fine-tuning of techniques that allow the increase in oxidative stability without affecting the quality of vegetable oils (such as microencapsulation processes or the addition of natural antioxidants) are excellent resources to guarantee the proper oxidation state of vegetable oils.

­Acknowledgments Noemí Echegaray acknowledges Consellería de Cultura, Educación e Ordenación Universitaria (Xunta de Galicia) for granting with a predoctoral scholarship (Grant number IN606A-2018/002). The authors are the members of the Healthy Meat network, funded by CYTED Ciencia y Tecnología para el Desarrollo (ref. 119RT0568). The authors thanks GAIN (Axencia Galega de Innovación) for supporting this project (Grant number IN607A2019/01).

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Tayeb, A. H., Sadeghifar, H., Hubbe, M. A., & Rojas, O. J. (2017). Lipoxygenase-mediated peroxidation of model plant extractives. Industrial Crops and Products, 104, 253–262. https://doi.org/10.1016/j.indcrop.2017.04.041. Van Ruth, S. M., Roozen, J. P., & Jansen, F. J. H. M. (2000). Aroma profiles of vegetable oils varying in fatty acid composition vs. concentrations of primary and secondary lipid oxidation products. Nahrung – Food, 44(5), 318–322. https://doi. org/10.1002/1521-3803(20001001)44:53.0.CO;2-4. Vargas-Ramella, M., Pateiro, M., Barba, F. J., Franco, D., Campagnol, P. C. B., Munekata, P. E. S., et al. (2020). Microencapsulation of healthier oils to enhance the physicochemical and nutritional properties of deer pâté. LWT- Food Science and Technology, 125, 109223. https://doi.org/10.1016/j.lwt.2020.109223. Velasco, J., Andersen, M. L., & Skibsted, L. H. (2004). Evaluation of oxidative stability of vegetable oils by monitoring the tendency to radical formation. A comparison of electron spin resonance spectroscopy with the Rancimat method and differential scanning calorimetry. Food Chemistry, 85(4), 623–632. https://doi.org/10.1016/j.foodchem.2003.07.020. Venturi, F., Sanmartin, C., Taglieri, I., Nari, A., Andrich, G., Terzuoli, E., et  al. (2017). Development of phenol-enriched olive oil with phenolic compounds extracted from wastewater produced by physical refining. Nutrients, 9(8), 1–13. https://doi.org/10.3390/ nu9080916. Vieira, S. A., Zhang, G., & Decker, E. A. (2017). Biological implications of lipid oxidation products. JAOCS, Journal of the American Oil Chemists’ Society, 94, 339–351. https://doi. org/10.1007/s11746-017-2958-2. Wang, Y., Zhu, M., Mei, J., Luo, S., Leng, T., Chen, Y., et al. (2019). Comparison of furans formation and volatile aldehydes profiles of four different vegetable oils during thermal oxidation. Journal of Food Science, 84(7), 1966–1978. https://doi.org/10.1111/1750-3841.14659. Wasowicz, E., Gramza, A., Hes, M., Jelén, H. H., Korczak, J., Maecka, M., et  al. (2004). Oxidation of lipids in food. Polish Journal of Food and Nutrition Sciences, 13(S1), 87–100. Wilson, R. F. (2012). The role of genomics and biotechnology in achieving global food security for high-oleic vegetable oil. Journal of Oleo Science, 61(7), 357–367. https://doi. org/10.5650/jos.61.357. Yang, X., & Boyle, R. A. (2016). Sensory evaluation of oils/fats and oil/fat-based foods. In M. Hu, & C. Jacobsen (Eds.), Oxidative stability and shelf life of foods containing oils and fats (pp. 157–185). https://doi.org/10.1016/B978-1-63067-056-6.00003-3. Yun, J. M., & Surh, J. (2012). Fatty acid composition as a predictor for the oxidation stability of Korean vegetable oils with or without induced oxidative stress. Preventive Nutrition and Food Science, 17(2), 158–165. https://doi.org/10.3746/pnf.2012.17.2.158. Zambiazi, R. U. I. C., Przybylski, R., Zambiazi, M. W., & Mendonça, C. B. (2007). Fatty acid composition of vegetable oils and fats. Boletim Do Centro de Pesquisa de Processamento de Alimentos, 25(1), 111–120. Zamuz, S., Purriños, L., Tomasevic, I., Domínguez, R., Brncic, M., Barba, F. J., et al. (2020). Consumer acceptance and quality parameters of the commercial olive oils manufactured with cultivars. Food, 9, 427. https://doi.org/10.3390/foods904042. Zhang, W., Cao, X., & Liu, S. Q. (2020). Aroma modulation of vegetable oils—A review. Critical Reviews in Food Science and Nutrition, 60(9), 1538–1551. https://doi.org/10.1080 /10408398.2019.1579703.

PART

Lipid analysis in food

3

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CHAPTER

Fat and fatty acids

8

Sol Zamuza, Mirian Pateiroa, Carlos A. Conte-Juniorb, Rubén Domíngueza, Asad Nawazc, Noman Walayatd, and José M. Lorenzoa,e a

Centro Tecnológico de la Carne de Galicia, Ourense, Spain Programa de Pós-Graduação em Ciência de Alimentos, Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, Brazil c Jiangsu Key Laboratory of Crop Genetics and Physiology, College of Agriculture, Yangzhou University, Yangzhou, People’s Republic of China d Department of Food Science and Engineering, College of Ocean, Zhejiang University of Technology, Hangzhou, China e University of Vigo, Ourense, Spain b

­C hapter outline 1  Fat and fatty acids analysis in food........................................................................ 155 2  Extraction methods................................................................................................ 156 3  Derivatization methods.......................................................................................... 161 4  Separation methods: Gas chromatography and other chromatographic techniques.... 162 5  Detection methods................................................................................................ 167 5.1  GC detectors....................................................................................... 167 5.2  HPLC detectors................................................................................... 168 5.3  TLC detectors...................................................................................... 169 5.4  SFC detectors...................................................................................... 170 6  Key findings.......................................................................................................... 170 Acknowledgments..................................................................................................... 170 References............................................................................................................... 170

1 ­Fat and fatty acids analysis in food Lipid analysis in food is a complex process due to several factors. Firstly, lipids include a high number of compounds with different chemical properties and structures, which will be analyzed by different analytical techniques depending on whether you want to determine the total fat content (gravimetric determination) or lipid profile (chromatographic methods: (GC-MS, LC-MS, GC-FID)) and with Food Lipids. https://doi.org/10.1016/B978-0-12-823371-9.00012-5 Copyright © 2022 Elsevier Inc. All rights reserved.

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different methodology (short-chain fatty acids and volatile fatty acids are typically analyzed in their free acid form, while large-chain fatty acids are converted to fatty acid methyl esters (FAMEs)). Moreover, the lipids are present in a wide variety of food (vegetables, meat products, seeds, milk, dairy products, fish, fruits, flour products, etc.) forming complex matrices and each food has characteristic lipids (Table  8.1). The lipid fraction extraction depends on how fat is found in the food matrix (Hewavitharana, Perera, Navaratne, & Wickramasinghe, 2020). Fat and fatty acid analysis includes two methods: extraction of lipid fraction of the food sample and determination of fatty acids. In both these methods, several steps are involved (Fig. 8.1). In this chapter, a description of the different analytical methods that have been developed for analysis of fat and fatty acids analysis in the past few decades is provided.

2 ­Extraction methods This step is common both to determine the total fat content and to extract the lipid fraction for fatty acids profile analysis. It is usually a gravimetric method and extraction is with organic solvents. Prior to extraction itself, the food samples must be prepared for efficient extraction. As many organic solvents are immiscible in water, it is necessary to dry the samples for they can penetrate. The sample drying process (AOAC 981.11, 2000) is carried out by adding 1 g Na2SO4/10 g sample and drying it in an oven at 45–50°C. It should be borne in mind that high temperature can cause lipid oxidation and increase bound lipids (Hewavitharana et al., 2020). Also, hydrolysis can be necessary to release the bound lipids linked to protein and/or carbohydrates (Nielsen, 2017). Acid hydrolysis is a suitable method for most of the food products, but for cheese and other dairy products alkaline hydrolysis or a combination of two methods is better due to the high content of acid-labile conjugated linoleic acids (CLA), short-chain fatty acids, and t,t-CLA (AOAC 996.06, 2002). The Roese-Gottlieb method uses ammonia for casein elimination and ethyl alcohol to break the emulsion and link between fat and protein (Crocker et  al., 1955). In other cases, such as tissues vegetables, lipids are in cytoplasm protected with a cell wall, and it is necessary to break this wall with mechanical methods, ultrasonication, osmotic pressure changes, etc. There are various official methods for the extraction process which can be applied to different types of food samples: Association of Official Analytical Collaboration (AOAC) International, American Oil Chemistry Society (AOCS), American Association for Clinical Chemistry (AACC), International Organization for Standardization (ISO), International Union of Pure and Applied Chemistry (IUPAC), and International Dairy Federation (FIL). They are all based on the interaction between the solvent and lipids; therefore, their efficiency depends on the polarity of the lipids and solvents. Polar lipids (glycolipids, phospholipids) are more soluble in polar organic solvents (alcohols) and nonpolar lipids (triacylglycerols) are more soluble in nonpolar organic solvents (hexane, chloroform, ethyl ether, petroleum ether, etc.).

Table 8.1  How fat is found in food matrices and sample preparation methods. Extraction Food matrix

Lipid type

Official method

Method

Solvent

Derivatization

Seeds and nuts

Free

AOAC 948.22 (2012)

EE/Hex

Milk and dairy derivates

Free with a phospholipid layer

AOAC 905.02 (1973)

Soxhlet UAE Modified Folch

BF3-MeOH TMSH BF3-MeOH

Animal and plant butter

Meat and meat products

Free with a phospholipid layer

Free and bounded

AOAC 996.06 (2002)

Modified Bligh and Dyer

AOAC 9380.6 (2012)

Soxhlet Solvent extraction Rose-Gottlieb Bligh and Dyer Folch Soxhlet Bligh and Dyer Folch Hara-Radin Rapid microwave solvent extraction SFE Folch

Hex EE/PE

Nonmeat foods: Solvent extraction Meat foods: Folch MAE SFE Solvent extraction Folch Soxhlet MAE Bligh and Dyer

PE/Hex

AOAC 960.39 (2012) AOAC 991.36 (2012) AOAC 985.15 (2012) AOAC 969.33 (2000)

Viscera and egg yolk

Heat-processed foot

Into tissues as phospholipids and/or complex lipids Linked to protein and carbohydrates

Flour products and chocolate –

Chloroform:methanol (2:1, v/v) Chlorofom:methanol:water (1:4:008, v/v/v)

AOAC 996.06 (2002)

AOAC 996.06 (2002)

NaOCH3/KOH TMAH H2SO4 (95%) BF3-MeOH

PE/EE

NaOCH3

BF3-MeOH

NaOCH3

BF3-MeOH PE/Hex

NaOCH3

Hex

BF3-MeOH TMSH

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CHAPTER 8  Fat and fatty acids

FIG. 8.1 Steps of fat and fatty acids analysis in food.

Ethyl ether and petroleum ether are the most used solvents, and a combination of two or three solvents is frequently used (Hewavitharana et al., 2020). The Soxhlet method is a traditional technique that is one of those most used for extracting lipids, and it has been the standard technique for over a century. It is a solid-liquid separation technique based on a semicontinued extraction working with hot solvent reflux which is carried out in an extractor equip named Soxhlet with three main compartments: flash, extraction chamber, and condenser (Fig.  8.2). A dried sample is placed in a porous thimble. The solvent is poured into a distillation flask which is heated. The solvent is evaporated and moved up to the condenser and it is converted into a liquid that is collected in the thimble. The solvent passes through the sample and extracts the fat. When the solvent reaches the overflow level, it is aspirated by a siphon carrying the extracted fat and unloads into the distillation flask. The process is repeated several cycles until complete extraction. Finally, the solvent is evaporated and a lipid fraction is obtained (López-Bascón-Bascon & Luque de Castro, 2019). A high number of official methods are based on this method, and automated methods based on Soxhlet are being accepted as official (AOAC approved technique based on a filter bag proposed by Ankom Technology Inc.). The Soxhlet method is used with food samples with low moisture (  2 μg/mL)

DHA

1.7 g DHA and 0.6 g of EPA for 6 months. After 6 months, all patients received DHA and EPA for another 6 months DHA (2 g/d for 18 months)

Decline in cognitive function was similar in the supplemented group and placebo group at 6 months. However, individuals with very mild cognitive dysfunction (n = 32, MMSE score > 27) in the EPA + DHA-supplemented group experienced a significant decrease in MMSE score decline rate at 6 months A DHA‐enriched ω‐3 FA supplement can have a positive impact on weight and appetite in patients with mild-to-moderate AD DHA supplementation had no beneficial effect on rate of cognitive and functional decline Relative to the control phase, DHA supplementation reduced the LPS-stimulated gene expression of proinflammatory TNFα, IL6 MCP1 as well as antiinflammatory IL10 and the secretion of TNF-α, MCP-1 and IL-10 in monocytes. On the other hand, EPA supplementation increased serum concentrations of IL-10 and lowered only TNFα expression in monocytes. When compared to EPA supplementation, DHA decreased serum concentrations of MCP-1 and MCP-1 secretion in monocytes, while lowering IL10 expression

Jisun, Dayong, Alice and Stefania (2019)

Oleic acid sunflower + DHA or EPA

4-week lead-in control phase (high oleic acid sunflower oil, 3 g/ day) followed by two sequential 10-week supplementation phases with pure DHA or EPA (3 g/day each) separated by a 10-week washout phase

Faxén Irving et al. (2009)

Quinn et al. (2010)

AD, Alzheimer's disease; DHA, docosahexaenoic acid; EPA, eicosapentaenoic acid; HR, heart rate; hsCRP, high-sensitivity C-reactive protein; IgE, immunoglobulin E; IL, interleukin; LC-PUFA, long-chain polyunsaturated fatty acids; LDL/HDL, low-density lipoproteins/high-density lipoproteins; LPS, lipopolysaccharides; MCP1, monocyte chemoattractant protein-1; MMSE, mini mental state examination; NF-α-tumor necrosis factor; PAD, peripheral arterial disease; TAG, triacylglyceride; Th1/2, T helper.

5 ­Contribution of polyunsaturated fatty acids to human health

5.2.3 ­Inflammation

Long-chain FA affects inflammation by means of several mechanisms; some mediated by, or at least related to, fluctuations in FA composition of cell membranes. These variations may alter membrane fluidity and cell signaling leading to a change in gene expression and the pattern of lipid mediator production (Calder, 2010a). Circulating markers of inflammation, such as C-reactive protein (CRP), tumor necrosis factor alpha (TNF-α), and some interleukins (ILs), namely, IL-6, IL-1, correlate with an increased probability of experiencing a cardiovascular event (Micallef & Garg, 2009). On the other hand, inflammatory markers such as IL-6 enable CRP production by the liver and raised levels of CRP are related to an increased risk of the development of cardiovascular illness (Ebrahimi et al., 2009). The antiinflammatory effect of fish oil composed of DHA and EPA has been extensively studied along with the antiinflammatory effect of marine ω-3 FA (Calder, 2006, 2008, 2010b, 2011). However, the different mechanisms by which DHA and EPA control inflammation are not completely identified. High-dose supplementation with DHA and EPA modify the equilibrium among pro- and antiinflammatory cytokines in serum and blood monocytes in subjects with long-lasting inflammation. DHA hinders an extensive variety of pro- and antiinflammatory cytokines, whereas EPA has a moderately minor role in depressing proinflammatory cytokines but conserves the antiinflammatory IL-10 (Jisun et  al., 2019). Also, EPA and DHA have been directly associated with the immunological aspects of viral infections (Calder, Carr, Gombart, & Eggersdorfer, 2020; Messina et  al., 2020). Among the intricate immune-modulatory effects, interleukin-6 (IL-6) and interleukin-1ß (IL-1β) may be affected by dietary EPA and DHA ingestion. Based on the existing results, the supplementation of EPA and DHA in COVID-19 patients seems to present a beneficial effect in handling the “cytokine storm.” Hence, the employment of EPA and DHA supplementation may be studied as both a supportive therapy and a prevention strategy against the SARS-Cov-2 contagion (Szabó et al., 2020).

5.2.4 ­Diabetes and cholesterol

Optimum glycemic regulation is the keystone of diabetes control. Grounded on the discoveries of early epidemiological study proposing an inverse relationship between fish ingestion and glucose intolerance (Feskens, Bowles, & Kromhout, 1991), ω-3 PUFA supplementation was stated to improve glycemic regulation (Itsiopoulos et al., 2018). However, the relationship between ω-3 PUFA from seafood (i.e., EPA and DHA) sources and danger of type 2 diabetes mellitus (DM) stays unclear (Wu et  al., 2012). Early studies have shown that above 6  weeks, both EPA and DHA headed to a mild deficiency of glycemic regulation in temperately obese type 2 diabetic patients with treated hypertension. However, the most probable elucidation seems to be a rise in hepatic glucose output, even though this was not directly evaluated (Woodman et  al., 2002). In contrast, in a meta-analysis of controlled supplementation trials, ω-3 PUFA supplementation did not provoke larger alterations in biomarkers of glucose-insulin homeostasis in subjects with DM (Friedberg, Janssen, Heine, & Grobbee, 1998; Hartweg et al., 2008; Montori, Farmer, Wollan,

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& Dinneen, 2000). Moreover, a total of 10 cohort studies with three dietary factors (EPA, DHA, and mixed ω-3) were included in a meta-analysis by Bloomer et al. (2009). This study has displayed that the overall effect of total ω-3 fatty acids on the risk of type 2 diabetes was insignificant, as well as the association of mixed ω-3 fatty acids supplementation with type 2 diabetes. In spite of hopeful animal projects, the current clinical sign for the use of ω-3 supplementation for the control of T2DM and related conditions is insufficient and contradictory. Data from current clinical trials do not support the use of ω-3 PUFA for glycemic regulation and there are only few projects in T2DM populations to base the use of ω-3 PUFAs for related difficulties of diabetes. Promising contributors to the inconsistent evidence base are study design issues, such as inappropriate intervention period, sample size, ω-3 supplement dose, modifications in the EPA to DHA ratio, and clinical heterogeneity among diabetic populations (Itsiopoulos et al., 2018). Counterbalancing, there were significant reductions in serum triacylglycerol and significant increments in high-density lipoprotein (HDL) cholesterol with both EPA and DHA (Woodman et al., 2002). The longest duration trial was a crossover study in healthy subjects with low-grade inflammation, which demonstrated that dosages of 2.7 g/day for a period of 10 weeks using EPA and DHA may meaningfully reduce triglycerides (by 12% and 13%, respectively) and increase low-density lipoprotein (LDL) cholesterol (by 2% and 7%, respectively) compared to corn oil (Allaire et al., 2016). In addition, a systematic review by Innes and Calder (2018) concluded that five of the six encompassed projects confirmed a noteworthy triglyceride-lowering result for EPA and DHA when compared to placebo, with reductions varying from 12% to 26% in comparison with the baseline (Innes & Calder, 2018). Moreover, there is some proof that DHA reflects a higher triglyceride-lowering effect in comparison with EPA (Allaire et  al., 2016; Grimsgaard, Bonaa, Hansen, & Nordøy, 1997). Regarding the other lipid parameters, the effect of each individual ω-3 FA was not so clear. EPA presented a dropping effect on HDL cholesterol (Mori et al., 2000; Woodman et al., 2002) and apolipoprotein B (Grimsgaard et al., 1997; Park & Harris, 2003), whereas DHA presented a significant rise in LDL cholesterol (Allaire et al., 2016; Mori et al., 2000) as well as LDL particle size (Mori et al., 2000; Woodman et al., 2002). There exists a proof that DHA has an increasing effect on HDL cholesterol (Allaire et al., 2016; Grimsgaard et al., 1997).

5.2.5 ­Alzheimer's disease

EPA and DHA have also been associated with promising effects in prevention, weight control, and cognitive function in those patients with a very mild Alzheimer's disease (AD). AD patients have displayed a lacking of DHA, and supplementation with EPA and DHA allows to revert this absence, besides improving their cognitive functioning (Swanson et al., 2012). Several studies related to the use of ω-3 FA supplement to improve AD have been conducted. DHA is available in large amounts in neuron membrane phospholipids, where it is involved in suitable function of the nervous system that can be associated with AD (Tully et al., 2003). Moreover, unintentional weight loss is an issue that numerous AD patients might confront, and a

­References

combination of EPA and DHA supplements has had a positive effect on weight gain in these patients (Faxén Irving et al., 2009). Even though data from projects associated with the disease processes of AD appear to be promising, there are contradictory data concerning the use of ω-3 FA in terms of cognitive function. In fact, a work that dealt with DHA supplementation in patients with mild-to-moderate AD concluded that DHA supplementation presented a scarce positive effect on cognition during the 18-month trial period for the DHA group vs placebo (Quinn et al., 2010).

6 ­Conclusions Currently, the valorization of food derivatives to manufacture high value-added goods following the green economy concept is booming. In this sense, the massive production of fish byproducts together with its interesting characteristics makes them very suitable to obtain bioactive lipids that may improve human health and the economic profit of the sector. Additionally, it is essential to set the more appropriate extraction technologies, prioritizing the use of novel eco-friendly ones that enhance the recovery of high-quality bioactive lipids, such as UAE, MAE, or SFE. Eventually, the PUFAs extracted, such as DHA and EPA, can be play a key role in the control and prevention of various diseases, bringing beneficial effects to the human health.

­Acknowledgments The authors acknowledge the financial support received from “Xunta de Galicia” (Project ED431F 2020/03). P.G.d.R. and B.G. express their gratitude to the Ministry of Science, Innovation and Universities of Spain for his FPU research grant (FPU16/04077) and her RYC grant (RYC2018-026177-I), respectively. G.A. thanks the Universidade de Vigo for his contract supported by “Programa de retención de talento investigador da Universidade de Vigo para o 2018.”

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Pingret, D., Fabiano-Tixier, A. S., & Farid, C. (2013). Chapter 3—Ultrasound-assisted Extr. In Natural product extraction: Principles and applications (pp. 89–112). The Royal Society of Chemistry. https://doi.org/10.2212/spr.2009.5.1. Prato, E., & Biandolino, F. (2012). Total lipid content and fatty acid composition of commercially important fish species from the Mediterranean, Mar Grande Sea. Food Chemistry, 131, 1233–1239. https://doi.org/10.1016/j.foodchem.2011.09.110. Quinn, J. F., Raman, R., Thomas, R. G., Yurko-Mauro, K., Nelson, E. B., Van Dyck, C., et al. (2010). Docosahexaenoic acid supplementation and cognitive decline in Alzheimer disease: A randomized trial. JAMA, 304, 1903–1911. https://doi.org/10.1001/jama.2010.1510. Rahimi, M. A., Omar, R., Ethaib, S., Siti Mazlina, M. K., Awang Biak, D. R., & Nor Aisyah, R. (2016). Microwave-assisted extraction of lipid from fish waste. In 29th symposium of Malaysian chemical engineers (SOMChE). IOP conference series: Materials science and engineering. https://doi.org/10.1088/1757-899X/206/1/012096. Rep Health Soc Subj, (Lond). (1994). Nutritional aspects of cardiovascular disease. In Report of the cardiovascular review group committee on medical aspects of food policy no 46. London. Rubio-Rodríguez, N., Beltrán, S., Jaime, I., de Diego, S. M., Sanz, M. T., & Carballido, J. R. (2010). Production of omega-3 polyunsaturated fatty acid concentrates: A review. Innovative Food Science and Emerging Technologies, 11, 1–12. https://doi.org/10.1016/j. ifset.2009.10.006. Rubio-Rodríguez, N., de Diego, S. M., Beltrán, S., Jaime, I., Sanz, M. T., & Rovira, J. (2008). Supercritical fluid extraction of the omega-3 rich oil contained in hake (Merluccius capensis-Merluccius paradoxus) by-products: Study of the influence of process parameters on the extraction yield and oil quality. Journal of Supercritical Fluids, 47, 215–226. https://doi. org/10.1016/j.supflu.2008.07.007. Rubio-Rodríguez, N., De Diego, S. M., Beltrán, S., Jaime, I., Sanz, M. T., & Rovira, J. (2012). Supercritical fluid extraction of fish oil from fish by-products: A comparison with other extraction methods. Journal of Food Engineering, 109, 238–248. https://doi.org/10.1016/j. jfoodeng.2011.10.011. Russo, G. L. (2009). Dietary n − 6 and n − 3 polyunsaturated fatty acids: From biochemistry to clinical implications in cardiovascular prevention. Biochemical Pharmacology, 77, 937– 946. https://doi.org/10.1016/j.bcp.2008.10.020. Schiano, V., Laurenzano, E., Brevetti, G., De Maio, J. I., Lanero, S., Scopacasa, F., et  al. (2008). Omega-3 polyunsaturated fatty acid in peripheral arterial disease: Effect on lipid pattern, disease severity, inflammation profile, and endothelial function. Clinical Nutrition, 27, 241–247. https://doi.org/10.1016/j.clnu.2007.11.007. Schubert, R., Kitz, R., Beermann, C., Rose, M. A., Baer, P. C., Zielen, S., et  al. (2007). Influence of low-dose polyunsaturated fatty acids supplementation on the inflammatory response of healthy adults. Nutrition, 23, 724–730. https://doi.org/10.1016/j.nut.2007.06.012. Serhan, C. N., Chiang, N., & Van Dyke, T. E. (2008). Resolving inflammation: Dual antiinflammatory and pro-resolution lipid mediators. Nature Reviews. Immunology, 8, 349–361. https://doi.org/10.1038/nri2294. Simopoulos, A. P. (2002a). Omega-3 fatty acids in inflammation and autoimmune diseases. Journal of the American College of Nutrition, 21, 495–505. https://doi.org/10.1080/07315 724.2002.10719248. Simopoulos, A. P. (2002b). The importance of the ratio of omega-6/omega-3 essential fatty acids. Biomedicine & Pharmacotherapy, 56, 365–379. https://doi.org/10.1016/ S0753-3322(02)00253-6.

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Smith, G. I., Atherton, P., Reeds, D. N., Mohammed, B. S., Rankin, D., Rennie, M. J., et al. (2011). Dietary omega-3 fatty acid supplementation increases the rate of muscle protein synthesis in older adults: A randomized controlled trial. The American Journal of Clinical Nutrition, 93, 402–412. https://doi.org/10.3945/ajcn.110.005611. Swanson, D., Block, R., & Mousa, S. A. (2012). Omega-3 fatty acids EPA and DHA: Health benefits throughout life. Advances in Nutrition, 3, 1–7. https://doi.org/10.3945/ an.111.000893. Szabó, Z., Marosvölgyi, T., Szabó, É., Bai, P., Figler, M., & Verzár, Z. (2020). The potential beneficial effect of EPA and DHA supplementation managing cytokine storm in coronavirus disease. Frontiers in Physiology. https://doi.org/10.3389/fphys.2020.00752. Tully, A., Roche, H., Doyle, R., Fallon, C., Bruce, I., Lawlor, B., et al. (2003). Low serum cholesteryl ester-docosahexaenoic acid levels in Alzheimer's disease: A case-control study. The British Journal of Nutrition, 89, 483–489. https://doi.org/10.1079/BJN2002804. Týskiewicz, K., Konkol, M., & Rój, E. (2018). The application of supercritical fluid extraction in phenolic compounds isolation from natural plant materials. Molecules, 23, 2625. https:// doi.org/10.3390/molecules23102625. Valenzuela, R., Ortiz, M., Hernández-Rodas, M. C., Videla, F. E., & Videla, L. A. (2020). Targeting n-3 polyunsaturated fatty acids in non-alcoholic fatty liver disease. Current Medicinal Chemistry. https://doi.org/10.2174/0929867326666190410121716. Woodman, R. J., Mori, T. A., Burke, V., Puddey, I. B., Watts, G. F., & Beilin, L. J. (2002). Effects of purified eicosapentaenoic and docosahexaenoic acids on glycemic control, blood pressure, and serum lipids in type 2 diabetic patients with treated hypertension. The American Journal of Clinical Nutrition, 76, 1007–1015. https://doi.org/10.1093/ajcn/76.5.1007. Wu, J. H. Y., Micha, R., Imamura, F., Pan, A., Biggs, M. L., Ajaz, O., et al. (2012). Omega-3 fatty acids and incident type 2 diabetes: A systematic review and meta-analysis. The British Journal of Nutrition, 107l, S214–S227. https://doi.org/10.1017/S0007114512001602. Xiao, L., Ji, Y., Zhaoshuo, Y., Wenjiao, L., Xing, Z., & Chengjin, M. (2017). Ultrasoundassisted extraction of bighead carp viscera oil and its physiochemical properties. Journal of Jishou University (Natural Sciences Edition), 38, 1461–1500. https://doi.org/10.5833/ jjgs.20.1461. Yi, T., Li, S.-M., Fan, J.-Y., Fan, L.-L., Zhang, Z.-F., Luo, P., et  al. (2014). Comparative analysis of EPA and DHA in fish oil nutritional capsules by GC-MS. Lipids in Health and Disease, 13, 190. https://doi.org/10.1186/1476-511X-13-190. Yuan, Y., & Macquarrie, D. J. (2015). Microwave assisted acid hydrolysis of brown seaweed Ascophyllum nodosum for bioethanol production and characterization of alga residue. ACS Sustainable Chemistry & Engineering, 3, 1359–1365. https://doi.org/10.1021/ acssuschemeng.5b00094. Zhu, H., Fan, C., Xu, F., Tian, C., Zhang, F., & Qi, K. (2010). Dietary fish oil n-3 polyunsaturated fatty acids and alpha-linolenic acid differently affect brain accretion of docosahexaenoic acid and expression of desaturases and sterol regulatory element-binding protein 1 in mice. The Journal of Nutritional Biochemistry, 21, 954–960. https://doi.org/10.1016/j. jnutbio.2009.07.011.

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CHAPTER

Encapsulation techniques to increase lipid stability

17

Aurora Cittadinia,b, Paulo Eduardo Sichetti Munekatab, Mirian Pateirob, María V. Sarriésa, Rubén Domínguezb, and José M. Lorenzob,c a

Institute on Innovation and Sustainable Development in Food Chain (IS-FOOD), Public University of Navarre, Pamplona, Spain b Centro Tecnológico de la Carne de Galicia, Ourense, Spain c University of Vigo, Ourense, Spain

­C hapter outline 1 Introduction.......................................................................................................... 414 2  Measurements of effectiveness of encapsulation process........................................ 417 2.1  Encapsulation efficiency...................................................................... 417 2.2 Payload.............................................................................................. 418 2.3  Particle size........................................................................................ 418 2.4 Stability.............................................................................................. 418 2.5  Encapsulation yield.............................................................................. 419 3  Technology for encapsulation of lipids................................................................... 419 3.1 Emulsification..................................................................................... 422 3.2 Spray-drying........................................................................................ 423 3.3 Freeze-drying...................................................................................... 425 3.4 Coacervation....................................................................................... 425 3.5  Fluidized bed coating........................................................................... 427 3.6  Coaxial electrospray system.................................................................. 428 3.7  Ionic gelation...................................................................................... 429 3.8  Supercritical fluid technology............................................................... 430 3.9  Liposome entrapment.......................................................................... 431 4  Shell materials used for lipid encapsulation........................................................... 432 4.1 Carbohydrates..................................................................................... 433 4.2 Proteins.............................................................................................. 434 4.3 Lipids................................................................................................. 435 4.4  Combination of different bio-based materials.......................................... 435 5  Applications of micro/nanoencapsulated oils.......................................................... 436 5.1  Cereals and bakery products................................................................. 444 5.2  Dairy products..................................................................................... 446 5.3  Meat products..................................................................................... 447 Food Lipids. https://doi.org/10.1016/B978-0-12-823371-9.00010-1 Copyright © 2022 Elsevier Inc. All rights reserved.

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6 Conclusions.......................................................................................................... 450 Acknowledgments..................................................................................................... 451 References............................................................................................................... 451

1 ­Introduction Modern consumers have a major awareness of the relationship between diet and health. Actually, there is a growing interest and demand for foods containing bioactive or functional ingredients (such as antioxidants, unsaturated fatty acids, probiotics, vitamins, and minerals), which improve their nutritional value and functionality, also known as functional foods (Chew et al., 2019; Şahin-Yeşilçubuk & Akoh, 2017). In particular, healthy and nutritious oils have recently gained great popularity and scientific interest. In fact, their application in food products is highly requested due to their multifunctional properties and nutritional value (Chew et al., 2019; Mohammed, Tan, Manap, Muhialdin, & Hussin, 2020). Marine and vegetable oils (such as fish oil, olive oil, chia seed oil, flaxseed oil, sunflower oil, and others) are generally characterized by a high content of monounsaturated (MUFAs) and polyunsaturated fatty acids (PUFAs) (as omega-3 and omega-6) and represent an excellent source of essential fatty acids (EFAs), including α-linolenic acid (ALA), eicosapentaenoic acid (EPA), and docosahexaenoic acid among others, that are beneficial for human health (Chew et al., 2019; Kaushik, Dowling, Barrow, & Adhikari, 2015). Furthermore, these oils can provide the desired amount of lipid-soluble bioactive compounds such as tocopherols, phytosterols, carotenoids, and polyphenols with significant antioxidant activity (Chew, Tan, Long, & Nyam, 2016). Nevertheless, due to their high level of unsaturation, these oils are chemically unstable and susceptible to oxidative deterioration, especially when exposed to oxygen, light, moisture and heat, limiting their application. The oxidative degradation can cause the loss of nutritional quality, formation of unpleasant tastes, and undesirable flavors, thereby affecting the stability, sensory properties, and overall acceptability of the oils (Bakry et al., 2016; Şahin-Yeşilçubuk & Akoh, 2017). In addition, multiple toxic compounds are produced during lipid oxidation and can implicate several human pathologies (Domínguez et al., 2019). Thus, the incorporation of oils and fatty acids represents a major challenge to the food industry. It is necessary to protect them in order to improve their stability during handling, processing, and storage (Eratte, Dowling, Barrow, & Adhikari, 2018). In this context, encapsulation technology is an emerging and effective technology able to guarantee the stability of these functional ingredients and allow their application in a variety of food matrices (Chew et al., 2019). Encapsulation consists of a technological process able to incorporate a compound(s) known as active compound or core (solid, liquid or gas) within another substance(s) known as coating wall, wall material or membrane with the formation of very small “packages” (Da Veiga, Aparecida Da Silva-Buzanello, Corso, & Canan, 2019; Franco et al., 2017; Gómez et al., 2018). In this entrapping process, it produces micrometric or nanometric particles called microparticles (from 100 nm to 1000 μm) or nanoparticles ( 20 h) Poor protection of ingredients due to porous coating Time-consuming technique Complex process (require a careful monitoring) Production of chemical residue during processing Low stability for complex coacervates Limit number of shell material available

Yang et al. (2020) and ŞahinYeşilçubuk and Akoh (2017)

Fluidized bed coating

Coaxial electrospray system

Ionic gelation

Supercritical fluid technology

Low cost process Particle size distribution is controllable Time and energy saving Easy to operate Fast Maximum encapsulation efficiency Effective protection of bioactivity Uniform size distribution Time saving Eco-friendly Organic solvent and extreme conditions of pH and temperature are avoided High production capacity High encapsulation efficiency No toxic Easy elimination of the solvent

Liposome entrapment

No permission required.

No degradation of the product Wide variety of materials available Controlled size and morphology Eco-friendly Used for encapsulation of hydrophilic, hydrophobic, and amphiphilic bioactive compounds Deliver encapsulated content to right site at right time (unique targetability) Moderate stability against oxidation Possible preparation with biodegradable, biocompatible and nontoxic components Efficient controlled delivery

Degradation of temperature sensitive active compounds

Alemzadeh et al. (2020), Raza, Khalil, Ayub, and Banat (2020), and Bakry et al. (2016)

Complex process control

Sagiri et al. (2016) and Bakry et al. (2016)

Low stability

Gómez et al. (2018), Suganya and Anuradha (2017), and Comunian and Favaro-Trindade (2016)

Mainly used on a laboratory scale Moderate solubility of substances as a solvent Time-consuming technique (longer washing period)

Sagiri et al. (2016), Bakry et al. (2016), and Fahim et al. (2014)

Expensive materials and high production cost

Raza et al. (2020), de Souza Simões et al. (2017), Ðordević et al. (2016), and McClements (2014)

Time-consuming and complex production process Low loading capacity Fast release Quite limited physical and chemical stability Mainly used on a laboratory scale

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Table 17.1 shows a summary of the advantages and disadvantages of these encapsulation methods.

3.1 ­Emulsification Emulsification technology has a key role in the microencapsulation of oils. It is normally employed for the encapsulation of bioactive compounds (both hydrophobic and hydrophilic) in aqueous solutions, which can either be used completely in a liquid state or can be dried (spray- or freeze-drying) in order to form powders after emulsification. Thus, emulsification constitutes a relevant part of the microencapsulation process (Bakry et al., 2016). Briefly, an emulsion consists of at least two immiscible liquids (as oil and water), where one of them is dispersed as small droplets in the other. Therefore, when a system is composed of oil droplets dispersed in an aqueous phase, it is called an oil-in-water (O/W) emulsion and when water droplets are dispersed in the oil phase, it is known as water-in-oil (W/O) emulsion. In the same manner, multiple emulsions have been developed. The presence of core materials in the first liquid allows the encapsulation of the active part (Alemzadeh et al., 2020). However, emulsifiers or texture modifiers are generally included in emulsions in order to obtain a kinetically stable solution (Bakry et al., 2016). This process is characterized by two phases of transformation and distribution of particles due to the mechanical agitation of oil, water, and emulsifier. Successively, the newly formed phase emulsion is stabilized by the conversion of large particles into smaller particles by colloidal stirring or homogenization (Dehkordi, Alemzadeh, Vaziri, & Vossoughi, 2020). Therefore, the positive points of this technique are its easy preparation and low cost. On the other hand, emulsions are physically unstable when exposed to environmental stressors (heating, chilling, freezing, drying, extreme pH, and high mineral concentrations) and have limited control release (Bakry et al., 2016). In addition, the wide distribution of particles size, the absence of an automated mechanism and the relatively large particle size (between 100 and 200 μm) represents other weaknesses of this technique. Nevertheless, in the last years, nanoemulsions with tiny droplets can be realized owing to the combination of high-energy processes such as high-speed or high-­ pressure homogenization and ultra-sonication (Anandharamakrishnan, 2014). The small droplet size offers nanoemulsion stability avoiding sedimentation and creaming, as well as a transparent or slightly turbid appearance which is appropriate for food applications. In this manner, lipophilic active agents such as EFAs can be encapsulated and delivered by O/W emulsion (Anandharamakrishnan, 2014). The elaboration of nanoemulsion can be grouped into high-energy and low-energy approaches. The former process transforms oils and aqueous components into minute droplets by mechanical tools such as high-pressure homogenizers, sonicators, and micro fluidizers. Whereas, in low energy approaches, nanoemulsions are the results of phase modifications occurring when the environmental conditions are changed during the emulsification process. The maintaining of the droplets into spherical shapes is possible owing to the generation of disruptive forces higher than the restoring forces,

3 ­ Technology for encapsulation of lipids

which requires an elevated energy level (Alemzadeh et al., 2020). In nanoemulsion, the size of droplets are affected by distinct properties such as the design of homogenizer (rotor-stator homogenizer, pressure homogenizer, ultrasonic homogenizer), homogenizer operating conditions (pressure, temperature, the number of passes or cycles, valve and impingement design, flow rate), environmental conditions (temperature), sample composition (oil phase, aqueous phase, surfactant concentration, and/or cosurfactant concentration), as well as, its physicochemical characteristics (Bhavsar, 2011). Thus, effective preparation of a nanoemulsion consists of two main steps: firstly, rotor-stator devices convert the separate oil and water phases into a “coarse emulsion” with nearly large emulsion droplet size (EDS), subsequently, high-pressure systems decrease EDS. However, the obtainment of nanoemulsion with the required EDS involves extremely high pressure and different passes. Droplet sizes are also determined by the disperse-to-continuous viscosity ratio and the use of a suitable emulsifier. Therefore, a reduction in particle size and physical stability can be favored by an increment in homogenization pressure and cycle (Alemzadeh et al., 2020; Bhavsar, 2011).

3.2 ­Spray-drying Spray-drying is one of the oldest and widely used encapsulation techniques in the food industry since it is continuous, easy to operate, flexible, fast, suitable for mass production and, especially an economical process (Şahin-Yeşilçubuk & Akoh, 2017; Yang et al., 2020). It consists of a single-step process in which a liquid product is transformed into a fine powder, a dry and stable form (Alemzadeh et al., 2020). This feature has positive effects from a sensorial standpoint and on the textural characteristics of the final products since these powders can be included in food matrices without changing mouthfeel hugely (Barrow, Wang, Adhikari, & Liu, 2013; Heck et al., 2021). In fact, spray-drying supplies high-quality powders and can preserve difference type of oils against oxidation and environmental deteriorating factors, as light, temperature, and humidity (Geranpour et al., 2020). Encapsulation requires an initial dissolution, emulsification or dispersion of the core substance in an aqueous solution of the carrier material, which is followed by atomization of the mixture into a hot chamber (Anandharamakrishnan, 2014). In particular, the spray-drying process involves four stages (Fig. 17.3): (1) preparation of a dispersion or emulsion; (2) homogenization of the dispersion; (3) atomization of the feed emulsion into little droplets through a heated nozzle within a spray chamber, and (4) dehydration of the atomized particles (Alemzadeh et al., 2020; Şahin-Yeşilçubuk & Akoh, 2017). Thus, spray-drying microencapsulation consists of the atomization of the emulsion of wall and core material in a dry and high-temperature environment, which evaporates the moisture via heat exchange between the drying medium and droplets and solidifies the wall of the droplet rapidly to wrap and protect the core material. This method normally obtains high EE due to its capability to reduce the quantity of surface oil and subsequently increasing the EE (Bakry et  al., 2016; Geranpour et  al., 2020). Nevertheless, this technique has some limitations. In fact, during the preparation

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FIG. 17.3 Representation of the microencapsulation process by spray-drying: (1) oils are mixed with shell material by agitation; (2) homogenization of the feed solution; (3) solution is pumped and atomized into droplets through a heated nozzle. Droplets are dried by the hot air in the drying chamber; (4) then, particles are collected by a cyclone in a collection vessel. Yellow arrows (gray in print version) show the flow of particles in the device; Red arrows (black in print version) show the drying gas in the device, and the blue (light gray in print version) ones the exhausting dry (out) gas. No permission required.

process, the core material is exposed to high-temperature airflow, where temperature sensitive compounds can be easily inactivated (Bakry et  al., 2016). Moreover, the wall materials required by this method should be water-soluble, with low v­ iscosity and with good fluidity, so there is a limited number of shell materials available, such as gum Arabic and modified starch, limiting its application (Bakry et al., 2016; Yang et al., 2020). Furthermore, the obtained fine microcapsule powder may require further processing since low water evaporation can cause agglomeration or hardening, whereas excessive water evaporation can damage the wall material and reduced compactness (Bakry et al., 2016; Yang et al., 2020). In addition, for this technology,

3 ­ Technology for encapsulation of lipids

the control of particle size is complicated and it can be solved by adjusting process formulation and parameters (Anandharamakrishnan, 2014). Hence, spray-drying can be combined with other technologies such as agglomeration or fluid bed coating, granulation or multicore encapsulation and coating, in order to overcome some of the abovementioned problems (Dyvelkov & Sloth, 2014).

3.3 ­Freeze-drying Freeze-drying, also called lyophilization or cryodesiccation, is a simple process and is used for the dehydration of thermosensitive materials and aromas (Bakry et al., 2016; Şahin-Yeşilçubuk & Akoh, 2017). This method employs low temperature and consists of freezing the samples followed by vacuum dehydration (elimination of ice by sublimation) until the creation of stable freeze-dried material. This process is suitable for oils rich in omega-3 PUFAs, allowing the preservation of their nutritional quality since it can be carried out at low temperatures (Heck et al., 2021). In particular, this method supplies a stable (in dry form), rapidly soluble (large surface area), and elegant (uniformly colored) product. This process includes five phases, namely: (1) Freezing. The substance is frozen until the formation of crystallized size. Many components can remain in an amorphous state and do not crystallize; however, the water component crystallizes. (2) Primary drying. Ice removal occurs by sublimation at low temperatures and pressure. This step happens between the dry and frozen material and gives rise to the ice surface. (3) Secondary drying. Unfrozen water is removed by desorption. This phase normally requires one-third of the drying period. The final moisture content for foodstuffs is about 2%–10% while it is 0.1%–3% for biological products. (4) Final treatment. The drying chamber is charged with an inert gas (nitrogen for foodstuffs, argon for biological products) in order to conserve the products after the dehydration (Anandharamakrishnan, 2014; Şahin-Yeşilçubuk & Akoh, 2017). (5) Milling to obtain the powdered product. In the case of oils, before these steps, oils are dissolved in water. This process generates high-quality products and seems to have the maximum retention of volatile compounds compared with spray-drying. In addition, besides allowing the stability of heat-sensitive materials, this process is simple and easy to carry out, and freeze-dried samples are more resistant to oxidation. On the other hand, this technique presents some drawbacks including high-energy use, long processing time (> 20 h), and high production costs. In addition, materials submitted to this treatment may have higher porosity, exposing the core material to the surrounding environment (Bakry et al., 2016; Şahin-Yeşilçubuk & Akoh, 2017).

3.4 ­Coacervation Coacervation is one of the oldest and most commonly used encapsulation techniques. The principle of this technology is phase separation, for this reason it is frequently called “phase separation” and is normally described as the separation of two liquid phases in a colloidal system (Şahin-Yeşilçubuk & Akoh, 2017). Actually, coacervation consists of a gradual desolvation of a homogeneous polymer solution

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into two phases, coacervate (polymer-rich phase) and coacervation medium or equilibrium solution (polymer-poor phase) (Sagiri et al., 2016; Timilsena et al., 2020). This process is possible when the surface energy of the core and wall materials are ­adjusted through the modification of some system parameters such as temperature, pH or composition. Subsequently, the coating material is solidified by means of heat, crosslinking, or solvent removal techniques. The obtained microcapsules are generally gathered by filtration or centrifugation, being washing in a proper solvent, and are successively dried by some standard techniques such as spray-drying, freeze-­ drying, or fluidized bed-drying in order to obtain free-flowing and separate particles (Alemzadeh et al., 2020). Briefly, the coacervation process is the following: firstly, the polymer (1%–10%) is dissolved and the core material (oil) is dispersed in water at 40–50°C; secondly, the liquid polymer (the coating) is deposited upon the core material; and thirdly, the coating is stabilized and hardened to form microcapsules (Rodríguez, Martín, Ruiz, & Clares, 2016). This method can be classified into two categories: simple coacervation and complex coacervation. They follow the same mechanism of microencapsulation, except for the way in which the phase separation is carried out (Timilsena et al., 2020). In fact, in simple coacervation, there is only one polymer. In this method, the polymer is salted out by the activity of electrolytes (as sodium sulfate), or desolvated by the use of a water-miscible nonsolvent (as ethanol), or by increasing/decreasing the temperature. These conditions promote macromolecule-macromolecule interactions. This process allows the production of microcapsules including hydrophobic substances, such as vegetables, marine and essential oils. Simple coacervation presents relevant advantages compared with complex coacervation since it is characterized by costsaving and flexible operations. Therefore, simple coacervation employs inexpensive inorganic salts to induce phase separation. On the other hand, complex coacervation implicates the interaction of two oppositely charged polymers, usually proteins and polysaccharides. This process consists of three basic steps. Firstly, three immiscible phases are formed consisting of the core material, wall material, and liquid vehicle. The core material is generally dispersed in a solution of coating polymeric material. The coating material is made immiscible either by adding desolvating agent or salt, producing polymer-polymer interactions, or modifying the temperature of the polymer solution or incompatible polymer. Secondly, the liquid polymer is formed and deposited on the core material. Finally, the third step consists of the stabilization of microcapsules by cross-­linking, desolvation or thermal treatment. In general, protein-polysaccharide complexes are employed in complex coacervation, such as gelatin-pectin, whey protein-gum Arabic, gelatin-acacia gum, among others (Sagiri et  al., 2016). Complex coacervation is one of the commercially successful methods employed to encapsulate temperature-­sensitive compounds and fat-soluble food ingredients, as oils rich in omega-3 PUFAs and flavor oils (Ðordević et al., 2016; Raza et al., 2020). In addition, it reports different benefits since it does not require special equipment, works with mild process conditions, and as there is only small damage to core quality it is characterized by higher product encapsulation efficiency, as well as a better ­antioxidant

3 ­ Technology for encapsulation of lipids

and release c­ ontrolling properties (Yang et  al., 2020). Moreover, this method has the main advantage of producing microcapsules with smaller particles ranging from about 1–1000 μm (Kaushik et al., 2015). Nevertheless, complex coacervation presents some limits, in fact, it has a high cost, uses quite expensive materials, is complicate to control the conditions of its reaction, and produces easily chemical residue during processing. It is considered time-consuming since it works as a batch and needs an extra step to enable crosslinking of protein. In addition, coacervates formed are stable only on a very narrow range of pH and ionic strength, reaching the correct endpoint before crosslinking, requiring careful monitoring even at production levels. Another disadvantage of this process is related to the wall materials. Gelatin is commonly used as a coating agent (as a positively charged polymer) but animal-derived gelatin is not acceptable to the vegetarian population or can be a problem for patients that have alimentary restrictions (Kaushik et al., 2015; Rodríguez et al., 2016). Fish gelatin can be used as a substitute for animal-based gelatin, however, it is high-priced and the raw material for its production is limited (Kaushik et al., 2015). Thus, considering the aforementioned drawbacks associated with pork and fish gelatins, it is worth noting that it is necessary to find alternative coacervating agents that can provide high payload, structural strength, and oxidative stability (Kaushik et al., 2015; Şahin-Yeşilçubuk & Akoh, 2017). Microcapsules obtained by coacervation can be classified into mononuclear (single core—single oil droplet surrounded by the shell) and multinuclear (multicore—multiple oil droplets surrounded by a common shell). However, the shape and size of cells are influenced by both the methods employed for the emulsion formation and the material-based parameters, such as the typology of polymers, their molecular weight, charge density, concentration, and their ratio. In the same way, the cells’ size and shape depend on process-based parameters at temperatures, pH, cooling, and solidification levels. Hence, considering the interdependence of the abovementioned factors, optimization of this method is extremely challenging. Thus, this technique is still at the experimental stage and has not been widely applied in the food industry owing to its shortcomings. Nevertheless, it is still a technique with great potential due to its great release control ability (Yang et al., 2020).

3.5 ­Fluidized bed coating Fluidized bed coating is one of the most efficient coating methods and is arousing growing interest in the food and pharmaceutical sectors. This process is considered energy-saving and has the advantage to reduce the material handling and processing times compared to the other wet granulation technique. Actually, in this method, ingredients can be mixed, granulated, and dried in the same vessel. This method is also called “air suspension coating” or “spray coating.” In this technique, the solid particles of the core material are initially suspended in an air stream under controlled temperature and humidity, subsequently, they are covered by spraying the liquid wall

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material. The coating material gradually solidifies and forms a layer on the surface of the suspended particles (Alemzadeh et al., 2020; Bakry et al., 2016). This method can be accomplished in three ways: top-spray, bottom-spray, and tangential-spray. The bottom- and top-spray are the most widely used methods. In the top-spray system, the wall solution is sprayed counter currently descending on the fluid bed. In this way, when the solid or porous particles move to the coating zone, they are microencapsulated. The opposite flows of the core and coating materials provide increased encapsulation efficiency and prevent cluster formation. This method allows to obtain small microcapsules ranging between 2 and 100 μm and produces higher yields of encapsulation than the other two coating systems as abovementioned. Hence, top-spray is considered a promising method and with a high possibility of success in the food industry owing to its excellent versatility, high size of the bed, and relative simplicity (Alemzadeh et al., 2020; Bakry et al., 2016). The bottom-spray consists of a coating chamber provided with a cylindrical stainless-steel nozzle and a cribriform bottom plate. The coating material is sprayed by the nozzle during the process. Whereas, particles move from the bottom to the top through the bottom plate and pass the nozzle zone and are microencapsulated by the coating material, which adheres to the microcapsules’ surface by the cooling of the particles or evaporation of the solvent. This process continues up to the point the desired thickness and weight are achieved. Although it is a time-consuming process, this multilayer coating system reduces particle defects and is widely used for coating particles as small as 100 μm (Bakry et al., 2016). Nevertheless, this technique is normally employed to form a secondary coating on primarily encapsulated products in order to increase stability (Timilsena et  al., 2020). On the other hand, it is not suitable for thermos-sensitive compounds, since it can cause their degradation (Raza et al., 2020).

3.6 ­Coaxial electrospray system The coaxial electrospray system represents an innovative technology used to encapsulate oils for food, cosmetics, and pharmaceutical industries (Bakry et  al., 2016). Actually, this method could be a good alternative to the common encapsulation methods used for oils as spray-drying or coacervation. These methods require the application of mechanical forces, chemical reagents, and thermal treatment, which can cause polymer deterioration. Moreover, these methods generally produce micro/nanoparticles with broad size distribution and can present a reduced encapsulation efficiency due to the presence of multiple steps in each process (Sagiri et al., 2016). Thus, the limitations related to these processes has led to the fabrication of the electrospray method. Previously, this technique was born as single-axial electrospray, where a single liquid was sprayed in the drying chamber under the influence of an electrical field. Successively, technical advancements allowed the design of a 2-phase coaxial electrospray system. During coaxial electrospray, outer and inner solutions are coaxially and simultaneously sprayed through two separate feeding

3 ­ Technology for encapsulation of lipids

channels into one nozzle under the influence of an electrical field. The resultant electrical shear stress extends the shell (polymer) liquid and core (oil) liquid on the top of the spray needle forming an inverted triangle shape or “Taylor cone” and the outer polymeric solution encapsulates the inner liquid. At the end of the cone, the liquid is broken into droplets by Coulomb repulsion. Thus, this method is characterized by positive features, actually, it is easy, rapid, and efficient with maximum retention of the core material achieving the maximum encapsulation efficiency with precise control over the core-shell geometry (Bakry et al., 2016; Sagiri et al., 2016). Encapsulated particles obtained by this technique have uniform size distribution, are homogeneous and nanometer in size. Moreover, it does not require additional reaction solvent and could be realized in one step (time-saving) and it is eco-friendly. On the other hand, in this method, the process control is enough complicated (Bakry et al., 2016; Sagiri et al., 2016; Yang et al., 2020).

3.7 ­Ionic gelation Ionic gelation or ionotropic gelation by extrusion procedures generate core-shell particles, depending on nozzle design. These encapsulation methods possess high production capacity and encapsulation efficiency and are continuous. Normally, the most popular extrusion process employs alginate as coating material and depends on the gelification ability of this polymer in the presence of ionic calcium, without requiring heating. This method is realized using mild conditions at lower temperatures with vigorous stirring or organic solvents. Thus, this encapsulation technique could be suitable for omega-3 rich oils and other sensitive substances owing to the mild process conditions required. Nevertheless, considering lipid encapsulation, there is a limited number of studies about the encapsulation of omega-3 fatty acids using this technique. It could be explained by the fact that the shell materials used, as alginate and carrageen, do not have surface properties and are hydrophilic materials. Therefore, for the encapsulation of hydrophobic materials, the addition of an emulsifier is necessary to prepare an emulsion before the gelation process. Hence, this method, which is mainly used on a laboratory scale, could be considered an innovative and emerging technique, which provides an interesting field for future investigations and applications in the food industry (Comunian & Favaro-Trindade, 2016; Gómez et al., 2018; Suganya & Anuradha, 2017). In particular, it is characterized by two gelling techniques: external and internal gelation. In external ionic gelation, soluble calcium salt is included in the emulsion, particle size is complicated to control, and particles are prone to coagulate in large masses before obtaining consistency (Gómez et al., 2018). This method can be used to produce microparticles resistant to higher temperatures using alginate as coating material (Onwulata, 2013) and allows the controlled release of active compounds in the human intestine (Soliman, El-Moghazy, Mohy El-Din, & Massoud, 2013). Conversely, internal gelation consists of the release of calcium ions from an insoluble complex in a sodium alginate solution. This method is realized by the acidification of a soluble oil-acid system, including alginate in the aqueous phase. Thus, normally,

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the oil phase is added to the aqueous phase, composed of alginate and calcium carbonate (Gómez et  al., 2018). Nevertheless, hydrophilic and low-molecular-weight materials can easily diffuse and can be quickly released through the ionic-gel network despite the surrounding pH (Kim, Lee, & Lee, 2016). The main drawbacks of this method are the low stability and large size of particles. On the other hand, the low polydispersity and the high encapsulation efficiency represent some positive points of this technique.

3.8 ­Supercritical fluid technology Supercritical fluid technology emerged in order to minimize and overcome the weaknesses related to the traditional encapsulation methods. Actually, this technique is characterized by relevant advantages: nontoxicity, easy elimination of the solvent, no degradation of the product, use of a large variety of materials producing controlled particle sizes and morphologies (Bakry et al., 2016). In addition, it can be defined as an eco-friendly approach, where supercritical carbon dioxide (sc-CO2) is generally employed as a green solvent. Sc-CO2 has a lower viscosity, higher diffusivity, lower surface tension, faster process, and high solubility than the active compound. This technique is also known as supercritical solvent impregnation and it has been confirmed to be successful in the encapsulation of oil, fragrances, pharmaceutical ingredients, among others (Sagiri et al., 2016). The supercritical impregnation system is composed of a high-pressure stainless steel impregnation cell, a magnetic stirrer plate, a temperature-controlled water bath, a high-pressure CO2 pump, and a pressure transducer. The impregnation cell contains two chambers divided by a mesh. The lower chamber is loaded with the core material (oil) and the upper chamber is loaded with microparticles or materials in which the oil needs to be impregnated. During the process, the cell is immersed in a water bath (40–50°C) and CO2 is pumped into the cell after achieving the desired temperature. For better impregnation, homogenization is used by a magnetic stirrer. After an impregnation time (about 2 h), the system is depressurized after reducing the temperature of the water bath (~ 10°C). At lower temperatures, the dissolving of oil in sc-CO2 can be reduced. Slow depressurization is preferred over fast depressurization. After depressurizing, the oil-impregnated microparticles are collected (Sagiri et  al., 2016). However, the application of this method is limited in food products due to the moderate solubility of substances as fats, vegetable oils, and vitamin with sc-CO2 as a solvent. However, different methods have been developed. In particular, sc-CO2 antisolvent process is suggested for the abovementioned insoluble compounds (Gómez et al., 2018). The supercritical antisolvent technique is a promising method since carbon dioxide (CO2) is nontoxic, nonflammable, nonpolluting, and relatively cheap. In addition, its critical state of temperature (Tc = 31.1°C) and pressure (Pc = 7.3 MPa) are easily accessible in practical applications. Supercritical antisolvent processes consist of the solution of the solutes into a conventional liquid solvent using supercritical fluid. The sc-CO2 saturates the liquid solvent resulting in the precipitation of solute by an

3 ­ Technology for encapsulation of lipids

antisolvent effect. This process includes relevant strength points as the control of the particle morphology on a very wide range from nanoparticles to microparticles. Supercritical antisolvent is adaptable to continuous processing which is important for large-scale production of micro/nanosized particles. Freshly precipitated particles can easily be gathered from the high-pressure vessel and the supercritical fluid can be drained continuously from the system. On the other hand, the weaknesses of these processes are the longer washing period due to agglomeration and accumulation of the particles in the nozzle (Fahim et al., 2014).

3.9 ­Liposome entrapment Liposomes are spherical vesicles composed of a membrane-like phospholipid bilayer surrounded by an aqueous medium. This delivery system is composed of a combination between surfactants and water, under low shear forces. Nanoliposome technology is a nanoencapsulation method widely employed for the encapsulation and delivery of bioactive agents. Nanoliposomes (d  100 nm) owing to their smaller diameters. In this technique, phospholipids are the fundamental materials employed as coating agents. Liposomal systems possess regions with different polarities, so they can be used to entrap hydrophilic, hydrophobic, and amphiphilic bioactive compounds. Thus, these systems can be considered suitable carriers to be applied to food products (Anandharamakrishnan, 2014; Đorđević et  al., 2014). Shariat, Hakimzadeh, and Pardakhty (2020) have recently reported that liposomes in micro/nanoscale could be employed to encapsulate and protect omega-3 PUFAs for the production of functional foods with appropriate organoleptic properties. According to the literature, the oil encapsulated in the liposome is enough stable against oxidation, since this delivery structure are able to the encapsulated material against changes in the environment (temperature, moisture, pH, ionic strength) during processing and storage (Ðordević et al., 2016). This technique has enormously attracted the attention of scientists and food technologists, due to its outstanding characteristics. In fact, its delivery systems are characterized by their singular targetability, making them attractive both in the pharmaceutical and food fields. Furthermore, the implementation of these carriers in food products is faster and easier since liposomes can be prepared using natural ingredients (biodegradable, biocompatible, and nontoxic), overcoming all the regulatory limitations (Ðordević et  al., 2016). However, the raw materials employed are rather expensive and these liposomal systems have high production costs (Raza et  al., 2020). Furthermore, these delivery systems are characterized by a low loading capacity (is challenging to incorporate high amounts of bioactive components), fast release, and relatively high physical and chemical instability. These carriers, in fact, are prone to breakdown during storage, mostly when exposed to extreme conditions, such as acidic conditions, high salt concentrations, and high temperature. Besides, most of the methods employed for the elaboration of liposomes require a large time and are complex. Thus, the drawbacks

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of this technique limit its application in the food industry and for this, it is generally used on a laboratory scale (de Souza Simões et al., 2017; Ðordević et al., 2016; McClements, 2014).

4 ­Shell materials used for lipid encapsulation Core materials to be coated may be either in liquid or solid form. The liquid component may be dispersed or dissolved, whereas the solid core may include a mixture of active ingredients, stabilizers and solvents (Raza et al., 2020; Şahin-Yeşilçubuk & Akoh, 2017). The addition of natural antioxidants, such as essential oils, into the core material, represents an emerging trend. This procedure occurs previously in the encapsulation process and it was designed to prolong the core stability and to reinforce the effect of the successive encapsulation (Heck et al., 2018; Sharma, Cheng, Bhattacharya, & Chakkaravarthi, 2019). As aforementioned, the objective of wall materials is to protect the core from external stressors, such as harsh temperature changes, oxygen or moisture permeation during processing and storage (Geranpour et al., 2020; Yang et al., 2020). Hence, before selecting an encapsulation carrier, it is essential to consider some aspects such as bioactive compound properties, nature of the food matrix in which it will be incorporated, functionality that the coating material should provide to the final product, possible restrictions for the wall material, the concentration of encapsulates, the desired type of release, and stability requirements. Thus, the selection of encapsulating agents requires an accurate understanding of the physicochemical and rheological properties of both the shell and core material, since it may have a decisive effect on the functional properties of the final encapsulated product and it is at the base of a successful product development (Ðordević et al., 2016; Raza et al., 2020). It is evident that wall material has a key role in the oil encapsulation stability and protection efficiency of the core material (Mohammed et al., 2020). Therefore, the choice of coating material depends on physicochemical features such as solubility, toxicity, molecular weight, film-forming capacity, emulsifying properties, and availability in the market. Coating material corresponds to 1%–80% of the microcapsule by weight and an ideal wall material should possess the following characteristics: low viscosity at high concentration; low hygroscopy to prevent agglomeration problem and to favor its manipulation; ability to stabilize the core material in an emulsion forming a continuous film; favorable covering (filmforming) features such as strength, stability, flexibility, and impermeability; nonreactive with the core material; high solubility in aqueous media or solvent; to provide maximum protection to the core compounds; controlled release under specific conditions; absence of taste and flavor; to be available with a reasonable price; and, finally to be food-grade and biodegradable. Actually, from a health and safety standpoint, encapsulating carriers have to be approved as “generally recognized as safe” (GRAS) materials for food application and biodegradable by governmental organizations. Although different materials can satisfy these requisites, there is a limited number of food-grade wall materials (Franco et al., 2017; McClements, 2014; Shishir, Xie,

4 ­ Shell materials used for lipid encapsulation

Sun, Zheng, & Chen, 2018). In general, for lipid encapsulation, these coating agents are biopolymeric materials, which can be divided into three main groups of carbohydrates, proteins, and lipids. (Geranpour et al., 2020; Mohammed et al., 2020; Timilsena et  al., 2020). The first two groups are the most commonly employed, while the third group is normally used for encapsulation techniques as emulsion and liposome systems (Geranpour et al., 2020). However, the ensuing sections provide more detailed information about the coating materials most frequently used.

4.1 ­Carbohydrates Carbohydrates derive from three subgroups of sources: plant-based, including cellulose, maltodextrin, starch, gum Arabic, guar gum, galactomannans, corn syrup, cyclodextrins, pectin, among others; marine-based, such as carrageenan, alginate, sodium alginate; microbial, and animal-based, as chitosan, lactose, xanthan, gellan, dextran. This class of wall materials stands out for remarkable qualities, as abundant availability, bland flavor, excellent water solubility, low viscosity at high concentration, remarkable core protection ability, nontoxicity, biodegradability, bioadhesibility, and low cost. Among them, gum Arabic and maltodextrin represent some of the most commonly used materials (Geranpour et al., 2020). Gums are polysaccharide polymers that can be employed as an emulsifier, stabilizer, and thickener owing to their hydrocolloid attributes, which enable their application as wall materials (Raeisi, Ojagh, Pourashouri, Salaün, & Quek, 2021). Gum Acacia, known as gum Arabic (GA), has relevant functional properties as an emulsifier, flavoring agent, humectant, thickener, odorless and tasteless material, and surface-finishing agent. It is the most used gum in encapsulation technology. Several studies have reported the employ of GA for the encapsulation of oils, such as fish oil (dos Vaucher et al., 2019), echium oil (Comunian et al., 2019) and palm fiber oil (Carmona et al., 2018). However, its usage as sole material is restricted due to its high cost and limited availability. Maltodextrins are starch hydrolysates and are very popular in food processing since they are inexpensive, nutritious, with a neutral aroma and taste, highly soluble, low viscosity, and provide good flavor protection against oxidation. Moreover, this shell material provides structural integrity to the final product and is characterized by excellent thermal resistance and film formation properties. Nowadays, maltodextrin is commonly mixed with gum Arabic and employs for oil encapsulation (Ðordević et al., 2016; Mohammed et al., 2020). Actually, gum Arabic, owing to its limitations, is normally blended with other shell materials, such as maltodextrin, in order to reduce the cost of encapsulating oils and flavors (Comunian & Favaro-Trindade, 2016; Mohammed et  al., 2020; Timilsena et al., 2020). This mixture was used by different authors for the encapsulation of lipid compounds as sour cherry oil (Başyiğit, Sağlam, Kandemir, Karaaslan, & Karaaslan, 2020), squash seed oil (Pino, Sosa-Moguel, Sauri-Duch, & Cuevas-Glory, 2019), grape seed oil (Böger, Georgetti, & Kurozawa, 2018), Nigella sativa oil (Edris, Kalemba, Adamiec, & Piątkowski, 2016), and pepper seed oil (Karaaslan et al., 2021).

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Moreover, recent studies have been conducted using other carbohydrates-based wall materials for oil encapsulation such as chitosan (Akbari-Alavijeh, Shaddel, & Jafari, 2020; Haider, Majeed, Williams, Safdar, & Zhong, 2017; Raza et al., 2020), alginate (Bannikova, Evteev, Pankin, Evdokimov, & Kasapis, 2018; Martins, Poncelet, Rodrigues, & Renard, 2017; Wang, Waterhouse, & Sun-Waterhouse, 2013), ­cellulose (Karim et  al., 2017), and cyclodextrins (dos Santos, Buera, & Mazzobre, 2017). These materials are under study for different use in the food sector and can be applied to isolates or blended with other polysaccharide coating agents (Chang et al., 2020).

4.2 ­Proteins Proteins can be organized according to their biological origin: plant-based, comprising soy protein, pea protein, barley protein, zein, gluten, among others; animal-based, such as whey protein, casein, gelatin, albumin. Proteins possess superior physicochemical and functional features including biocompatibility, excellent emulsifying capacity, gel and fil forming properties, molecule chain flexibility, and biodegradability (Geranpour et al., 2020; Timilsena et al., 2020). Gelatin is a hydrocolloid widely used in the food industry to manufacture highly stable soft gels of omega-3 fatty acids and oils using techniques as spray-drying and complex coacervation (Devi, Hazarika, Deka, & Kakati, 2012; Wang, Adhikari, & Barrow, 2014). However, milk proteins, in particular, whey protein and sodium caseinate, represent the most commonly used materials and they have been widely studied as oil encapsulating agents owing to their amphiphilic characteristics, the presence of a hydrophilic group and a hydrophobic group, as well as their high diffusivity, which allows a better distribution around the enclosed oil surface (Mohammed et al., 2020). Some authors (Timilsena et al., 2020) reported that whey proteins possess a major encapsulation efficiency (up to 89.6%) over other proteins. Whereas sodium caseinate has been described as the most effective emulsion stabilizer for fats (Mohammed et al., 2020). Actually, recent studies showed the application of these shell materials for lipid encapsulation and their effectiveness as lipid coating materials (Chang & Nickerson, 2018; Hosseini, Ghorbani, Jafari, & Sadeghi Mahoonak, 2019). Plant-based proteins have been the object of study for oil and fatty acids encapsulation. Soy protein represents an inexpensive and high available material, which was employed for lipid encapsulation (Quintero, Rojas, & Ciro, 2018). Actually, recent studies described the use of soy protein for the encapsulation of fish oil (Di Giorgio, Salgado, & Mauri, 2019) and chia oil (Ganañ, Bordón, Ribotta, & González, 2020). Furthermore, pea protein was investigated and used as encapsulating agent. Bajaj, Tang, and Sablani (2015) described the use of pea protein as a novel coating material for flaxseed oil encapsulation. This class of proteins are considered cheaper and more available than animal-based proteins. Nevertheless, although proteins possess excellent functional features, this group of polymers presents an important drawback, their allergenicity (Geranpour et al., 2020). Soy proteins, wheat protein, and peanut proteins are reported to be allergenic to a large number of individuals. In addition, proteins of animal origin can

4 ­ Shell materials used for lipid encapsulation

be ­restricted by diet limitations and religions. These factors, not only limits their application but also requires manufacturer declaration of their presence on the label of the final product. Furthermore, proteins are sensitive to structural changes and their effectiveness as shell materials is greatly dependent on factors such as pH, ionic strength, and temperature of the emulsions or solutions (Timilsena et al., 2020).

4.3 ­Lipids Lipids include compounds such as phospholipids, milk fat, waxes, mono, and diglycerides. Their microstructural features, colloidal stability, as well as rheological and moisture barrier properties, depend on their physicochemical characteristics (de Souza Simões et al., 2017). Lipid-based coating materials present some positive qualities as the ability to entrap and retain materials with different solubility, mainly those highly hydrophobic, protecting bioactive ingredients from chemical and biological deterioration and providing stability during the storage. Furthermore, they may enhance the encapsulation efficiency of hydrophobic core ingredients, such as oil and fatty acids, thus increasing its bioavailability and reducing its potential toxicity (Anandharamakrishnan, 2014). Phospholipids are considered the most effective emulsifiers owing to their structure, glycerol attached to two fatty acids (hydrophobic) and phosphoric acid (hydrophilic). Among them, lecithin represents one of the most widely and practical emulsifiers employed in the food industry (Barrow et al., 2013; Feizollahi, Hadian, & Honarvar, 2018). Encina et al. (2018) showed in fact that lecithin enhances the fish oil stability and encapsulation efficiency when incorporated as an emulsifier in ethanol spray-drying. Lipid-based encapsulation technology represents an emerging and promising field and it is arousing interest as means of delivering bioactive compounds. The most common systems consist of nanoemulsions, nanoliposomes, solid lipid nanoparticles, and nanostructure lipid carriers (Timilsena et al., 2020).

4.4 ­Combination of different bio-based materials Combinations of different materials are generally employed since a single coating agent could not meet all the ideal features required for an encapsulating material. As commented above, each singular compound or group of materials could present certain weaknesses, thus the appropriate combination of two or more agents (as proteins, polysaccharides, lipids, and other materials) may improve the properties of micro- and nanodelivery systems in terms of mechanical, thermal, and barrier resistance, encapsulation efficiency, ameliorated stability, and bioavailability of bioactive compounds, and droplet size distribution for the emulsions (de Souza Simões et  al., 2017; Mohammed et  al., 2020; Shamaei, Seiiedlou, Aghbashlo, Tsotsas, & Kharaghani, 2017). The combination of proteins and polysaccharides has been widely reported in the literature by several authors for successful encapsulation of oils and fatty acids (Can Karaca, 2020; Comunian, Grassmann Roschel, da Silva Anthero, de Castro, & Dupas

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Hubinger, 2020; Cortés-Morales, Mendez-Montealvo, & Velazquez, 2021; Karrar et  al., 2021; Mohammed, Tan, Manap, Alhelli, & Hussin, 2017; Quispe, Chaves, Santos, Bastos, & Castro, 2020; Yildiz et al., 2018). In fact, researchers demonstrated that blending proteins with carbohydrate-based biopolymers represents a promising method to improve their encapsulating properties and to minimize the environmental effect on their functionality as encapsulating compounds. Actually, the protein ­portion possesses high nutritional properties and acts as an exceptional emulsifier, while carbohydrates present high stability and behave as the matrix-forming material (de Souza Simões et al., 2017; Mohammed et al., 2020; Timilsena et al., 2020).

5 ­Applications of micro/nanoencapsulated oils Nowadays, the perception of food as a “medicine” is widely shared among consumers. In this sense, there has been an increased request and consumption of healthy foods and functional products. Several researches have confirmed the fact that nutrients and bioactive compounds found in food can represent an exceptional source for the development of innovative food products in order to enhance the health and wellbeing of consumers (Gullón et al., 2020; López-Pedrouso et al., 2020). In this context, the enrichment and fortification of food products with functional ingredients, as healthy oils and its valuable omega-3 and omega-6 PUFAs, has been arousing great interest, due to the beneficial health effects of these fatty acids (Şahin-Yeşilçubuk & Akoh, 2017). Thus, the food sector is currently in continuous growth and development in order to find effective technology and formulations that allow obtaining innovative and healthy food products that meet consumers’ demands. Encapsulation is acquiring a leading position in the food industry owing to its wide application for food fortification and elaboration of functional foods (Feizollahi et al., 2018; Geranpour et al., 2020; Heck et al., 2021; Mohammed et al., 2020). In particular, considering its successful use for entrapping healthy oils and their valuable components, this technique is considered a promising solution to overcome the problems normally related to these sensitive ingredients. Indeed, the addition of bioactive compounds in food formulations can provide different health benefits, but their pure form is chemically unstable and sensitive to oxidative deterioration (Delshadi, Bahrami, Tafti, Barba, & Williams, 2020). The use of their free forms can also face more barriers such as their low solubility, fast release, and reduced bioavailability. In this regard, encapsulation technology is able to protect and preserve the bioactive compounds against adverse environmental conditions, significantly improving their physicochemical functionalities and health-promoting activities, allowing their successful applications in food products (Delshadi et al., 2020). A wide range of marine, vegetable, and seed oils have been used in food manufacturing to obtain functional food products with stable properties in the final product. Nevertheless, different factors are fundamental to consider for optimizing the oxidative stability of enriched foods: the quality of the oil, composition and quality of the other ingredients, emulsifier, emulsification conditions, type of equipment, and emulsion delivery system

Table 17.2  Recent studies on the fortification of food products with encapsulated oils. Food category

Encapsulated oil

Technique of encapsulation

Product

Results

References

Cereals and bakery products

Chia oil

Soybean protein isolate

Freeze-drying

Pasta

González et al. (2021)

Chia oil

SC and carnauba wax

Freeze-drying

Cookies

Chia oil

Soy protein isolated

Freeze-drying

Bread

Any significant changes in cooking parameters. Oxidative stability during the storage period (150 days) Improvement of nutritional profile, significant ↓ of SFAs and MUFAs, remarkable ↑ of PUFAs (mainly αlinolenic acid), ↓ of AI and TI indices and ↑ H/h ratio Cookies with 30% wt substitution presented the highest storage color stability Good acceptability for the sample with 15% wt margarine substitution Oxidative stability, in alteration of the technological quality of breads and consumers preference (95% of purchase intention was obtained) Low protection and instability of EFAs contents with a significant reduction of α-linolenic acid content during storage (14 days) A ratio of encapsulated oilcontaining bread contributes 60% of the recommended dietary intake of omega-3 PUFAs

Wall materials

Venturini et al. (2019)

González, Martínez, León, and Ribotta (2018)

Continued

Table 17.2  Recent studies on the fortification of food products with encapsulated oils—cont’d Food category

Encapsulated oil

Wall materials

Technique of encapsulation

Fish oil

Lecithin and sunflower oil

Shrimp oil

Fish oil

Product

Results

References

Nanoliposomes (Mozafari method)

Bread

Ojagh and Hasani (2018)

SC, fish gelatin, and glucose syrup

Spray-drying

Biscuits

MD, fish gelatin

Spray-drying

Cookies

Emiliorated oxidative stability against lipid oxidation Improvement of the nutritional profile due to the protection of UFAs (mainly EPA and DHA) from oxidation during 25 days of storage Positive effects on technological and sensory properties Positive effects on the biscuit quality and sensory properties Microencapsulated shrimp oil up to 6% w/w could be incorporated into biscuits to improve the nutritional profile without affecting the sensorial properties Storage in dark condition retards lipid oxidation during the storage (12 days) Improved oxidative stability in microcapsule containing MD or fish gelatin as wall materials during storage (6 months) The hardness of cookies decreased Improved nutritional quality of cookies Any significant changes in sensory properties and acceptability

Takeungwongtrakul and Benjakul (2017)

Jeyakumari, Janarthanan, Chouksey, and Venkateshwarlu (2016)

Dairy products

Chia oil

Chitosan

Spray-drying

Butter

Rapeseed oil

Pectin and CaCl2

Ionic gelation

Yogurt

Fish oil (mixture of trevally, catfish and tuna fish oil)

SC

Freeze-drying or spray-drying

Ice cream

Fish oil

Soy lecithin and sunflower oil

Nanoliposome (Mozafari method)

Yogurt

Microencapsulated chia oil up to 8% ↑ the omega-3 PUFAs concentration with reasonable oxidative stability and no effect on sensory characteristics Supplementation at 2%, 4%, 6%, and 8% concentrations significantly enhanced omega-3 PUFAs in butter Stability of fatty acids content during the storage of 90 days Higher acceptability of appearance and showed stability for 30 days Technical feasibility, supplying color and functionality to the final product Good influences from the health point of view, fortification with 15 g w/w of microencapsulated fish oil decrease SFA and increment of MUFA and PUFA contents Considering PUFAs contents, freeze-drying is the most effective strategy to encapsulate this oil mixture Good strategy to obtain potential functional ice-cream ↑ EPA and DHA contents Avoid strong odors and rapid deterioration Good sensory attributes (sensorial characteristics closer to control sample) ↓ Syneresis, acidity and peroxide values

Ullah et al. (2020)

de Moura et al. (2019)

Andajani (2017)

Ghorbanzade, Jafari, Akhavan, and Hadavi (2017)

Continued

Table 17.2  Recent studies on the fortification of food products with encapsulated oils—cont’d Food category

Encapsulated oil

Meat products

Fish oil

Whey protein and tragacanth gum, whey protein, and carrageenan

Fish oil

Soy protein isolated and inulin

Fish oil

Wall materials

Lecithin and MD, lecithin with MD and chitosan

Technique of encapsulation

Product

Results

References

Freeze-drying

Chicken nuggets

Pourashouri, Shabanpour, Heydari, and Raeisi (2021)

Freeze-drying

Beef burger

Protective action against lipid and protein oxidation Enhanced oxidative shelf-life (tested until 90 days) Emiliorated nutritional profile (↑ EPA and DHA contents) Stability of EPA and DHA during storage Improved sensory properties Stability of EPA and DHA after cooking ↓ pH, ↑ hardness and chewiness

Spray-drying

(Cooked and drycured) sausages

↑ Oxidative processes, ↑ volatiles compounds related to lipid oxidation Sensory attributes were negatively affected causing ↓ overall liking of burgers Cooked and dry cured products can be claimed as “source of omega-3 fatty acids” Any significant effects on physicochemical characteristics, oxidative stability, and overall acceptability

Rios-Mera, Saldaña, Patinho, Selani, and Contreras-Castillo (2021)

Solomando, Antequera, and Perez-Palacios (2020)

Tigernut, chia, and linseed oils

SC and lactose

Spray-drying

Pâtés

Chia oil enriched with rosemary

Sodium alginate and CaCl2

External ionic gelation

Burgers

Modified fatty acid composition, ↓ SFAs and ↑ PUFAs (chia and linseed pâtés) or ↑ MUFAs contents (tigernut pâtés) Pâtés prepared with oils containing high omega-3 PUFAs levels (as chia oil) displayed higher TBARS values Sample with high PUFAs contents presented softer textures and lower acceptability values Decrease in fat and cholesterol contents Higher TBARS values found in burgers containing chia oil microparticles without rosemary Burgers produced with chia oil microparticles enriched with rosemary showed greater oxidative stability than other treatments, mainly after cooking Groups enriched with rosemary presented an ↑ in terpenic volatiles and were characterized by the descriptors herbal and pleasant aroma, and ideal texture Improved sensory profile for samples contained chia oil enriched with rosemary Chia oil microparticles enriched with rosemary can be used as replacers of 50% of animal fat

Vargas-Ramella et al. (2020)

Heck et al. (2018, 2019)

Continued

Table 17.2  Recent studies on the fortification of food products with encapsulated oils—cont’d Food category

Encapsulated oil

Wall materials

Technique of encapsulation

Fish oil

MD, chitosan

Fish oil

Lecithin with chitosan and MD

Product

Results

References

Spray-drying

Pork burgers

Aquilani et al. (2018)

Spray-drying

Chicken nuggets

Decreased oxidative reactions of oil in microcapsules compared to the bulk fish oil/TBARs values similar to control group Better preservation of EPA and DHA (after storage and cooking) both under refrigeration and freezing Thermal behavior of the microparticles were similar before and after incorporation into the burgers Improved sensory traits with respect to the control Effectiveness of the method to fortify meat with omega-3 PUFAs ↓ lipid and protein oxidation were found during storage Sample containing fish oil microparticles showed the lowest content of volatile compounds related to lipid oxidation (as hexanal) Any significant differences in sensory attributes were detected in comparison with control Fish oil microparticles can be employed as replacers of 50% of animal fat

Pérez-Palacios, Ruiz-Carrascal, Jiménez-Martín, Solomando, and Antequera (2018)

Fish oil

MD, GA and caseinate

Spray-drying

Frankfurter sausages

Fish oil

MD and chitosan

Spray-drying

Spanish salchichon (dryfermented pork sausage)

The lipid reformulation ↑ MUFAs and omega-3 PUFAs levels The microencapsulation process ↑ lipid oxidation probably due to the thermal treatment during pasteurization ↑ TBARS values and volatile compounds derivate from lipid oxidation Not suitable for 50% back fat substitution in frankfurter sausages Improved nutritional profile, ↑ EPA and DHA amounts, ↓ omega-6/ omega-3 ratio Increased lipid oxidation, ↑ TBARS values Alteration of texture parameters, ↑ hardness, gumminess and chewiness Sensory parameters were negatively affected

Domínguez et al. (2017)

Lorenzo, Munekata, Pateiro, Campagnol, and Domínguez (2016)

Abbreviations: AI, atherogenic index; DHA, docosahexaenoic acid; EFAs, essential fatty acids; EPA, eicosapentaenoic acid; GA, gum Arabic; H/h, hypo/hypercholesterolemic fatty acids ratio; MD, maltodextrin; MUFAs, monounsaturated fatty acids; PUFAs, polyunsaturated fatty acids; SC, sodium caseinate; SFAs, saturated fatty acids; TI, thrombogenic index; UFAs, unsaturated fatty acids. No permission required.

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(Şahin-Yeşilçubuk & Akoh, 2017). Bakery products, cereals and derivates, dairy products, and meat products are the main food categories fortified with this type of nutrients (Feizollahi et al., 2018). Most studies reported successful incorporation of encapsulated oils in various food products, observing higher oxidative stability and high sensory acceptability. Hence, the most recent applications of encapsulated oils are summarized in Table 17.2 and are described in the following sections.

5.1 ­Cereals and bakery products Fortification of cereals and derivate products as well as bakery products with micro/ nanoencapsulated oils are attracting the attention of food industry researchers due to their functional properties such as high content of UFAs and antioxidant activity (Delshadi et al., 2020). Pasta is one of the most widely consumed foods in the world and represents a traditional and highly accepted food owing to its nutritional and sensory properties. It is recognized as an excellent “device” for incorporating healthy ingredients given its easy handling, storage, and preparation, accessible price, easy processing and cooking, and extended shelf-life (Filipović, Pezo, Filipović, Brkljača, & Krulj, 2015; González et al., 2021). Similarly, bakery products have been investigated for enrichment with encapsulated oils due to their frequent consumption and low cost (Şahin-Yeşilçubuk & Akoh, 2017). Recently, González et al. (2021) has encapsulated chia seed oil, by using soybean protein isolate as wall material, through emulsification and freeze-drying. The obtained powder was applied for the fortification of durum wheat pasta and its effect on the cooking quality of dry pasta was studied. Results showed that no significant variations were detected in cooking parameters, as optimal cooking time, cooking loss, and texture of cooked pasta. In addition, considering the whole storage stability test (until 150 days), the oil microcapsules presented a protective effect delaying the lipid oxidation, preventing the formation of primary oxidation products such as hydroperoxides radicals. Thus, this study demonstrated that microencapsulation of chia oil may be a procedure that allows developing omega-3 fortified foods, such as dry pasta. Promising results were reported also by Venturini et  al. (2019), who studied the incorporation of chia seed oil microcapsules obtained by freeze-drying (suing sodium caseinate and carnauba wax as coating materials) in cookie’s formulation as a partial substitute of margarine. Data reported a significant reduction of saturated fatty acids (SFA) and MUFAs fractions and a remarkable increase of PUFAs, mainly of α-linolenic acid, in samples containing the oil microcapsules compared to the control sample. Furthermore, the atherogenicity (AI) and thrombogenic (TI) indices of the treatments were significantly reduced compared with the control. Considering the color, cookies with 30% wt substitution exhibited better storage color stability. Furthermore, from a sensorial standpoint, samples with the substitution of margarine by 15% wt oil-loaded microparticles reported the highest

5 ­ Applications of micro/nanoencapsulated oils

a­ cceptability among consumers. An improvement of the nutritional quality of fortified cookies was also obtained by other authors (Jeyakumari et al., 2016), who incorporated fish oil encapsulated using spray-drying (fish gelatin and maltodextrin as wall materials). In addition, samples with fish oil microcapsules contained fish gelatin and maltodextrin revealed better oxidative stability. On the other hand, although oil microcapsules application seemed to decrease the hardness of the samples, the sensory analysis reported that the use of maltodextrin as wall material for fish oil encapsulation did not alter the cookies’ acceptability, obtaining values comparable with control (without fish oil). In the same way, Ojagh and Hasani (2018) investigated the effect of 5% w/w nanoencapsulated fish oil on the technological and sensory quality of fortified bread. In this work, the authors encapsulated fish oil in nanoliposomes employing lecithin and sunflower oil as wall materials. This formulation was demonstrated to be effective to enrich bread. In fact, samples with fish oil nanoliposomes showed an enhanced nutritional value and oxidative stability (highest resistance to lipid oxidation). Furthermore, fortified bread did not show significant differences in aroma, texture, and overall acceptability compared with the control sample. Similar results were achieved by González et al. (2018), who studied the effect of using encapsulated chia oil by freeze-drying on the functional properties of bread (soy protein isolated as shell material). Oxidative stability was guaranteed by chia oil microcapsules, while a remarkable increment in the hydroperoxide values was observed in the bread fortified by unencapsulated oils. Furthermore, the addition of microencapsulated oil did not modify the breads’ texture, no significant differences were reported in the consumers’ preference among the treatments, and fortified breads with microparticles obtained a 95% of purchase intention by tasters. However, considering the lipid profile, treated samples reported a reduction of α-linolenic FAs during storage (14 days) which suggests that the baking process could have slightly affected the structure of this molecule in the matrix and that the microencapsulation method did not have the expected protective action on this essential fatty acid. Moreover, the fortification of biscuits with microencapsulated shrimp oil (0, 3, 6, 9, and 12% w/w) was studied by Takeungwongtrakul and Benjakul (2017). Microcapsules were obtained by spray-drying and sodium caseinate, fish gelatin, and glucose syrup were employed as coating agents (at a ratio of 1:1:4). In this study, the authors investigated the effects of shrimp oil microcapsules on the features and sensory properties and the impact of the illumination on the quality of biscuits during storage. Results demonstrated that the application of shrimp oil microcapsules affected the biscuit quality and sensory characteristics, showing that a dose up to 6% could be incorporated to improve the nutritional profile (increased concentration of EPA and DHA) without altering the sensory properties of the final product. Furthermore, considering the oxidative stability, data indicated that biscuits should be stored in dark conditions in order to delay lipid oxidation during the storage (12 days), thus avoiding rancid odors resulted from oxidation reactions.

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5.2 ­Dairy products Dairy products represent a fundamental part of the human diet, these products contain some omega-3 PUFAs, but the concentration is generally lower than the biologically recommended values (Ullah et  al., 2020). Thus, the enrichment of dairy products with omega-3 rich healthy oils is considered an encouraging manner to supplement milk and its derivative products (butter, ice cream, yogurt, cheese, etc.), enhancing their nutritional values, stability, and beneficial health properties (Pateiro et al., 2021). In this context, Ullah et al. (2020) demonstrated that microencapsulation could be an effective strategy to ameliorate the stability of vegetable oils in butter. They added into butter formulation chia oil powders (2%, 4%, 6%, and 8% of microencapsulated chia oil), obtained by the microencapsulation of chia oil (MCO) by using chitosan as wall material through spray-drying. Determinations were performed at 0, 45, and 90 days of storage and outcomes showed that MCO did not alter the physicochemical characteristics and standards of identity of butter. Microencapsulation did not affect the lipid profile of MCO, reporting α-linolenic values stable over the storage time (17.44% in fresh vs 17.11% at 90 days stored). Similarly, the storage time did not alter the concentration of eicosatetraenoic acid (EPA), docosapentaenoic acid (DPA), and docosahexaenoic acid (DHA), recording after 90 days of storage a mean of 0.05% loss of these valuable fatty acids. Besides, as expected, supplementation of butter with MCO favored a significant improvement of omega-3 PUFAs contents in butter. Furthermore, MCO had superior antioxidant activity, observing DPPH free radical scavenging activity of microcapsules at 0, 45, and 90 days of storage of 36.51%, 36.43%, and 365.96%, respectively. Finally, the sensory properties of experimental samples resulted similarly to the control. Thus, MCO can be used to enrich butter and to improve its functional value. Yogurt has also been an object of study since it is one of the most popular products worldwide and its matrix is extremely homogeneous (Bakry, Chen, & Liang, 2019; Hermida & Gallardo, 2015). In fact, some researchers (de Moura et al., 2019) investigated the application of rapeseed oil microparticles in yogurt and its behavior over 30 days. Oil microcapsules were obtained using pectin and CaCl2 as shell materials through ionic gelation. The application of microparticles demonstrated technical feasibility, supplying color and functionality to the final product. Actually, samples with microcapsules reported high acceptability of appearance with a mean score of 6.5 (in a 9-point hedonic scale), corresponding to values from “like slightly” to “liked moderately,” and showed stability for 30 days. Interesting and encouraging results were obtained by Ghorbanzade et al. (2017), who studied the effects of fish oil encapsulated in nanoliposomes (soy protein and sunflower oil) in yogurt matrix. Physicochemical properties, fatty acid profile, oxidative stability, and sensory profile were determined during 3 weeks of storage at 4°C. Data reported that nanoliposome encapsulation reduced significantly acidity, syneresis, and peroxide values. On the other hand, considering fatty acids profile, outcomes obtained after 21 days storage, indicated that the addition of nanoencapsulated fish oil into yogurt increased DHA

5 ­ Applications of micro/nanoencapsulated oils

and EPA stability in comparison with samples containing free fish oil. Moreover, that sample fortified with nanoencapsulated fish oil revealed sensorial characteristics closer to the control sample than yogurts with unencapsulated fish oil. Thus, considering the results obtained, this study demonstrated that fish oil could be effectively encapsulated by nanoliposomes and could be employed for yogurt fortification. Furthermore, the application of encapsulated fish oil was also tested for the fortification of ice-cream. In particular, Andajani (2017) examined and compared the fatty acid profiles of ice-cream fortified with a fish oil mixture encapsulated using spray-drying and freeze-drying (sodium caseinate as shell material). Data showed that SFAs, MUFAs, and PUFAs contents of fish oil mixture microcapsules obtained by freeze-drying method were 53.74%, 32.20%, and 1.91%, whereas using spraydrying were 61.30%, 38.7%, and 0% (not detected), respectively. Hence, it can be deduced that freeze-drying technology is the most effective strategy to encapsulate this oil mixture considering PUFAs contents. Moreover, it was determined that the enrichment of 15 g w/w microencapsulated fish oil in ice-cream could decrease SFAs and increment MUFAs and PUFAs contents, improving its nutritional value and representing a good strategy to obtain potential functional ice-cream.

5.3 ­Meat products Today, meat industry has to face consumer demands for healthier products. It is wellknown that meat and meat products are characterized by a high amount of fat, mainly SFAs, cholesterol, and other compounds that can damage human health (Barros et al., 2020). Thus, the meat sector is actually forced to reformulate its products in order to meet consumers’ requirements. In particular, the meat industries and the scientific community have made significant efforts to limit the use of animal fat and to find suitable strategies to replace it with healthier lipids (Cittadini et al., 2021). The substitution of animal fat with healthy oils (rich in omega-3 PUFAs) represents in fact an efficient approach to enhance the nutritional profile of meat products as well as to obtain reformulated products with remarkable beneficial effects on human health (Heck et al., 2021; Lorenzo et al., 2016). Nevertheless, this lipid reformulation can alter the technological properties, oxidative stability, and sensory quality of meat products. In this sense, encapsulation has stood out as promising technology able to improve oxidative stability and prevent the thermal deterioration of oils rich in omega-3 PUFAs, allowing their application in meat products (Heck et al., 2021). Moreover, microencapsulated oils possess functional properties similar to pork back fat, which allow to preserve the technological features of the products (Fernandes, Trindade, Lorenzo, & de Melo, 2018; Kouzounis, Lazaridou, & Katsanidis, 2017). Various encapsulation methods have been developed; however, it is important to choose one of them depending on the specific conditions of each food. Hence, cooked meat products require microcapsules resistant to high temperatures, which is not necessary in the case of raw meat products (Heck et al., 2021). Numerous studies have employed various technologies and wall materials to encapsulate oils for application in meat products. The most interesting and successful investigations are described as follows.

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The burger is one of the most common meat products used to examine the effectiveness of applying encapsulated oils in this type of food. Rios-Mera et al. (2021) investigated the effect of NaCl and the incorporation of long-chain polyunsaturated fatty acids (LCPUFAs) on the quality parameters of a beef burger. In this regard, fish oil was either added in free form or encapsulated by freeze-dried microparticles (soy protein and inulin as shell compounds). Considering the effects of fish oil application, data showed that microparticles affected significantly the quality of burgers. Actually, albeit encapsulated fish oil maintained the contents of EPA and DHA stable after cooking, a reduction was observed in pH and an increase of hardness, chewiness, and oxidation processes (increased volatile compounds), which negatively affected the sensory attributes and overall liking of burgers. Thus, this work demonstrated that the use of fish oil freeze-dried microcapsules is not a recommended approach for fortifying meat products as burgers with LCPUFAs. On the contrary, Aquilani et al. (2018) recorded positive and encouraging results using spray-dried fish oil as a fat substitute in pork burgers. In this work, researchers compared the effect of the application of fish oil in free form vs. microparticles (containing maltodextrin and chitosan as wall materials) in burgers, considering factors as lipid profile, oxidative stability, and sensory attributes. The analysis reported that fish oil microcapsules were able to protect EPA and DHA from oxidation during burgers storage both under refrigeration and freezing. This oxidative stability was reflected also in TBARs values and sensory parameters, which were very similar to the control samples (elaborated with pork back fat). Moreover, Heck et  al. (2019, 2018) have recently suggested an innovative methodology to increase the oxidative stability of microparticles including oils rich in omega-3 PUFAs. Authors enriched chia oil with bioactive compounds from rosemary and successively encapsulated rosemary-enriched chia through external ionic gelation. At this point, the obtained microparticles were employed in burger formulation as replacers of 50% of animal fat, and the oxidative stability and sensory profile were studied. Data showed that burgers containing rosemary-enriched chia microparticles presented higher oxidative stability (especially after cooking) compared to samples with encapsulated chia without rosemary. Furthermore, sensory defects caused by the lipid reformulation were reduced by the addition of rosemary antioxidants into chia oil, enhancing the sensory profile of the final product. In addition, the presence of rosemary caused an increase in terpenic volatile compounds providing a herbal and pleasant aroma. Hence, these outcomes proved that the mixture of healthy oils and natural antioxidants is a promising and successful manner to enhance the oxidative stability of microparticles, allowing the elaboration of safe and healthier meat products (Granato et al., 2020; Munekata et al., 2020). According to our frenetic lifestyle, today there is a growing request for convenience and ready-to-eat products, as prefried frozen ones, and chicken nuggets are the most popular (Jiménez-Martín, Pérez-Palacios, Carrascal, & Rojas, 2016). The fortification of this product with omega-3 rich oils was treated by several authors. Pourashouri et al. (2021) enriched chicken nuggets with fish oil and freeze-dried microencapsulated oil to evaluate the physicochemical, fatty acid profile, and oxidative stability of prefried samples during frozen storage. Fish oil was encapsulated using

5 ­ Applications of micro/nanoencapsulated oils

two different wall materials, tragacanth (TRG) vs carrageenan (CGN) and their effectiveness were evaluated. Results revealed that fish oil microencapsulation exerted a protective action against lipid and protein oxidation, enhanced the oxidative shelf life, and the sensory features of the fortified nuggets. Considering fatty acids profile, samples with fish oil (free or encapsulated) reported higher EPA and DHA contents as expected, however nuggets with encapsulated oil demonstrated a major capability to preserve these EFAs during storage (until 90 days). Thus, this work proved the suitability of this method and reported that tragacanth as shell material was more efficient in maintaining the sensory properties. Similar results were obtained by Pérez-Palacios et al. (2018), who also employed fish oil to improve the fatty acid composition of chicken nuggets. In this case, the authors compared the oxidative stability between nonencapsulated and spray-dried fish oil and reported that samples enriched with fish oil microparticles presented less lipid and protein oxidation during storage in comparison with the other treatments. The results were also reflected in volatile results, where volatile compounds, considered lipid oxidation biomarkers (as hexanal), showed the lowest values in the sample fortified with encapsulated fish oil. In addition, no differences were detected in comparison with the control group. Thus, fish oil encapsulated in this study could be employed as replacers of 50% of animal fat in chicken nuggets. Another noteworthy approach to fish oil encapsulation has been suggested by Solomando et  al. (2020). In this study, fish oil was encapsulated by spray-drying and using different shell compounds, lecithin mixed with maltodextrin vs lecithin blended with chitosan and maltodextrin, and the obtained powders were incorporated both in raw and cured sausages. As expected, microencapsulated oil increased the contents of EPA and DHA, enabling the products to be claimed as “source of omega-3 PUFAs,” without any effects on physicochemical features, oxidative stability, overall acceptability or changes that can take place during the culinary heating or dry-cured processing. Thus, this work confirmed the viability of these oil encapsulation systems, as EPA and DHA vehicles, to fortify meat products subjected to low and high temperatures for manufacturing, storage with refrigeration, and culinary eating. Spray-dry technology was employed also in the study carried out by Domínguez et al. (2017), who elaborated low-fat frankfurter sausages with healthier fatty acid profiles by replacing 50% of animal fat with microencapsulated fish oil and nonencapsulated mixture of oil and fish oil (1:1). In this study, maltodextrin, gum Arabic, and caseinate were employed as coating materials. Unsurprisingly, samples containing fish oil reported higher MUFAs and omega-3 PUFAs contents. Nevertheless, in this case, sausages with encapsulated oil reported higher lipid oxidation when compared to the sample containing oil in free form. Considering that sausages were pasteurized at 90°C for 30 min, it is possible that the thermal treatment may have caused the breakdown of microparticles and the successively fish oil oxidation. Similarly, Lorenzo et al. (2016) studied the effect of the partial substitution (25%, 50%, and 75%) of pork back fat by fish oil microencapsulated by spray-drying (maltodextrin and chitosan as coating agents) on physicochemical properties, oxidative stability, and fatty acid profile of “Spanish salchichón.” As expected, the addition of fish oil

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microparticles enhanced the lipid profile of samples, increasing the amount of EPA and DHA, and decreased the omega-6/omega-3 ratio. On the other hand, batched where microencapsulated oil was used as pork back fat replacer reported higher TBARs values, corresponding to increased lipid oxidation of samples. The sensory analysis also reported negative results, detecting increase hardness, gumminess, and chewiness in the samples with fish oil microcapsules. Finally, Vargas-Ramella et al. (2020) also described unstable encapsulated oils and higher lipid oxidation values in samples containing chia oil, studying the addition of chia, linseed, and tigernut oils spray-dried microparticles in deer pâté. These results could be due to the higher content of omega-3 PUFAs in chia oil in comparison with the other oils (Mohamed Basuny, Mohammed, & Basuny, 2020). It was reported a decrease of SFAs and a significant increase of PUFAs (in chia and linseed pâté) or MUFAs contents (tigernut pâté). In addition, this remarkable increment of PUFAs could be the explanation for softer textures and lower acceptability values. Otherwise, they also observed a significant decrease in fat and cholesterol contents.

6 ­Conclusions Vegetable and marine oils are a source of health-promoting lipids, such as omega-3 and omega-6 PUFAs, with relevant biological and functional properties. In the last decades, the fortification of foods with these healthy and nutritious oils has gradually drawn the attention of the food industry and scientific community due to consumers’ demand for functional foods. However, owing to the high content of unsaturated fatty acids, these oils are prone to instability and oxidative degradation, limiting their applicability in food industries. In this context, encapsulation technology has been demonstrated to be a favorable strategy able to overcome oil drawbacks and allow the application of these oils in different food matrices. Nevertheless, from an application standpoint, it is worth noting that the manner in which oils are incorporated into foods is a crucial factor, actually the choice of the encapsulation technique and wall materials to use plays a key role. Spray-drying and freeze-drying represent one of the most common and economic and effective micrometric encapsulation technologies employed. Besides, carbohydrates and proteins, used alone or blended in different ratios, corresponds to the wall materials mainly used. Although, this selection should be carefully made based on different factors as core materials characteristics, the matrix where it will be applied and the processing conditions are involved. Moreover, encapsulated oil, before its application, should be characterized in order to assess the encapsulation effectiveness. In the last decades, multiple studies have been realized about oil encapsulation and its employ for the elaboration of fortified foods. The most widely used food matrices were cereals, pasta, bakery products, dairy products, and meat products. Promising results were obtained, but most of the studies reflected that the addition of encapsulated oils increased lipid stability and enhanced the lipid profile without affecting the technological and sensorial properties of the final products.

­References

However, future trends point to the search of novel coating agents and strategies in order to improve the efficiency of the encapsulation process and the protection of the bioactive compounds. The addition of natural antioxidants to the core material, before the encapsulation, is in fact one of these emerging trends since it was demonstrated that this combination improved effectively the oxidative stability of micro/ nanoparticles, enabling the production of healthier and safe food products. In addition, considering the limited information about the bioaccessibility, bioavailability, and behavior in the gut microbiota of these oil microparticles within food matrices, further studies are necessary in order to ensure their absorption. Finally, future investigations should be directed toward the implementation of innovative processes in order to reduce the operating costs and environmental footprint, improve the adaptability for industrial needs, and the effectiveness of the encapsulation systems.

­Acknowledgments The authors acknowledge Universidad Pública de Navarra for granting Aurora Cittadini with a predoctoral scholarship (Resolution 787/2019). They also thank GAIN (Axencia Galega de Innovación) for supporting this book chapter (grant number IN607A2019/01). The authors (Rubén Domínguez, Paulo E.S. Munekata, Mirian Pateiro and José M. Lorenzo) are the members of the HealthyMeat network, funded by CYTED Ciencia y Tecnología para el Desarrollo (ref. 119RT0568).

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Pino, J. A., Sosa-Moguel, O., Sauri-Duch, E., & Cuevas-Glory, L. (2019). Microencapsulation of winter squash (Cucurbita moschata Duchesne) seed oil by spray drying. Journal of Food Processing and Preservation, 43(10). https://doi.org/10.1111/jfpp.14136. Pourashouri, P., Shabanpour, B., Heydari, S., & Raeisi, S. (2021). Encapsulation of fish oil by carrageenan and gum tragacanth as wall materials and its application to the enrichment of chicken nuggets. LWT - Food Science and Technology, 137, 110334. https://doi. org/10.1016/j.lwt.2020.110334 (May). Quintero, J., Rojas, J., & Ciro, G. (2018). Vegetable proteins as potential encapsulation agents: A review. Food Research, 2(3), 208–220. https://doi.org/10.26656/fr.2017.2(3).261. Quispe, N. B. P., Chaves, M. A., Santos, A. F., Bastos, T. D. S., & Castro, S. S. (2020). Microencapsulation of virgin coconut oil by spray drying. Brazilian Journal of Development, 6(1), 1510–1529. https://doi.org/10.34117/bjdv6n1-103. Raeisi, S., Ojagh, S. M., Pourashouri, P., Salaün, F., & Quek, S. Y. (2021). Shelf-life and quality of chicken nuggets fortified with encapsulated fish oil and garlic essential oil during refrigerated storage. Journal of Food Science and Technology, 58(1), 121–128. https://doi. org/10.1007/s13197-020-04521-3. Raza, Z. A., Khalil, S., Ayub, A., & Banat, I. M. (2020). Recent developments in chitosan encapsulation of various active ingredients for multifunctional applications. Carbohydrate Research, 492, 108004. https://doi.org/10.1016/j.carres.2020.108004 (March). Rios-Mera, J. D., Saldaña, E., Patinho, I., Selani, M. M., & Contreras-Castillo, C. J. (2021). Enrichment of NaCl-reduced burger with long-chain polyunsaturated fatty acids: Effects on physicochemical, technological, nutritional, and sensory characteristics. Meat Science, 177. https://doi.org/10.1016/j.meatsci.2021.108497 (November 2020). Rodríguez, J., Martín, M. J., Ruiz, M. A., & Clares, B. (2016). Current encapsulation strategies for bioactive oils: From alimentary to pharmaceutical perspectives. Food Research International, 83, 41–59. https://doi.org/10.1016/j.foodres.2016.01.032. Sagiri, S. S., Anis, A., & Pal, K. (2016). Review on encapsulation of vegetable oils: Strategies, preparation methods, and applications. Polymer - Plastics Technology and Engineering, 55(3), 291–311. https://doi.org/10.1080/03602559.2015.1050521. Şahin-Yeşilçubuk, N., & Akoh, C. C. (2017). Encapsulation technologies for lipids. In C. C. Akoh (Ed.), Food lipids: Chemistry, nutrition and biotechnology (4th ed.). CRC Press. Shamaei, S., Seiiedlou, S. S., Aghbashlo, M., Tsotsas, E., & Kharaghani, A. (2017). Microencapsulation of walnut oil by spray drying: Effects of wall material and drying conditions on physicochemical properties of microcapsules. Innovative Food Science and Emerging Technologies, 39, 101–112. https://doi.org/10.1016/j.ifset.2016.11.011. Shariat, S., Hakimzadeh, V., & Pardakhty, A. (2020). The physicochemical and organoleptic evaluation of the nano/micro encapsulation of Omega-3 fatty acids in lipid vesicular systems. Nanomedicine Journal, 7(1), 80–86. https://doi.org/10.22038/nmj.2020.07.010. Sharma, S., Cheng, S. F., Bhattacharya, B., & Chakkaravarthi, S. (2019). Efficacy of free and encapsulated natural antioxidants in oxidative stability of edible oil: Special emphasis on nanoemulsion-based encapsulation. Trends in Food Science and Technology, 91, 305–318. https://doi.org/10.1016/j.tifs.2019.07.030 (May). Shishir, M. R. I., Xie, L., Sun, C., Zheng, X., & Chen, W. (2018). Advances in micro and nano-encapsulation of bioactive compounds using biopolymer and lipid-based transporters. Trends in Food Science and Technology, 78, 34–60. https://doi.org/10.1016/j. tifs.2018.05.018 (May). Soliman, E. A., El-Moghazy, A. Y., Mohy El-Din, M. S., & Massoud, M. A. (2013). Microencapsulation of essential oils within alginate: Formulation and in vitro evaluation

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CHAPTER

Replacement of saturated fat by healthy oils to improve nutritional quality of meat products

18

Rosane Teresinha Hecka, Bibiana Alves Dos Santosa, José M. Lorenzob,c, Claudia Ruiz-Capillasd, Alexandre José Cichoskia, Cristiano Ragagnin de Menezesa, and Paulo Cezar Bastianello Campagnola a

Federal University of Santa Maria, Santa Maria, Rio Grande do Sul, Brazil b Centro Tecnológico de la Carne de Galicia, Ourense, Spain c University of Vigo, Ourense, Spain d Institute of Food Science, Technology and Nutrition (ICTA-CSIC), Madrid, Spain

­C hapter outline 1 Introduction.......................................................................................................... 462 2  Health benefits of reducing SFA and increasing PUFA intakes.................................. 464 3  Fatty acid profile of the main oils used in meat products......................................... 465 3.1  Oils rich in monounsaturated fatty acids (MUFA)..................................... 465 3.2  Oils rich in n-6 PUFA............................................................................ 467 3.3  Oils rich in n-3 PUFA............................................................................ 468 4  Approaches for the addition of healthy oils in meat products................................... 469 4.1  Addition of liquid healthy oils to meat products....................................... 469 4.2  Addition of preemulsified healthy oils to meat products............................ 471 4.3  Addition of healthy oils microencapsulated to meat products.................... 474 4.4  Addition of gelled healthy oils to meat products....................................... 476 4.5  Addition of healthy oils enriched with bioactive compounds to meat products..................................................................................................... 479 5  Final remarks........................................................................................................ 481 Acknowledgments..................................................................................................... 481 References............................................................................................................... 482

Food Lipids. https://doi.org/10.1016/B978-0-12-823371-9.00008-3 Copyright © 2022 Elsevier Inc. All rights reserved.

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1 ­Introduction The fat content of most processed meat products is greater than 30%, which represents a high amount of saturated fatty acids (SFA) in these products (Fig. 18.1). Several studies have shown an association between a diet rich in SFA and the incidence of obesity, cardiovascular disease, and some types of cancer (Boada, HenríquezHernández, & Luzardo, 2016). The consumption of monounsaturated fatty acids (MUFA), among which oleic acid stands out due to its high prevalence, has also been related to a reduction in LDL cholesterol and triglycerides in the blood. Recently, however, there has been a controversy in the real effect of the SFA and MUFA in human health (Liu et al., 2017; Ruiz-Capillas & Herrero, 2021). Meat products also have a high ratio of dietary n-6/n-3 polyunsaturated fatty acids (PUFA) (15–20:1), which is nutritionally unfavorable for human health (Wood et al., 2004). Thus, frequent consumption of meat products can lead to inflammation and the appearance of several chronic diseases (Klurfeld, 2015). Therefore, improving the lipid profile of meat products is necessary to meet the demands of health-conscious consumers. The replacement of animal fat, mainly SFA, by healthy oils is one of the most effective approaches to increase MUFA and the PUFA/SFA ratio and to reduce the n-6/n-3 PUFA ratio. Traditionally, the incorporation of this healthy oil for the development of a healthier lipid meat product has been done by adding it directly in liquid form. However, the use of liquid oils can negatively affect the important technological and sensory attributes of meat products, as well as reduce their shelf life due to increased lipid oxidation (Triki et al., 2013). In order to avoid this important problem, different techniques have been applied (preemulsion, emulsion gelled, microencapsulation, etc.) (Herrero & Ruiz-Capillas, 2021; Jimenez-Colmenero et al., 2015). The microencapsulation technique is one of the available alternatives to protect oils from lipid oxidation, which basically consists of the production of microparticles, in which the core material is coated with an encapsulating agent (Champagne & Fustier, 2007). Gelation is another strategy that improves the oxidative stability of oils. This technique retains and locks oil and leads to a reduction of fat migration and control phase separation (water and oil), providing properties similar to solid fats. The kinds of gels formed depend on the polarity of the liquid phase and can be classified as hydrogels, emulgels, and oleogels/organogels (Jimenez-Colmenero et al., 2015). Hydrogels are formed when water is used as the continuous phase, while emulgel corresponds to the formation of a biphasic emulsion (Dickinson, 2012). In turn, oleogels/organogels are formed from the dispersion and structuring of the oil by an organogelator (Balasubramanian, Sughir, & Damodar, 2012). Heck et al. (2017), Heck, Fagundes, et al. (2019), Heck, Saldaña, et al. (2019), and Gómez-Estaca et al. (2019) used microencapsulation and gelation techniques to incorporate oils rich in n-3 PUFA in meat products, aiming at the use of natural products and healthy ingredients in the food industry. The results showed that the application of these oils was effective in nutritionally improving meat products. However, the use of healthy oils should be carried out with caution even for microencapsulated

1 ­ Introduction

FIG. 18.1 Lipid reformulation in meat products. No permission required.

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or gelled oils, once these techniques do not completely protect PUFA from lipid oxidation. Recently, new strategies have been studied to improve the oxidative stability of healthy oils applied to meat products. Promising results have been reported by some authors on the incorporation of bioactive compounds in healthy oils through emerging green extraction techniques, which have been developed and optimized in recent years (Heck, Fagundes, et al., 2019; Heck, Saldaña, et al., 2019; Heck et al., 2020; Pintado et al., 2021). In this context, this chapter will present the health benefits of reducing SFA and increasing PUFA intake. The fatty acid composition of the main oils used in meat products will also be presented. In addition, the main approaches to improve the nutritional quality of meat products through the replacement of saturated fatty acid by healthy oils will be discussed. Studies about the use of liquid, preemulsified, gelled, and microencapsulated oils as substitutes for animal fat in meat products, as well as the strategies to enrich healthy oils with bioactive compounds, will be presented.

2 ­Health benefits of reducing SFA and increasing PUFA intakes The World Health Organization (WHO) recommends that total fat should not exceed 30% of the total energy intake, and the total consumption of SFA should not exceed 10%. Therefore, SFA should be replaced by MUFA and PUFA in foods (Prado et al., 2004). Each SFA affects differently the cholesterol concentrations in the different plasma lipoprotein fractions. For example, lauric (C12:0), myristic (C14:0), and palmitic (C16:0) acids increase LDL (low-density lipoprotein) cholesterol, which is not observed for stearic acid (C18:0). Some studies have shown that replacing SFA (C12:0-C16:0) with PUFA can lead to a decrease in total and LDL cholesterol concentrations and an increase in HDL (High Density Lipoprotein) cholesterol, which reduces the risk of cardiovascular disease (CVD) (IOM, 2005). To achieve these goals, the recommended minimum intake of PUFA is around 6% of the total energy intake. According to the statements by both the WHO and FAO, the recommended proportion of SFA and PUFA in diets should be between 0.4 and 1.0 (WHO, 2003). The substitution of SFA (C12:0—C16:0) by MUFA can also confer a similar effect than with PUFA, although on a smaller scale (WCRF/AICR, 2007). The PUFA Linoleic (LA, C18: 2) (n-6/omega 6) and α-linolenic (ALA, C18: 3) (n-3/omega 3) acids are considered essential acids, as they cannot be synthesized by humans. It is recommended that 2.5% and 0.5% of the dietary energy come from LA and ALA, respectively (WHO, 2003). In addition, the intake of n-3 long-chain PUFA, such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), can also decrease the risk of CVD and possibly other aging-related degenerative diseases. To obtain these benefits, the consumption of 0.25 g of EPA + DHA per day is recommended. However, some studies have shown that high n-3 PUFA concentrations can increase lipid peroxidation and reduce cytokine production. Therefore, it is recommended to consume up to 2 g of EPA + DHA as an acceptable daily limit.

3 ­ Fatty acid profile of the main oils used in meat products

Currently, in most Western countries, there is a higher consumption of n-6 PUFA when compared with n-3 PUFA, with an n-6/n-3 ratio around 20:1. The high n-6 PUFA and low n-3 PUFA intake is related to the increased incidence of inflammatory and autoimmune diseases, various types of cancer, and cardiovascular diseases (Lee et  al., 2006). This increased risk is due to a high intake of LA, which leads to an increase in arachidonic acid concentration (AA), thus increasing the production of 2- and 4-series eicosanoids (prostaglandin E2 and leukotriene B4) through the cyclooxygenase and lipoxygenase pathways, respectively. A high production of eicosanoids is related to the occurrence of immunological disorders, cardiovascular and inflammatory diseases. On the other hand, the intake of fatty acids from the n-3 PUFA family, such as ALA, EPA, or DHA, which compete with AA for the same enzymatic routes, competitively inhibits the oxidation of arachidonic acid by cyclooxygenase (COX) to prostaglandins and its conversion into leukotrienes (LTs) via 5-lipoxygenase (LOX) (Bhangle & Kolasinski, 2011). Thus, an n-6/n-3 ratio below 4 is recommended for a healthy diet (Simopoulos, 2002). Likewise, the atherogenicity (IA) and thrombogenicity (TI) indexes indicate the relationship between the main classes of SFA, MUFA, and PUFA and, according to (Hulya, 2007), indicate a potential for stimulating platelet aggregation. Thus, the lower these indexes, the greater the potential of the lipid fraction to protect the organism against the occurrence of CVD (Senso et al., 2007). The health benefits of reducing SFA and increasing PUFA intake are summarized in Fig. 18.2.

3 ­Fatty acid profile of the main oils used in meat products The lipid reformulation in meat products can be performed by replacing animal fat with other lipids containing higher MUFA and PUFA contents (Weiss et al., 2010). Various vegetable and marine oils can be used for this purpose, leading to an improvement of the nutritional profile of meat products. The vegetable oils used in meat products include soybean, cotton, canola, linseed, and chia oils, which are sources of MUFA and PUFA fatty acids, in addition to being ­cholesterol-free (Pelser et  al., 2007). Long-chain fatty acids (EPA, docosapentaenoic acid (DPA), and DHA) are found mainly in fish and algae oils (Weiss et al., 2010). In this context, several studies have reported the improvement of the lipid profile of meat products by replacing animal fat with oils of vegetable and marine origin. The fatty acid profile of the main oils used in meat products will be presented below.

3.1 ­Oils rich in monounsaturated fatty acids (MUFA) Vegetable oils rich in MUFA are used in meat products to increase the oleic acid content, once regular consumption of this fatty acid (FA) is associated with the prevention of diseases and clinical conditions such as type 2 diabetes, infections, neurological and cardiovascular disorders (Baǧdatli, 2018; Câmara et al., 2020).

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FIG. 18.2 Health benefits of reducing SFA and increasing PUFA intake. No permission required.

3 ­ Fatty acid profile of the main oils used in meat products

Olive oil is one of the most used oils in meat products due to its high oleic acid content, which corresponds to about 70%–80% of the total FA and also contains 8%–9% PUFA (linoleic and linolenic acids) (Fernandes et  al., 2020). It also contains lower concentrations of SFA (13%) (mainly palmitic and stearic). It is worth mentioning that the FA composition of olive oil is strongly related to environmental conditions, including soil, altitude, and temperature. The unsaponifiable fraction of olive oil has more than 200 constituents at lower concentrations, such as α- and γtocopherols, tocotrienols, β-carotene, phytosterols, flavonoids, and hydrophilic phenolic compounds, which are responsible for the antioxidant and inflammatory effects of this oil (Fernandes et al., 2020). In addition, the European Food Safety Authority Turck et al. (2018) authorized health claims for olive oil due to its nutritional benefits to the health of consumers. Palm oil is another example of vegetable oil rich in MUFA used successfully in the reformulation of meat products. It presents a 50/50 balance of SFA and MUFA in the composition and can be used in technological applications as a semisolid lipid base at room temperature (Chaves, Barrera-Arellano, & Ribeiro, 2018). In addition, palm oil contains a high palmitic acid content, which distinguishes it from other types of vegetable oils and provides differentiated crystallization characteristics. Tiger nut oil can also be used in meat product formulations. It contains high oleic acid (67%–69%) content, followed by palmitic acid (14%), linoleic acid (10%), and stearic acid (3.5%–5%) (Roselló-Soto et  al., 2018). Tiger nut oil is also rich in α-tocopherol (5–87 μg/g) and phytosterols, such as β-sitosterol (43–61 mg/100 g), campesterol (11–17 mg/100 g), and stigmasterol (17–21 mg/100 g) (Lopéz-Cortés et al., 2013). Recently, high oleic sunflower oil has been developed through conventional plant breeding through the use of chemical mutagenesis. It contains about 75%–88% oleic acid and low SFA levels (3%–5% palmitic acid, 2%6% stearic acid). It presents oxidative stability about 10 times greater than soybean, canola, and sunflower oils due to its lower content of linolenic acid (˂1%) (Chaves et al., 2018). Currently, studies have been directed toward the production of ultrahigh oleic sunflower oil, which contains more than 90% oleic acid and presents greater thermooxidative stability when compared to high oleic sunflower oil (Alberio et al., 2016). Hazelnut oil is also rich in MUFA, with oleic acid (73.48%–81.57%) as the major FA, followed by linoleic acid (10.76%–14.95%). It also has a lower concentration of linolenic, palmitic, and stearic acids (Balta et al., 2006).

3.2 ­Oils rich in n-6 PUFA Vegetable oils are a rich source of n-6 PUFA, which in an adequate relationship with the n-3 PUFA presents health benefits well as was documented in the literature. Soybean oil is one of the main oils used to increase PUFA and reduces SFA in meat products due to its high availability and lower cost when compared to other oils (Chaves et al., 2018). Soybean oil is mainly composed of n-6 PUFA (> 50% linoleic acid). It also has a considerable oleic acid level (~ 20%) and a small amount of n-3 PUFA (