Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach 9780128233498

Table of contents :
Cover
Half Title
Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach
Copyright
Contents
Contributors
1. Introduction to agro-industrial waste
1.1 Introduction
1.2 Types and sources of agro-industrial wastes
1.2.1 Agricultural residues
1.2.2 Industrial wastes
1.3 Problems of agro-industrial wastes
1.4 Benefits, recycle, and reuse of agro-industrial wastes
1.4.1 Bioconversion of agro-industrial wastes to industrially important enzymes
1.4.2 Agro-industrial wastes as sources of bioactive compounds for food, fermentation, and drug industries
1.4.3 Agro-industrial wastes and their utilization using solid state fermentation
1.4.4 Bioenergy and biorefineries
1.4.5 Green and sustainable separation of natural products from agro-industrial waste
1.4.6 Agro-industrial wastes as fertilizers in aquaculture
1.4.7 Other miscellaneous value-added applications
1.5 Conclusion and future perspective
References
2. Introduction to natural product
2.1 Natural product
2.2 Secondary metabolites
2.3 Alkaloid
2.3.1 Purine alkaloids
2.3.2 Tropane alkaloids
2.3.3 Calystegines
2.3.4 Pyrrolizidine alkaloids
2.3.5 Quinolizidine alkaloids
2.3.6 Benzyl isoquinoline alkaloids
2.3.7 Ipecac alkaloids
2.3.8 Amaryllidaceae alkaloids
2.3.9 Monoterpene indole alkaloids
2.4 Camptothecin
2.4.1 Lignans and lignins
2.4.2 Polyketides
2.4.3 Hemiterpenes
2.4.4 Monoterpenes
2.4.5 Sesquiterpenes
2.5 Triterpenes and steroids
2.5.1 Saponins
2.5.2 Tetraterpenes
2.5.3 The potential of the natural product
2.6 A source of natural product
2.7 Conclusion
References
3. Ionic liquids with microwave-assisted extraction of natural products
3.1 Introduction
3.2 Ionic liquids: general considerations, classification, and properties
3.3 Ionic liquids as solvents for microwave extraction
3.3.1 ILs and MAE for simultaneous extraction of different classes of compounds
3.3.2 ILs and MAE for targeted extraction of individual classes of compounds
4 Concluding remarks and future perspectives
Acknowledgments
References
4. Pressurized liquid extraction of natural products
4.1 Introduction
4.1.1 Pressurized liquid extraction (PLE)
4.1.2 Influence of operational parameters
4.1.3 Phytonic process
4.1.4 Negative pressure cavitation extraction (NPCE)
4.1.5 Influence of operational parameters
4.1.6 Process improvements
4.1.7 Combined processes
4.2 Instant controlled pressure drop
4.2.1 Hydrodistillation/steam distillation occurs by several physicochemical processes: hydrodiffusion, hydrolysis, decomposition of compounds
4.2.2 Process additional benefits and improvements
4.2.3 High hydrostatic pressure extraction (HHPE)
4.3 Conclusions
Acknowledgments
References
5. Supercritical CO2 extraction of natural products
5.1 Introduction
5.2 Preparation of samples for supercritical CO2 extraction
5.3 Supercritical CO2 extraction of bioactive compounds from natural products
5.4 Supercritical CO2 and novel methods of food processing
5.5 Controlled puffing in extrusion
5.6 Removal of hexane from soybean oil
5.7 Environmental applications of supercritical CO2 extraction
5.8 Conclusion
References
6. Solvent extraction of natural products
6.1 Introduction
6.2 Sample preparation
6.3 Extraction methods
6.3.1 Maceration
6.3.2 Percolation
6.3.3 Soxhlet extraction
6.3.4 Microwave-assisted extraction (MAE)
6.3.5 Ultrasound-assisted extraction (UAE)
6.3.6 Accelerated solvent extraction (ASE)
6.3.7 Supercritical fluid extraction (SFE)
6.3.8 Distillation methods
6.4 Determination of phytochemicals
6.4.1 Presence of alkaloids
6.4.2 Presence of flavonoids
6.4.3 Presence of phytosterols
6.4.4 Presence of phenols
6.4.5 Presence of diterpenes
6.4.6 Presence of proteins and amino acids
6.4.7 Presence of carbohydrates
6.5 Separation methods
6.5.1 Chromatographic techniques
6.6 Structure elucidation
6.6.1 UV-visible spectroscopy
6.6.2 Fourier transform infrared (FTIR) spectroscopy
6.6.3 Nuclear magnetic resonance (NMR) spectroscopy
6.7 Conclusion
References
7. Extraction of flavonoids from agrowaste
7.1 Introduction
7.1.1 General presentation of flavonoids
7.1.2 Uses of flavonoids
7.2 Extraction from agrowaste
7.2.1 General considerations
7.2.2 Different categories of agrowaste for flavonoids extraction
7.3 Conclusions
References
8. Extraction of bioactive compounds from agro-industrial waste
8.1 Introduction
8.2 Extraction processes
8.2.1 Pressurized liquid extraction (PLE)
8.2.2 Ultrasound-assisted extraction (UAE)
8.2.3 Microwave-assisted extraction (MAE)
8.2.4 Subcritical water extraction (SWE)
8.2.5 Supercritical fluid extraction (ScFE)
8.2.6 Enzyme-assisted extraction
8.3 Conclusion
References
9. Extraction of antioxidants from agro-industrial waste
9.1 Introduction
9.2 Antioxidants
9.3 Extraction methods
9.3.1 Ultrasound-assisted extraction
9.3.2 Microwave-assisted extraction (MAE)
9.3.3 Super critical extraction
9.3.4 Pulsed electric field
9.3.5 Pressurized liquid extraction
9.4 Conclusion
References
10. Extraction of carotenoids from agro-industrial waste
10.1 Introduction
10.2 Plants as source of carotenoids
10.3 Chemistry
10.4 Carotenoids and their health benefits
10.4.1 Carotenoids as provitamin A
10.4.2 Carotenoids as antioxidant
10.4.3 Anticancerous properties
10.4.4 Antiobesity effect
10.4.5 Bone health
10.4.6 Carotenoids and cellular signaling
10.4.7 Photosensitivity disorders
10.5 Effects of food processing on carotenoids stability and/or bioavailability
10.5.1 Postharvest storage
10.5.2 Thermal processing
10.6 Application of carotenoids in food industry
10.7 Extraction of carotenoids from agro-industrial waste
10.8 Conventional extraction techniques
10.9 Nonconventional extraction techniques
10.9.1 Supercritical fluid extraction
10.9.2 Ultrasound-assisted extraction (UAE)
10.9.3 Microwave-assisted extraction
10.9.4 Pressurized liquid extraction (PLE)
10.9.5 Electro technologies for extraction of bioactive compounds
10.10 Conclusion
References
11. Extraction of lycopene from agro-industrial waste
11.1 Introduction
11.2 Lycopene sources
11.3 Role of lycopene in human health
11.4 Extraction and purification
11.4.1 Extraction
11.4.2 Extraction methods
11.5 Conclusion
References
12. Extraction of natural dyes from agro-industrial waste
12.1 Introduction
12.2 Different methods of extraction of natural dyes
12.2.1 Ultrasonic and microwave extraction
12.2.2 Fermentation
12.2.3 Aqueous extraction
12.2.4 Enzymatic extractions
12.2.5 Acid and alkali extraction
12.2.6 Spray drying technique
12.2.7 Supercritical fluid extraction
12.3 Various sources of natural dyes
12.3.1 Chickpea husk
12.3.2 Pomegranate rinds
12.3.3 Myrobolan
12.3.4 Barberry
12.3.5 Peanut skin
12.3.6 Walnut husk
12.3.7 Marigold
12.3.8 Onion
12.4 Some demerits related to natural dyes
12.4.1 Cost
12.4.2 Poor color fastness properties and reproducibility
12.4.3 Availability
12.4.4 Harmful effects
12.4.5 Marketing
12.4.6 Storage
12.5 Biological methods for production of various pigments
12.5.1 Submerged fermentation
12.5.2 Solid state fermentation
12.6 Applications
12.6.1 Natural dyes used for coloration food stuff
12.6.2 Application of natural dyes in functional finishing of textiles
12.6.3 Application of natural dyes for medicinal purpose
12.6.4 Application of natural dyes in dye-sensitized solar cells
12.6.5 Few other applications of natural dyes
12.7 Conclusion
Acknowledgments
References
13. Extraction of lignin from agro-industrial waste
13.1 Introduction
13.2 Source of lignin
13.2.1 Organosolv lignin
13.2.2 Hydrolysis lignin
13.2.3 Kraft lignin
13.2.4 Pyrolytic lignin
13.3 Extraction of lignin by using various methods
13.3.1 Organosolv treatment
13.3.2 Steam explosion
13.3.3 Alkaline pulping method
13.4 Biochemistry of extracted lignin from agro-industrial waste
13.5 Challenges and future outlook
13.6 Conclusions
Acknowledgment
Conflicts of interest
References
14. Extraction of fatty acids from agro-industrial waste and its significance
14.1 Introduction
14.2 Characteristics of fatty acids
14.3 Fatty acids from agro-industrial waste
14.4 Processing of deodorizer (DO) distillate
14.4.1 Hydrolysis and recovery of fractions
14.4.2 Fatty acid composition
14.5 Conclusion
References
15. Extraction of pectin from agro-industrial waste
15.1 Introduction
15.2 Basic structure and classification of pectin
15.3 Properties of pectin
15.3.1 Colloidal properties
15.3.2 Gelation properties
15.3.3 Rheological properties
15.4 Sources and extraction of pectin from agro-industrial wastes
15.5 Pectin extraction from agro-industrial waste as affected by the parameters: pH, temperature, and time
15.6 Conclusion
Acknowledgment
References
16. Extraction of cellulosic fibers from date palm by-products
16.1 Introduction
16.2 Materials and methods
16.2.1 Materials
16.2.2 Fibers extraction
16.2.3 Testing and evaluation
16.2.4 Statistical analysis
16.3 Results and discussion
16.3.1 Cross-sectional area
16.3.2 Tensile strength
16.4 Optimum conditions
16.5 Conclusions
Acknowledgments
References
17. Recent developments in extraction of keratin from industrial wastes
17.1 Introduction
17.2 Sources of keratin protein
17.3 Structure keratin
17.4 Extraction of keratin
17.4.1 Reduction method for the extraction of keratin
17.4.2 Effect of different reducing, surfactant, pH, and denaturing agents
17.4.3 Sulfitolysis methods for the extraction of keratin
17.4.4 Alkali methods for the extraction of keratin
17.4.5 Ionic liquid methods for the extraction of keratin
17.5 Conclusion
References
18. Extraction of essential oils from coconut agro-industrial waste
18.1 Introduction
18.1.1 Coconut production and economic potential
18.1.2 Coconut agro-industrial waste and its problems
18.1.3 Coconut agro-industry residual potential in biorefineries utilization
18.1.4 Coconut agro-industrial waste challenges and opportunities
18.2 Chemical composition of essential oils
18.3 Extraction of essential oils
18.3.1 Essential oils extraction is conducted using two major techniques
18.4 Standard methods of extracting essential oil
18.4.1 Cold pressing
18.4.2 Solvent extraction
18.4.3 The "effleurage" method
18.4.4 Distillation
18.4.5 Extraction with supercritical gases
18.5 Extraction of essential oil from coconuts industrial waste
Calculations
18.5.1 Gas chromatography-flame ionization detector (GC-FID) analysis of essential oil
18.5.2 Gas chromatography-mass spectrophotometry (GCMS)
18.6 Volatile constituents of coconut industrial waste
18.6.1 Composition of volatile constituents
18.6.2 Structure of the major volatile compounds
18.7 Conclusion
References
19. Extraction of cellulose from agro-industrial wastes
19.1 Introduction
19.2 Cellulose
19.2.1 Structure
19.2.2 Chemical and mechanical properties
19.2.3 Sources of cellulose
19.3 Potential waste sources of cellulose
19.4 Cellulose extraction techniques
19.4.1 Cellulose fiber extraction
19.4.2 Cellulose microfibril/nanofibril extraction
19.4.3 Cellulose nanocrystal extraction
19.5 Applications
19.5.1 Applications of cellulose fiber
19.5.2 Applications of cellulose nanoparticles
19.6 Concluding remarks
References
Index

Citation preview

  

Extraction of Natural Products from Agro-industrial Wastes

  

Extraction of Natural Products from Agro-industrial Wastes A Green and Sustainable Approach Edited by

Showkat Ahmad Bhawani Faculty of Resource Science and Technology, Universiti Malaysia Sarawak (UNIMAS), Kota Samarahan, Sarawak, Malaysia

Anish Khan Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, Saudi Arabia

Fasihuddin Badruddin Ahmad Universiti Malaysia Sarawak, Sarawak, Malaysia

Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2023 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. ISBN: 978-0-12-823349-8 For Information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals Publisher: Susan Dennis Editorial Project Manager: Aera F Gariguez Production Project Manager: Rashmi Manoharan Cover Designer: Matthew Limbert Typeset by Aptara, New Delhi, India

  

Contents Contributors....................................................................................... xiii 1 Introduction to agro-industrial waste.........................................1 Abu Tariq, Showkat Ahmad Bhawani, Abdul Moheman and Khalid M. Alotaibi

1.1 Introduction................................................................................1 1.2 Types and sources of agro-industrial wastes................................2 1.3 Problems of agro-industrial wastes..............................................3 1.4 Benefits, recycle, and reuse of agro-industrial wastes..................4 1.5 Conclusion and future perspective.............................................11 References ........................................................................................... 11

2 Introduction to natural product ................................................ 19 Isaac John Umaru

2.1 Natural product ......................................................................... 19 2.2 Secondary metabolites .............................................................. 20 2.3 Alkaloid ..................................................................................... 20 2.4 Camptothecin............................................................................22 2.5 Triterpenes and steroids............................................................24 2.6 A source of natural product........................................................27 2.7 Conclusion ................................................................................ 30 References...........................................................................................30

3 Ionic liquids with microwave-assisted extraction of natural products......................................................................35 Irina Fierascu, Sorin Marius Avramescu, Elwira Sieniawska and Radu Claudiu Fierascu

3.1 Introduction .............................................................................. 35 3.2 Ionic liquids: general considerations, classification, and properties ........................................................................... 39 v

vi Contents

3.3 Ionic liquids as solvents for microwave extraction ..................... 41 3.4 Concluding remarks and future perspectives ............................ 46 Acknowledgments...............................................................................46 References...........................................................................................46

4 Pressurized liquid extraction of natural products....................53 Sorin Marius Avramescu, Irina Fierascu, Radu Claudiu Fierascu and Mihaela Cudalbeanu

4.1

Introduction .............................................................................. 53

4.2

Instant controlled pressure drop................................................63

4.3

Conclusions...............................................................................71

Acknowledgments...............................................................................71 References...........................................................................................71

5 Supercritical CO2 extraction of natural products.....................79 Saqib Farooq, Salma Farooq, Sajad Ahmad Rather and Tariq Ahmad Ganaie

5.1

Introduction .............................................................................. 79

5.2

Preparation of samples for supercritical CO2 extraction ............ 80

5.3

Supercritical CO2 extraction of bioactive compounds from natural products................................................................81

5.4

Supercritical CO2 and novel methods of food processing .......... 84

5.5

Controlled puffing in extrusion..................................................84

5.6

Removal of hexane from soybean oil ......................................... 85

5.7

Environmental applications of supercritical CO2 extraction ...... 85

5.8

Conclusion................................................................................86

References...........................................................................................86

6 Solvent extraction of natural products.....................................91 Abul Hasnat, Abdul Moheman, Mohd Amil Usmani, Mohd Azim Ansari, Showkat Ahmad Bhawani, Abu Tariq and Khalid M. Alotaibi

6.1

Introduction .............................................................................. 91

6.2

Sample preparation...................................................................92

Contents

6.3

Extraction methods ................................................................... 93

6.4

Determination of phytochemicals............................................100

6.5

Separation methods.................................................................101

6.6

Structure elucidation ............................................................... 104

6.7

Conclusion...............................................................................105

References ......................................................................................... 106

7 Extraction of flavonoids from agrowaste...............................111 Carlo Santulli

7.1 Introduction ............................................................................. 111 7.2 Extraction from agrowaste........................................................114 7.3 Conclusions.............................................................................124 References ......................................................................................... 125

8 Extraction of bioactive compounds from agro-industrial waste...........................................................................................131 Nayeem Ahmed

8.1 Introduction.............................................................................131 8.2 Extraction processes ................................................................ 134 8.3 Conclusion...............................................................................138 References ......................................................................................... 139

9 Extraction of antioxidants from agro-industrial waste.........143 Pir Mohammad Junaid, Aamir Hussain Dar, Ishfaq Hamid Dar, Shafat Ahmad Khan, Arshied Manzoor, Tariq Ahmad Ganaie and Rafeeya Shams

9.1 Introduction.............................................................................143 9.2 Antioxidants.............................................................................144 9.3 Extraction methods..................................................................146 9.4 Conclusion...............................................................................152 References ......................................................................................... 152

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Contents

10 Extraction of carotenoids from agro-industrial waste..........157 Sajad Ahmad Mir, Danish Rizwan, Rayees Ahmad Bakshi, Shoib Mohd Wani and Farooq Ahmad Masoodi

10.1

Introduction.............................................................................157

10.2

Plants as source of carotenoids ................................................ 158

10.3

Chemistry ................................................................................ 159

10.4

Carotenoids and their health benefits......................................159

10.5

Effects of food processing on carotenoids stability and/or bioavailability...............................................................161

10.6

Application of carotenoids in food industry.............................164

10.7

Extraction of carotenoids from agro-industrial waste...............164

10.8

Conventional extraction techniques ........................................ 166

10.9

Nonconventional extraction techniques .................................. 167

10.10 Conclusion...............................................................................172 References ......................................................................................... 172

11 Extraction of lycopene from agro-industrial waste...............179 Mohd Aaqib Sheikh, Nadira Anjum, Amir Gull, Charanjiv Singh Saini and Harish Kumar Sharma

11.1 Introduction.............................................................................179 11.2 Lycopene sources.....................................................................180 11.3 Role of lycopene in human health............................................181 11.4 Extraction and purification ...................................................... 185 11.5 Conclusion...............................................................................193 References ......................................................................................... 193

12 Extraction of natural dyes from agro-industrial waste.........197 Mohd Jameel, Khalid Umar, Tabassum Parveen, Iqbal M.I. Ismail, Huda A. Qari, Asim Ali Yaqoob and Mohamad Nasir Mohamad Ibrahim

12.1 Introduction.............................................................................197 12.2 Different methods of extraction of natural dyes ....................... 198

Contents

12.3 Various sources of natural dyes................................................200 12.4 Some demerits related to natural dyes.....................................204 12.5 Biological methods for production of various pigments...........206 12.6 Applications.............................................................................207 12.7 Conclusion...............................................................................210 Acknowledgments..............................................................................211 References..........................................................................................211

13 Extraction of lignin from agro-industrial waste.....................217 Asim Ali Yaqoob, Mohamad Nasir Mohamad Ibrahim, Mohammed B. Alshammari, Akil Ahmad, Khalid Umar and Mohd Rashid

13.1 Introduction.............................................................................217 13.2 Source of lignin ........................................................................ 219 13.3 Extraction of lignin by using various methods ......................... 222 13.4 Biochemistry of extracted lignin from agro-industrial waste....225 13.5 Challenges and future outlook.................................................226 13.6 Conclusions.............................................................................226 Acknowledgment...............................................................................227 Conflicts of interest............................................................................227 References.........................................................................................227

14 Extraction of fatty acids from agro-industrial waste and its significance............................................................................233 Abul Hasnat, Abdul Moheman, Mohd Amil Usmani and Showkat Ahmad Bhawani

14.1

Introduction ............................................................................ 233

14.2

Characteristics of fatty acids .................................................... 234

14.3

Fatty acids from agro-industrial waste ..................................... 236

14.4

Processing of deodorizer (DO) distillate .................................. 237

14.5

Conclusion .............................................................................. 240

References.........................................................................................240

ix

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Contents

15 Extraction of pectin from agro-industrial waste....................243 Arshied Manzoor, Bisma Jan, Rafeeya Shams, Qurat Ul Eain Hyder Rizvi, Aamir Hussain Dar, Saghir Ahmad, Shafat Ahmad Khan and Pir Mohammad Junaid

15.1 Introduction ............................................................................ 243 15.2 Basic structure and classification of pectin .............................. 245 15.3 Properties of pectin..................................................................247 15.4 Sources and extraction of pectin from agro-industrial wastes..249 15.5 Pectin extraction from agro-industrial waste as affected by the parameters: pH, temperature, and time ........................ 254 15.6 Conclusion .............................................................................. 255 Acknowledgment...............................................................................255 References.........................................................................................255

16 Extraction of cellulosic fibers from date palm by-products..261 Lobna A. Elseify, Mohamad Midani, Tamer Hamouda, Ramzi Khiari and Ahmed H. Hassanin

16.1 Introduction.............................................................................261 16.2 Materials and methods............................................................262 16.3 Results and discussion.............................................................267 16.4 Optimum conditions................................................................274 16.5 Conclusions.............................................................................275 Acknowledgments ............................................................................. 276 References ......................................................................................... 276

17 Recent developments in extraction of keratin from industrial wastes........................................................................281 Fayyaz Salih Hussain and Najma Memon

17.1 Introduction.............................................................................281 17.2 Sources of keratin protein........................................................282 17.3 Structure keratin......................................................................282

Contents

17.4 Extraction of keratin.................................................................283 17.5 Conclusion .............................................................................. 297 References.........................................................................................297

18 Extraction of essential oils from coconut agro-industrial waste...........................................................................................303 Isaac John Umaru, Hauwa A. Umaru and Kerenhappuch Isaac Umaru

18.1 Introduction ............................................................................ 303 18.2 Chemical composition of essential oils....................................307 18.3 Extraction of essential oils........................................................307 18.4 Standard methods of extracting essential oil............................308 18.5 Extraction of essential oil from coconuts industrial waste ........ 310 18.6 Volatile constituents of coconut industrial waste......................311 18.7 Conclusion...............................................................................316 References..........................................................................................316

19 Extraction of cellulose from agro-industrial wastes..............319 Syed Zubair Ali, Md Khalid Nahian and Md Enamul Hoque

19.1 Introduction.............................................................................319 19.2 Cellulose..................................................................................320 19.3 Potential waste sources of cellulose ......................................... 323 19.4 Cellulose extraction techniques...............................................324 19.5 Applications.............................................................................339 19.6 Concluding remarks.................................................................341 References ......................................................................................... 341

Index.................................................................................................. 349

xi

  

Contributors Akil Ahmad Chemistry Department, College of Sciences and Humanities, Prince Sattam Bin Abdulaziz University, Al-Kharij, Saudi Arabia Nayeem Ahmed Department of Chemistry, University of Kashmir, Srinagar, India Saghir Ahmad Department of Post-Harvest Engineering and Technology, Faculty of Agricultural Sciences, A.M.U., Aligarh, Uttar Pradesh, India Khalid M. Alotaibi Department of Chemistry, College of Science, King Saud University, Riyadh, Kingdom of Saudi Arabia Mohammed B. Alshammari Chemistry Department, College of Sciences and Humanities, Prince Sattam Bin Abdulaziz University, Al-Kharij, Saudi Arabia Nadira Anjum Division of Food Science and Technology, Sher-e-Kashmir University of Agriculture Sciences and Technology, Chatha, Jammu, Jammu & Kashmir, India Azim Ansari Department of Chemistry, Gandhi Faiz-E-Aam College, Shahjahanpur (Affiliated to Mahatma Jyotiba Phule Rohilkhand University, Bareilly), Uttar Pradesh, India Sorin Marius Avramescu Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, Bucharest, Romania; Research Center for Environmental Protection and Waste Management, University of Bucharest, Bucharest, Romania Rayees Ahmad Bakshi Department of Food Science and Technology, University of Kashmir Hazratbal Srinagar, Srinagar, Jammu and Kashmir, India Showkat Ahmad Bhawani Faculty of Resource Science and Technology, Universiti Malaysia Sarawak (UNIMAS), Kota Samarahan, Sarawak, Malaysia xiii

xiv

Contributors

Mihaela Cudalbeanu Research Center for Environmental Protection and Waste Management, University of Bucharest, Bucharest, Romania Aamir Hussain Dar Department of Food Technology, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir, India Ishfaq Hamid Dar Department of Post-Harvest Engineering and Technology, Faculty of Agricultural Sciences, A.M.U., Aligarh, Uttar Pradesh, India Lobna A. Elseify Department of Materials Engineering, German University in Cairo, Cairo, Egypt Salma Farooq Department of Food Technology, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir, India Saqib Farooq Department of Food Technology, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir, India Irina Fierascu National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM, Bucharest, Romania; University of Agronomic Sciences and Veterinary Medicine of Bucharest, Bucharest, Romania Radu Claudiu Fierascu National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM, Bucharest, Romania; Department of Science and Engineering of Oxide Materials and Nanomaterials, University “Politehnica” of Bucharest, Bucharest, Romania Tariq Ahmad Ganaie Department of Food Technology, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir, India Amir Gull Department of Food Science and Technology, University of Kashmir, Srinagar, Jammu & Kashmir, India Tamer Hamouda Textile Research Division, National Research Center, Cairo, Egypt Abul Hasnat Department of Chemistry, Gandhi Faiz-E-Aam College, Shahjahanpur (Affiliated to Mahatma Jyotiba Phule Rohilkhand University, Bareilly), Uttar Pradesh, India

Contributors

xv

Ahmed H. Hassanin Materials Science and Engineering Department, Egypt-Japan University of Science and Technology (E-JUST), New Borg El-Arab City, Egypt; Department of Textiles Engineering, Alexandria University, Alexandria, Egypt Md Enamul Hoque Department of Biomedical Engineering, Military Institute of Science and Technology (MIST), Dhaka, Bangladesh Fayyaz Salih Hussain National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, Pakistan Mohamad Nasir Mohamad Ibrahim Materials Technology Research Group (MaTRec), School of Chemical Sciences, Universiti Sains Malaysia, Minden, Penang, Malaysia Iqbal M.I. Ismail Centre of Excellence in Environmental Studies, King Abdulaziz University, Jeddah, Makkah, Saudi Arabia; Department of Chemistry, King Abdulaziz University, Jeddah, Makkah, Saudi Arabia Mohd Jameel Department of Zoology, Aligarh Muslim University, Aligarh, Uttar Pradesh, India Bisma Jan Department of Food Technology, School of Interdisciplinary Sciences, Jamia Hamdard University, New Delhi, India Pir Mohammad Junaid Department of Post-Harvest Engineering and Technology, Faculty of Agricultural Sciences, A.M.U., Aligarh, Uttar Pradesh, India Shafat Ahmad Khan Department of Food Technology, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir, India Ramzi Khiari Research Unity of Applied Chemistry & Environment, University of Monastir, Monastir, Tunisia; Department of Textile, Higher Institute of Technological Studies of Ksar Hellal, Monastir, Tunisia; CNRS, University of Grenoble Alpes, Grenoble, France Arshied Manzoor Department of Post-Harvest Engineering and Technology, Faculty of Agricultural Sciences, A.M.U., Aligarh, Uttar Pradesh, India

xvi Contributors

Farooq Ahmad Masoodi Department of Food Science and Technology, University of Kashmir Hazratbal Srinagar, Srinagar, Jammu and Kashmir, India Najma Memon National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, Pakistan Mohamad Midani Department of Materials Engineering, German University in Cairo, Cairo, Egypt; Wilson College of Textiles, NC State University, Raleigh, NC, United States Sajad Ahmad Mir Department of Food Science and Technology, University of Kashmir Hazratbal Srinagar, Srinagar, Jammu and Kashmir, India Abdul Moheman Department of Chemistry, Gandhi Faiz-E-Aam College, Shahjahanpur (Affiliated to Mahatma Jyotiba Phule Rohilkhand University, Bareilly), Uttar Pradesh, India Md Khalid Nahian Department of Metallurgical & Materials Engineering, The University of Alabama, Tuscaloosa, AL, United States Tabassum Parveen Department of Botany, Aligarh Muslim University, Aligarh, India Huda A. Qari Centre of Excellence in Environmental Studies, King Abdulaziz University, Jeddah, Makkah, Saudi Arabia; Department of Biological Science, King Abdulaziz University, Jeddah, Makkah, Saudi Arabia Mohd Rashid Materials Technology Research Group (MaTRec), School of Chemical Sciences, Universiti Sains Malaysia, Minden, Penang, Malaysia Sajad Ahmad Rather Department of Food Science and Technology, University of Kashmir, Hazratbal, Srinagar, Jammu and Kashmir, India Qurat Ul Eain Hyder Rizvi Department of Food Technology, Eternal University, Sirmour, Himachal Pradesh, India Danish Rizwan Department of Food Science and Technology, University of Kashmir Hazratbal Srinagar, Srinagar, Jammu and Kashmir, India

Contributors

xvii

Charanjiv Singh Saini Department of Food Engineering and Technology, Sant Longowal Institute of Engineering & Technology, Longowal, Punjab, India Carlo Santulli Università di Camerino, School of Science and Technology, Camerino, Italy Rafeeya Shams Division of Food Science and Technology, Sher-e-Kashmir University of Agricultural Sciences & Technology of Jammu, J&K, India Harish Kumar Sharma Department of Chemical Engineering, National Institute of Technology, Agartala, Tripura, India Mohd Aaqib Sheikh Department of Food Engineering and Technology, Sant Longowal Institute of Engineering & Technology, Longowal, Punjab, India Elwira Sieniawska Department of Pharmacognosy with Medicinal Plant Unit, Medical University of Lublin, Lublin, Poland Abu Tariq Department of Chemistry, Aligarh Muslim University, Aligarh, Uttar Pradesh, India Khalid Umar Materials Technology Research Group (MaTRec), School of Chemical Sciences, Universiti Sains Malaysia, Minden, Penang, Malaysia Hauwa A. Umaru Federal University Wukari, Taraba State, Nigeria; Modibbo Adama University Yola, Adamawa State; University of Maiduguri Borno State Isaac John Umaru Federal University Wukari, Taraba State, Nigeria; Modibbo Adama University Yola, Adamawa State; University of Maiduguri Borno State Kerenhappuch Isaac Umaru Federal University Wukari, Taraba State, Nigeria; Modibbo Adama University Yola, Adamawa State; University of Maiduguri Borno State Mohd Amil Usmani Department of Chemistry, Gandhi Faiz-E-Aam College, Shahjahanpur (Affiliated to Mahatma Jyotiba Phule Rohilkhand University, Bareilly), Uttar Pradesh, India Shoib Mohd Wani Department of Food Science and Technology, University of Kashmir Hazratbal Srinagar, Srinagar, Jammu and Kashmir, India

xviii

Contributors

Asim Ali Yaqoob Materials Technology Research Group (MaTRec), School of Chemical Sciences, Universiti Sains Malaysia, Minden, Penang, Malaysia Syed Zubair Ali Department of Materials & Metallurgical Engineering, Bangladesh University of Engineering & Technology (BUET), Dhaka, Bangladesh

1

  

Introduction to agro-industrial waste Abu Tariq a, Showkat Ahmad Bhawani b, Abdul Moheman c and Khalid M. Alotaibi d a DEPARTMENT

PRADESH, INDIA

OF CHEMISTRY, ALIGARH MUSLIM UNIVERSITY, ALIGARH, UTTAR b FACULTY

OF RESOURCE SCIENCE AND TECHNOLOGY, UNIVERSITI

MALAYSIA SARAWAK (UNIMAS), KOTA SAMARAHAN, SARAWAK, MALAYSIA c DEPARTMENT

OF CHEMISTRY, GANDHI FAIZ-E-AAM COLLEGE, SHAHJAHANPUR

(AFFILIATED TO MAHATMA JYOTIBA PHULE ROHILKHAND UNIVERSITY, BAREILLY), UTTAR PRADESH, INDIA

d DEPARTMENT

OF CHEMISTRY, COLLEGE OF SCIENCE,

KING SAUD UNIVERSITY, RIYADH, KINGDOM OF SAUDI ARABIA

1.1 Introduction The growth in world population resulted in increased demand of commodities required for the sustenance of life. The increased demand and consumption of resources lead to the repletion of forests and fertile land in turn giving space for the establishment and development of industries. Agricultural or agro-industries is one such establishment which is highly responsible for growth and development at one point and destroying ecological balance at other. However, agricultural reforms were witnessed on large scale throughout the globe, this is due to the increase in demand of food. The quality of production is improved through the use of advanced instruments and fertilizers which in turn need heavy industries to produce them resulting in fast paced development of food and agricultural industry. Agricultural sectors industrialization results in significant ecological and environmental dis-balance; it is estimated that around 5 million metric tonnes of biomass is annually obtained from agricultural activities [1]. It is well evident that global sustainability challenges are very much intertwined, for instance ecological imbalance caused by pollution, climatic changes, poverty, loss in biodiversity, food security and energy as well. In general, organic wastes arising from the agro-industries forms major portion of sources creating pollution and are of two types: (1) agricultural and forestry and (2) industrial activities. Forestry and agricultural activities tend to produce organic wastes such as slurry from livestock, manure, remains of crops in the form of husk, leaves, etc., pruning of plants also contribute in organic waste and the maintenance of woodland produce waste as well. On the other hand, agroindustries produce a large amount of organic wastes in the form of by-products from agricultural and food industries such as legumes, coffee dregs, degummed fruits, wool sludge, milk serum Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach. DOI: https://doi.org/10.1016/B978-0-12-823349-8.00008-3 c 2023 Elsevier Inc. All rights reserved. Copyright 

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Extraction of Natural Products from Agro-industrial Wastes

FIGURE 1.1 Representation of categories and examples of agro-industrial wastes.

and cellulose etc. These by-products have high nutritional values, therefore are considered for quality control [2]. The agricultural sector is producing approximately 140 billion tonnes of biomass every year in the world [3,4]; moreover, a substantial part of it is considered as waste without conflicting with the availability of food, such as roots, leaves, stalks, bark, straw residues, seeds, wood, bagasse and animal residues as well. The general composition of agro-industrial wastes are complex polysaccharides and proteins, various polyphenols, carbohydrates, oils, fat etc., with high values of chemical oxygen demand (COD), biological oxygen demand (BOD) and suspended solids [5,6]. The wastes obtained from food based agro-industries are rich in nutrients which could be utilized for various other purposes including production of renewable energy. A large portion of these agro-industrial wastes remain untreated and underutilized, burning, dumping or unplanned landfilling remains the only disposing options [7]. Such indecent disposal of agro-industrial wastes increases the greenhouse gases which results in different climate change problems.

1.2 Types and sources of agro-industrial wastes Agro-industrial wastes could be divided into two major categories; agricultural residues and industrial wastes (Fig. 1.1).

1.2.1 Agricultural residues Agricultural residues are the wastes obtained from various agricultural activities performed. It is further divided into field residues and process residues. Field residues are the wastes that are found on the farm lands or agricultural fields after the cultivation or harvesting of crop is completed. The field residues include leaves, stems, stalks, seed pods and other such material

Chapter 1 r Introduction to agro-industrial waste

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related to crops. Whereas, process residues can be defined as the wastes obtained after the processing of crops into valuable resources. These wastes comprise of husks, seeds, leaves, stem, shell, pulp, stubble, peel, roots, bagasse, molasses, etc. The obtained residues could be utilized as animal feed, in soil improvement, manure and fertilizers, manufacturing and various other processes. It is observed that a large amount of field residues are generated over the crop harvesting and processing period which unfortunately remains underutilized. If the same is used in controlled manner may enhances the field output, irrigation proficiency and controlled soil erosion. The agricultural wastes are characterized on the basis of their availability and properties which are found to be different from the other solid fuels such as wood, charcoal and char [8]. Moreover, livestock waste which includes cattle dung, poultry excreta, food remains, etc., further add-up to the already existing piles of wastes.

1.2.2 Industrial wastes A considerable amount of organic wastes and related effluents are produced annually through the agro-industrial activities specifically food processing industries such as coffee, juice, meat, chips, confectionary and different other fruit industries. The obtained wastes have both harmful and beneficial sides. At one point the untreated wastes could be causing great concern for different types of pollution; however, on the other hand, the nutrient rich organic wastes could be beneficially utilized for different purposes such as manure and fertilizers, clean energy, enzyme production etc. The fruits and vegetables waste are lignocellulosic in nature and are comprised of polysaccharides of different compositions such as cellulose and hemi-cellulose, an aromatic polymer lignin, ash, in addition to it, other nutrients such as proteins, lipids, pectins, nitrogen, carbon, polyphenols, etc. are present as well. These agro-industrial wastes have great potential in producing biogas, bioethanol or different other commercially viable products through biochemical treatment of the same owing to the fact that they contains high values of Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD), and other suspended solid particles. Most of the industrial residues remain untreated and unutilized, that cause the chronic effect on the environment and the health human and animals.

1.3 Problems of agro-industrial wastes The agro-industrial sector which includes food industry generates a huge amount of residues all around the year in the form of solid, liquid or gases wastes. The said residues are multicomponent, which totally depends on source of raw materials, operations, processing steps and nature of components as well. The residues creates ruckus in the environment in the form of waste water, solid residues and air pollution, accompanied by noise pollution as well. Among these three types of pollution, water pollution seems to be the most serious threat. It is due to the fact that a huge volume of water is utilized in various agro-industries for washing of raw materials, process steam, cooling, cleaning and as an ingredient in syrups and brine as well. The oil industry if considered as one example produces a large amount of processed wastes from the extraction of oils from seeds, known as oil cakes. The industry is considered as one of the most pollution producing industry as during the oil production huge amount of residues

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Extraction of Natural Products from Agro-industrial Wastes

containing oil, grease, fat, suspended and dissolved solids are released into the environment. Similarly, other industries are equally responsible in increasing pollution in one form or other.

1.4 Benefits, recycle, and reuse of agro-industrial wastes Since the origin of human kind and the evolution agricultural activities, people had been utilizing the biowaste materials such as fruits, peels, seeds, slurry and manure, etc. to improve soil for various agricultural processes. The advantage lies in the fact that the residues obtained from agro-industrial wastes are rich in nutrients which could be utilized for various purposes apart from agriculture that includes bioenergy, biofuels, organic materials in the form of preservatives, additives etc. The recycling of biowastes helped in continuous recycling of nutrients in earth which improves the level of organic matters present in the earth crust. The succeeding portion of the current write up will shed some light on the advantages of these agro-industrial wastes and their by-products.

1.4.1 Bioconversion of agro-industrial wastes to industrially important enzymes It is evident that agro-industrial wastes are highly rich in nutritional values and facilitates the growth of microbes. The waste obtained from agro-based food industries are rich in nutrients, thereby giving rise to the breeding of various micro-organisms leading to a variety of serious diseases. This all happen due to the under or no treatment of these obtained agro-based waste materials. These materials could serve as the base for the production of a large variety of valueadded products or as a source of renewable energy source. Most of the obtained agro-industrial wastes are lignocellulosic in nature rich polysaccharides such as cellulose and hemicellulose and an aromatic polymer called lignin. These materials are high in various other nutrients such as lipids, proteins, pectins, and various types of polyphenols. The various value added products of agricultural residual wastes includes enzymes which are highly required in industries for the production of other valuable resources. These wastes may consist of sugarcane bagasse, corn cob, and rice bran, which has been consistently investigated for the production of enzymes via different fermentation procedures [9]. Enzymes are biological catalysts that are used in various industries ranging from brewing to paper, pulp, baking and detergent manufacturing. The various types of enzymes produced at industrial level through these agro-industrial wastes are as follows:

1.4.1.1 Enzyme production at industrial scale 1.4.1.1.1 Enzymes that act on polysaccharides a) α-amylase: Alpha amylase is also known as endo-1,4-α-D-glucanglucanohydrolase EC 3.2.1.1. These belongs to a class of enzymes that randomly cleave α-1, 4 linkages between neighboring glucose subunits in polysaccharides that results in the formation of short chain oligomers and α-limit dextrans. A wide range of applications are attached to Alpha

Chapter 1 r Introduction to agro-industrial waste

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Table 1.1 List of other polysaccharide acting enzymes and its value-added applications. Enzymes

Microbial source

Applications

References

Cellulase

Trichoderma reesei, Schizophyllum commune, Melanocarpus sp., Aspergillus sp., Penicillium sp., Fusarium sp., Clostridium thermocellum, Bacillus circulans, Proteus vulgaris, Klebsiella pneumonia, Escherichia coli, and Cellulomonas sp. Filamentous fungi and bacterials species (A. niger and A. terreus) Streptococcus salivarius, Actinomyces viscosus, Kluyveromyces fragilis, Chrysosporium pannorum, Penicillium sp., and Aspergillus niger Bacillus sp., (B. subtitlis strains), Aspergillus sp., Clostridium sp., Pencillium sp., and Sterptomyces sp. Kluyveromyces lactis, Kluyveromyces fragilis, A. niger, and A. oryzae Candida pseudotropicalis

Bread, brewing, textiles, detergents, paper, and pulp sectors

[21–24]

Food, biomedical, animal feed, and bioethanol Production of bioethanol, citric acid, butanediol and lactic acid

[25–28]

Paper, food, oil, feed, and textile industries and pulp

[30–35]

Dairy and food industry

[36,37]

Xylanase Inulinase

Mannanase

Lactase

[29]

amylase, ranging from detergent manufacturing to production of beer, paper, bread, pulp and various pharmaceutical products [10]. Submerged fermentation techniques are applied to produce industrial Alpha amylses, wherein Bacillus and Aspergillus species are used during fermentation [11]. A variety of other bacterial and fungal species are studied for the production of Alpha amylase enzymes showing different strong characteristics such as thermos and alkali-stability, halo and psycho tolerance [12–14]. Various other researchers such as Francis et al. 2003, Rajagopalan and Krishnan 2008 [11,15] were able to produce Alpha amylase enzymes with enhanced properties. b) Amyloglycosidase (AMG): This is also known as glucoamylase or E.C. 3.1.2.3 with a capacity to cleave the α-1, 4 linkages of starch to produce glucose molecules. It also have tendency to break α-1, 6 glycosidic bonds at very slower rate [16]. The applications of AMG range from food, brewing to bakery industries [17]. Industrial production could be achieved via use of A. Niger and A. Oryzae strains; however, Bacillus sp., Rhizopus sp., and Saccharomyces sp. can also be used to produce industrial AMG [16,18,19]. c) Invertase: A glycoprotein that is also known as β-fructofuranosidase (EC.3.2.1.26) which cleave sucrose to dextrose and fructose. Saccharomyces cerevisiae is the main microbial entity used for the production of industrial invertase [20]. The application of invertase is the production of invert sugar which was earlier obtained from acid hydrolysis. Various other enzymes that could be obtained industrially and are considered valuable for value added products are mentioned in Table 1.1.

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Extraction of Natural Products from Agro-industrial Wastes

1.4.1.1.2 Enzymes that act on proteins a) Protease: These are the enzymes which undergoes proteolysis in polypeptide chains by hydrolyzing the peptide bonds of amino acids. They are considered as one of the most important hydrolytic enzymes of all time since the beginning of studies of enzymes as it plays an active role in cellular metabolism and various industrial applications as well. Various class of protease such as serine protease subtilisin A, Neutrase and trypsin are of high commercial value. Genetically modified strains of Bacillus and Aspergillus are applied to produce protease at industrial scale [38,39]. A oryzae was used to produce protease via culture of soyabeans [40]. Protease could also be produced by using tomato pomace and Jatropha seed cake [41,42]. b) Transglutaminase: They are also referred as protein-glutamine-γ -glutamyl transferase produced in mammalian muscle cells and microbial cells as well, which catalyze the formation of isopeptide bonds between the γ -carboxyamide groups of glutamine residues and the γ -amino groups of the lysine residues [43]. Streptoverticillium mobaraense strains are used to produce tarnsglutaminase enzymes at industrial scale [44]. Pythium sp. and Phytophthora sp. are two other fungal species which are commercially viable for the production of transglutaminase enzymes. Various industries such as flour baked goods, processed milk/cheese/meat and fish, cosmetics, leather finishing, wool and gelled food products found transglutaminase as important base product [45,46].

1.4.1.2 Other industrially important enzymes a) Lipase: Lipase are the enzymes responsible for the cleavage and mobilization of lipids within the cells. On industrial scale lipase catalyze variety of processes which includes hydrolysis, alcoholysis, aminolysis, acidolysis, esterification, and transesterification. Owing to this characteristic, lipase is considered important in industries such as detergents, bakery, dairy, oil, biopolymers, biodiesel, pharmaceuticals, and in the treatment of waste effluents of fat [47]. Thermomyces lanuginosus, Rhizomucor miehei, Bacillus, Serratia, Psuedomonas, and Staphylococcus are various species used for the production of lipase at industrial scale [48–50]. b) Phytase: Suzuki et al. in 1907 discovered phytase for the very first time from hydrolysis of rice bran [51]. It is classified as 3-phytase, 4-phytase, and 5-phytase based on the position of phosphate groups [52]. Aspergillus niger is used for the commercial production of phytase enzyme. Nocardia sp. and Klebsiella sp. were also used for the production of phytase enzymes at industrial scale [53,54].

1.4.2 Agro-industrial wastes as sources of bioactive compounds for food, fermentation, and drug industries Bioactive compounds are those substances which are biologically active and modulate metabolic processes for better health conditions. These compounds includes mainly phenols,

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carotenoids, phytosterols, organosulfurs and tocopherols [55,56], as well as secondary metabolites such as flavonoids, saponins, organic acids, thiosulfonates, and glucosinolates. These bioactive compounds are found in fruits, vegetables and whole grains with interesting antioxidant and antimicrobial properties. These compounds have shown applicability in various industries such as vegetable oils, meat and by-products processing, seafoods, bakery and dairy, and to ethanolic fermentation as well. These naturally occurring bioactive compounds are extensively investigated for various applications in wide range of human diseases or disorders. These compounds effectively interact with the likes of proteins, DNA and other molecules of biological origin to produce the results which are pleasing and desired, thus paving way for the designing and production of natural therapeutic agents [57]. Lemes et al. recently discovered the use of bioactive peptides as new generation of biologically active regulators that effectively prevents microbial degradation and oxidation in foods [58]. Flavonoids, tannins, anthocyanins and different alkaloids are variety of polyphenols obtained from fruits, vegetables and plants that have industrial significance. These phenolic complexes can be obtained from barks, shells, husk, leaves, and roots [59]. One such example is that of tomato peels and seeds, rich in bioactive compounds such as carotenes, sterols, tocopherols, terpenes and polyphenols [60], which is high in dietary fiber with excellent antioxidant and antimicrobial activities.

1.4.3 Agro-industrial wastes and their utilization using solid state fermentation Solid state fermentation (SSF) is a biotechnological process in which microorganisms are allowed to grow on solid substrates or nonsoluble materials in the very absence of or near absence of free water [61]. The solid substrates utilized in SFS are cereal grains which include corn, rice, barley and wheat, legume seeds, lignocellulosic materials such as wood shavings, straws, saw dust, etc. and white brans. Factors such as solid substrates, microorganisms, water supply, temperature, aeration and fermenter are considered as useful parameters for successful solid state fermentation processes. SSF is a multistep process that includes; a) Solid substrate and microorganism selection b) Pretreatment of solid substrates to improve its quality through chemical, mechanical, or biochemical treatments c) Hydrolysis of primarily polymeric substrates d) Fermentation of hydrolyzed products e) Purification and quantification of the resultant via downstreaming SSF has been in center of attraction due to its tendency to convert variety of organic wastes obtained from agro-industrial sources into large amount of value-added products [62,63]. Different value-added products such as organic acids, enzymes, bioethanol, biofertilizers, pigments and antibiotics are reported to be obtained from agro-industrial waste following SSF. Similarly, composting and ensiling are few natural microbiological activities which are reported in the light of SSF [64]. Agro-industries such as food, detergent, textile, beer and wine, animal feed and paper

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Extraction of Natural Products from Agro-industrial Wastes

are the one that contributes in the production of solid wastes which further could be used as solid substrates in SSF. SSF has been applied on large scale of agro-industrial wastes to produce variety of value-added resources such as biofuels, antioxidants, enzymes, mushrooms and antibiotics.

1.4.4 Bioenergy and biorefineries Fossil energy sources such as coal, petroleum products, natural gases, etc. are the backbone of economic growth via production of various value added resources such as electricity, fuels and other required things. The excessive use of fossil fuels makes us think about the suitable renewable alternative. Bioethanol, is one such alternative which is obtained from biomass arising from the agro-industrial wastes. Bioethanol can be achieved from agro-industrial waste through biorefineries which undergoes various processes such as fermentation, pyrolysis, physical treatments, physico-chemical treatments, enzymatic degradation, ultrasound-assisted treatments, etc. For the same purpose biorefineries are established and production of biofuels, bioactive compounds and biomaterials are achieved. Various researchers have extensively worked on the production of biofuels from the agroindustrial wastes such as rice straw, sweet potato, potato waste, corn stalks, sawdust, sugar beet waste, sugar cane bagasse, etc. [65–67]. Bioethanol is the most common of all renewable bioenergy that can be obtained through pretreatment, saccharification, fermentation and distillation [68]. Bioethanol is also produced from lignocellulosic compositions [69–71]. Saini et al. [72] and Mushimiyimana and Talapragada [73] reported that various agricultural waste materials such as potato peel, carrot peel, and onion peel can be used for the production of bioethanol for second generation through fermentation technique using yeast Saccharomyces cerevisiae. Biogas, another form of bioenergy was produced by using various agricultural wastes obtained from different sources as well as two weeds namely Typha angustifolia L. and Eichornia crassipes solms [74]. The biomass rich in lignocellulosic materials is a potential source of variety of organic compounds, glucose, xylose, mannose and arbinose which on anaerobic degradation produce biogas [75]. The steps involved in the anaerobic degradation are; hydrolysis, acidification, acetate production and methane using a microorganism consortium [76]. The resultant products obtained are mixture of methane, carbon dioxide, carbon monoxide, hydrogen, ammonia and traces of hydrogen sulfide [77].

1.4.5 Green and sustainable separation of natural products from agro-industrial waste Biorefineries were set up to produce biofuels, bioenergy and biomaterials for agro-industrial biomass. For healthy environmental balance, it was very important to separate natural products through using green and sustainable separation processes. Recent studies show that green extraction and purification have been applied to reduce energy consumption, via using solvents and renewable components keeping the resultant product at high quality [78]. The very aim of this initiative is to obtained natural materials from agro-industrial wastes [79]. The various value-added products from agro-industrial biomass such as essential oils, polyphenols and other

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medicinal friendly resources are extracted first followed by the lignoceluloses, waxes or polysaccharides via advanced separation and depolymerization processes. Supercritical CO2 (scCO2 ), subcritical water, microwave assisted acidolysis, gas expanded liquids and green solvents in general are mentioned by researchers for the extraction of various natural products [80]. The separation advantage showed by green solvents over regular solvents are numerous, supercritical fluids or near-supercritical fluids display outstanding properties such as mass transport, polarity and easiness of solvent removal once desired compound is extracted from the material [81]. Water is one of the most interesting solvent present, but a lot of compounds are insoluble in it thus limiting in applications. However, the use of subcritical water has shown potential for organic modification to depolymerize, gasify, hydrolyze and carbonize biomass for the production of a variety of biologically active compounds such as sugars, biogas and other important solid products [82,83]. The single extraction techniques have drawbacks that can be overcome by combining two or more green techniques integrating different strategies to achieve sustainable separation. For example, when high pressure solvent extraction is coupled with ultrasound-assisted treatment the temperature, time and consumption of solvent is substantially reduced [84,85]. The integration of two or more extraction/concentration process is very commonly used method, for instance, micro-wave and ultrasound technology was applied for removal of essential oil, pectin and polyphenols from orange waste present in agro wastes, without the addition of any solvents [86]. The nongreen chlorite method was successfully replaced by autoclavebased and ultrasonication pretreatments for the recovery of cellulose from oil palm bunches [87]. Apart from subcritical water, supercritical carbon dioxide (scCO2 ) is also successfully applied for extraction processes, scCO2 is a fluid with critical parameters of 31.3°C and 73 atm, thus providing miscibility to the variety of organic compounds, it is also considered cheap and highly available, high purity, low toxicity and have many other advantages for downstream processing for product purification and/or catalyst recycling [88]. Moreover, scCO2 has been widely applied in isolation and purification of chlorophylls, lipids, carotenoids, alkaloids, antioxidants from various matrices such as filter tea, spruce bark, grape, passiflora, coffee and cupuassu seed waste, tomato, and elderberry pomace [89–106]. In fact, green extraction, purification and modification of natural products obtained from agro-industrial wastes is considered as the sustainable approach to boost bioeconomy.

1.4.6 Agro-industrial wastes as fertilizers in aquaculture Aquaculture is one of the fastest growing fields in the world, where fishes and other aquatic animals are produced. Asia is among the world’s largest producer and about 90% of the global aquaculture production is from Asia. The production of aqua species is largely dependent on nutrients rich vegetation present in ponds. To obtain high yields of fishes, increase in quality and quantity of phytoplankton and zooplankton with improved water quality is done. Suitable environmental conditions are created by fertilization which is required for production of natural food for fishes. For this purpose, sugarcane by-products such as bagasse and molasses have been used owing to their potential as fertilizer. Another sugarcane by-product, pressmud is a popular

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manure used in aquaculture by aqua-farmers in India, its chemical composition is comparable with that of cattle dung. The two important nutrients which are required for fish production are phosphorous and nitrogen. Compositing is one approach which is used to obtain fertilizers for aquaculture. Compositing is a natural process of decomposition and recycling of organic materials obtained from agroindustrial wastes with environment friendly applications. Several methods have been used to obtain agro-industrial waste based composts that includes pilling or passive composting, aerated static piles, windrows, bins and in-vessel systems. Compost made for aquaculture is quite similar to humus in smell, appearance and touch. The finished compost is free from weeds and pathogens due to the tendency of compost to maintain ambient temperature. The obtained compost have a pH of 7.0 with 35%–50% moisture content, and a carbon–nitrogen ratio of 10:1 to 25:1, the organic content varies between 40% and 65%. Immature or unfinished compost is avoided by aqua-farmers due to possibility of presence of phytotoxins which may lead in death of phytoplankton plants. The conversion of fertilizers into fish flesh is obtained either by direct consumption of feed or stimulation of pond ecosystem that lead to enhanced autotrophic and heterotrophic production [107]. Common carp, an omnivore consume pressmud on a great dosage to give high yield [108]. Pressmud is cheaper than cattle dung when compared for cost effectiveness, around 26-30% cheaper than cattle dung [109]. Keshavnath et al. [110] reported that for carp production pressmud could be considered a potential and economical option. Other waste materials such as brewery waste and distillers dried grain can be considered as an alternative source of protein for fish meals in aqua-farming.

1.4.7 Other miscellaneous value-added applications Following are few value-added applications: Pigment production Agro-industrial waste materials have been utilized by various researchers for the production of microbial pigments through fermentation processes. Fruits by-products are highly recommended for the production of bio-based colors and pigments. Microbial pigments are biological pigments that have various advantages such as less toxic, biodegradable and eco-friendly when compared with the synthetic counterparts [111–114]. A large variety of species of microorganisms are used to produce biopigments such as Alteromonas rubra, Rugamonas rubra, Streptoverticillium rubrireticuli, Streptomyces longisporus, Serratia marcescens, Pseudomonas magneslorubra, Vibrio psychroerythrous, S. rubidaea, Vibrio gazogenes, etc. [115–117]. Monascus purpureus is a microorganism that is used to produce a yellow color pigments on fermentation of agro-industrial wastes. Citric acid production Large amount of agro waste is produced annually that are highly rich in carbohydrate and sugar contents. Variety of value-added products can be produced owing to the presence of large quantity of carbon content and other valuable nutrients. A novel method is required to cater the ever growing need of the citric acid, thus solid-state fermentation of agro-industrial wastes through

Chapter 1 r Introduction to agro-industrial waste 11

various microbial isolates is applied to produce organic acids including citric acids. More than 90% of global production of citric acid is obtained through fermentation. Researchers have found that pineapple wastes are better option for citric acid production via biomass-assistance than apple pomace [118]. Various other wastes such as orange peel were successfully utilized for citric acid production [119]. Food flavoring and preservative compounds Natural flavoring agents can be produced from agro-industrial wastes via microbial conversions thus making these wastes a low cost and sustainable resource for value added products. Vanillin is one such flavoring agent that is quite popular in food industry. Ferulic acid is another acid that is recovered from agro-industrial wastes specifically from agro-food industry by-products through biotechnological processes. Ascorbic acid or vitamin C is a potent natural product used in medicine and as food preservative can also be obtained from these wastes [120]. Brick formation Bricks are the building blocks of any construction, made up of clay bearing soil, sand and lime, can obtained either through fire hardening or air drying. Researches were made to produce bricks from different materials such as blast-furnace slag [121–123], float glass waste [124–128], fly ash, and sewage sludge ash [129–132]; moreover, coffee husk/grounds and sugarcane bagasse are considered as potential alternative additive to clay bricks. A large amount of agro-industrial wastes produced annually all over the globe consists of high lignocellulosic contents, thus can be considered as an alternative in building materials and additives. Demir [133] reported that agro wastes have various advantages to be used as potential biobricks.

1.5 Conclusion and future perspective Global perception of waste is rapidly changing with the change in advancement and technological developments. It is considered as dire need of the hour to preserve the environmental sustainability and conservation. Agro-industrial wastes falls in the disposal problem category creating pollution. Thus, a large number of processes have been introduced to utilize the agroindustrial wastes in order to reduce the pollution and producing large number of value added products. The list includes biofuel and biorefinery products, enzymes, pigments, organic acids, food flavoring agents, preservatives, bioactive compounds, etc.; moreover, agricultural composting, biodegradable PHA production are other aspects included in the very list. Therefore, a large amount of capital investment is required to carry out the abovementioned products to boost the commercial markets generating huge economical energy. To further enhance the quality of these value-added products and produce more such kinds, provide a gateway for researchers in future.

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Introduction to natural product Isaac John Umaru FEDERAL UNIVERSITY WUKARI, TARABA STATE, NIGERIA

2.1 Natural product Natural products are chemical substances produced by plants or animals, as well as chemical substances found in nature with particular pharmacological effects. Natural products are divided into several categories, including carbohydrates, lipids, proteins, nucleic acids, and others. They are commonly employed for traditional therapies based on herbal formulations for the treatment of many health problems such as body pain, exterior-relieving, digestive problems, blood regulating, physiological disorder swelling, and rheumatism. Despite the fact that this discovery yields beneficial products, the pharmaceutical sector virtually abandoned natural product discovery decades ago [1]. Natural products are classified into two types: primary and secondary metabolites. Primary metabolites, such as fermentation products (ethanol, acetic acid, citric acid, and lactic acid), cell constituents (lipids, vitamins, and polysaccharides), and the electron transport chain, are directly involved in normal growth, development, and reproduction. The term “primary metabolite” refers to intermediates of catabolic and anabolic pathways that occur in plants, share metabolic functions, and are required for plant survival. Amino acids, sugars, and fatty acids are among the compounds produced by these cycles. Small molecular weight compounds can form longer chains to form macromolecules such as protein, carbohydrate, lipids, and nucleic acids [2]. According to Hanson [3] and Sarker [4], the phrase “natural substance” refers to all substances of natural origin found in plants; however, secondary metabolites are the most common. Natural products are divided into three categories: primary metabolites, secondary metabolites, and polymeric molecules with a high molecular weight [3]. Nucleic acids, amino acids, and sugars are ubiquitous primary metabolites found in all cells and play an important role in cell metabolism and reproduction. Secondary metabolites, which are tiny compounds found in plants, play a vital role in their biological activity [5]. Secondary metabolites can be employed as natural chemicals in a variety of applications; therefore, natural product research focuses on identifying and evaluating them. These secondary metabolites, on the other hand, are not absolutely necessary for the producer organism’s growth and development. High molecular weight polymeric components including cellulose, lignin, and proteins, which make up the third group of natural chemicals, play an important role in plant cell structure [6]. Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach. DOI: https://doi.org/10.1016/B978-0-12-823349-8.00002-2 c 2023 Elsevier Inc. All rights reserved. Copyright 

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Plants’ medicinal value is conferred by secondary metabolites such as alkaloids, tannins, saponins, flavonoids, anthraquinones, glycosides, terpenes, essential oils, and resins. A review of scientific research revealed that secondary metabolites are found in plants that have a high commercialization potential and are important for medicinal purposes. Many plant species have antimicrobial, antifungal, antioxidant, insecticidal, allelopathic, and antitumor properties [7].

2.2 Secondary metabolites Primary metabolic pathways such as photosynthesis, the Calvin cycle, the citric acid cycle, glycolysis, and the pentose phosphate pathways all produce secondary metabolites. Because their role was unknown, plant secondary metabolites were initially thought to be waste products [8]. Plants’ defense and tolerance to pests, diseases, and biological and environmental stress are now heavily reliant on secondary metabolites. Secondary metabolites, as contrast to primary metabolites, are frequently found only in specific plant families and accumulate in specific tissues. These metabolites have antibacterial, antiinflammatory, and anticancer activities, as well as phytochemical-like flavors, fragrances, and colors. It is impossible to overstate the importance of using plants for their medicinal efficacy and their function in various traditional medical systems [9]. They can be used as herbivore and pathogenic organism defense substances, floral pigments that attract pollinators, hormones, and signal molecules, among other things. Aside from their physiological function in plants, alkaloids have had a long history of use as sauces, dyes, and medications [10].

2.3 Alkaloid Secondary products are basic N-containing heterocyclic compounds derived from higher plants, which frequently have significant physiological activity. They are found as a salt of formic, malic, tartaric, citric, oxalic, and acetic acids in flowers, leaves, stems, bark, roots, and fruits. They are derivatives of heterocyclic Nitrogenous basic compounds such as pyridine, quinoline, isoquinoline, and pyrrole. They are colorless, nonvolatile, crystalline (except nicotine) solids that are insoluble in water but soluble in organic solvents, optically active, bitter in taste, and poisonous to animals. They form salts with acids and precipitate with phospho-tungstic acid, phospho molybdic acid, picric acid, and mercuri. They are active participants in plant metabolism rather than byproducts of detoxification. Adenine plays an important role in nucleic acid metabolism, and certain purines act as growth regulators. Protect the plant from insects. Some act as coenzymes in oxidative processes, as stimulators, growth regulators, and as protein synthesis reservoirs. With over 12,000 known structures, alkaloids are one of the most diverse groups of natural products [11].

2.3.1 Purine alkaloids Purine alkaloids are nitrogen-containing chemicals that result from nucleoside metabolism. L-aspartic acid, L-glutamine, L-glycine, and formate are among the tiny molecules that make

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up the purine backbone in primary metabolism. The same metabolic process produces cytokinins, plant hormones that regulate stem development and differentiation, apical dominance, and senescence. Purine alkaloids are found in a wide range of taxonomically unrelated plant species [12].

2.3.2 Tropane alkaloids The amino acids ornithine and/or arginine are the source of tropane alkaloids. They all share a bicyclic tropane structure, which consists of a seven-membered ring with an N bridge between C1 and C5, as well as methylation nitrogen. N-methylation is absent in nortropane, while secotropane has a prepared N-bridge [13]. Many tropane alkaloids are aliphatic or aromatic acids esters of the alcohols tropin (Tropan 3 an ol) or pseudotropin (Tropan 3 b ol).

2.3.3 Calystegines Calystegins are made up of three to five hydroxyl groups in the nortropane molecule. The hydroxyl groups are not esterified, unlike most other tropane alkaloids, but they can be glycosylated. Calystegins have hydroxylated C1 bridgeheads, but only calystegin N 1 has an amino group linked to it [14].

2.3.4 Pyrrolizidine alkaloids The backbone of pyrrolizidine alkaloids is made up of a hydroxymethylpyrrolizidine (necin base), which is usually esterified with branching aliphatic mono- or dicarboxylic acids (necinic acids). The necin basis is made up of spermidine and putrescine, both of which are derived from arginine [15]. Only the pyrrolizidine alkaloids of the senecionin and licopsamine classes have had their origins examined; they arise from amino acid metabolism [16,17].

2.3.5 Quinolizidine alkaloids Quinolizidine alkaloids are produced by cadaverine from lysine. With the exception of the bicyclic lupinin, the majority of the chemicals in this group are tricyclic or tetracyclic. Quinolizidine alkaloids are prevalent in the Fabaceae, as well as in a number of other taxa, such as Berberidaceae [18].

2.3.6 Benzyl isoquinoline alkaloids Two tyrosine molecules are used to make benzyl isoquinoline alkaloids. The major intermediary in their biosynthesis, (S)- reticulin, can undergo a variety of rearrangements and alterations to produce the various structural classes of benzyl isoquinoline. There are currently roughly 2500 identified structures in this diverse group of alkaloids. The analgesic morphine, the analgesic and antitussive codeine, the muscle relaxant tubocurarine, and the antibacterial and antiinflammatory sanguinarine are all benzylisoquinoline alkaloids with high pharmacological properties that

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have led to their usage in medicine. These compounds have various modes of action due to their highly varied architectures [19].

2.3.7 Ipecac alkaloids They’re named terpenoidisoquinoline alkaloids since they’re made up of the amino acid tyrosine and the monoterpene secologanine. They’re found in the Eudicotyledon family of plants [20].

2.3.8 Amaryllidaceae alkaloids The alkaloids of the Amaryllidaceae family are only found in the monocot family that gave them their name. They are made up of a tyrosine molecule and protocatechuic aldehyde, which is made up of phenylalanine. Norbelladin is the metabolic pathway’s key intermediate. Amaryllidaceae has over 500 alkaloid structures, some of which have substantial medicinal effects [21].

2.3.9 Monoterpene indole alkaloids The key intermediate 3 a (S)-strictosidine is used to biosynthesize this class of alkaloids from tryptophan and secologanin. There are almost 2000 structurally different monoterpene indole alkaloids known, including a number of pharmacologically useful molecules [22]. These alkaloids are mostly found in the plant families Apocynaceae, Loganiaceae, Nyssaceae, and Rubiaceae.

2.4 Camptothecin Camptothecin is a monoterpenic indole alkaloids belonging to the quinolone class. Although it loses the indole ring, feeding experiments have revealed that it is made up of tryptamine and a monoterpene precursor, with the indole structural rearrangement to create a quinoline heterocycle [23,24]. Apocynaceae and Icacinaceae are two Eudicot families that contain the alkaloid. The mechanism of action of camptothecin is unique. It covalently binds and stabilizes DNA by binding to the cleavable topoisomerase I complex [25]. This nondegradable DNA/topoisomerase I combination prevents DNA synthesis and consequently kills cells [25]. As a result, topoisomerase “poisons” include camptothecin and its derivatives.

2.4.1 Lignans and lignins hydroxycinnamic alcohols (monolignol), coumaryl alcohol, coniferyl alcohol, and synapyl alcohol make up ligans and lignins. Lignans are polymers of monolignol produced by the stereoselective coupling of two hydroxycinnamic alcohol units. The monolignols p-coumaryl alcohol, coniferyl alcohol, and synapyl alcohol are also known as H (hydroxyphenyl), G (guaiacyl), and S (syringyl) units after being incorporated into polymeric lignin. G units make up the majority of lignin in Gymnosperms, with modest amounts of H units [26].

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2.4.2 Polyketides AcetylCoA and MalonylCoA are two carbon units that come from activated acetate and are used to make polyketides. All or most of the oxygen functions are carried out by polyketides. Highly reactive polyketone intermediates are formed during polyketide biosynthesis, which are frequently cyclized to yield six-membered aromatic rings or two pyrone rings. Some polyketides are phenols, similar to phenylpropanoids, but the aromatic ring substitution pattern distinguishes the two groups. Phenols generated from the phenylpropanoid route have an orthoxygenation pattern, despite the fact that polyketides typically have oxygen functions at alternate carbons (meta-position). Many polyketides are glycosylated, and the sugar unit may have acyl substituents. Plant polyketides are frequently of heterogeneous biosynthetic origin and are not always produced entirely from acetate units. The acetate-derived backbone may be referred to by the terms phenylpropanoid or terpenoid building components, or both [27].

2.4.3 Hemiterpenes The most prevalent genuine hemiterpene discovered in plants is isoprene. It’s a volatile substance made from DMAPP. Isoprene synthesis and emission are common in the plant kingdom, with species synthesizing this chemical including mosses, ferns, gymnosperms, and angiosperms. Trees, particularly poplars and poplars, as well as plants from the wet tropics, generate the most isoprene. Isoprene is released into the environment and shields the leaves from high temperatures for short periods of time. Furthermore, it improves the plant’s tolerance to ozone and reactive oxygen species [28].

2.4.4 Monoterpenes Monoterpenes are made up of one DMAPP molecule and one IPP molecule, which are usually joined head-to-tail to form all-trans geranyl diphosphate (GPP). GPP may be folded into mono, bi, and tricyclic structures and subsequently modified to provide over 1000 distinct monoterpenes. Monoterpenes are lipophilic volatile chemicals found in protective resins of conifers, essential oils, and floral scents, and they contribute to many plants’ distinctive flavor or aroma [29].

2.4.5 Sesquiterpenes Sesquiterpenes are made up of three isoprene units and are made by combining two DMAPP molecules with two IPP molecules. Farnesyl diphosphate (FPP), a central C15 intermediate, can be folded into mono, bi, or tricyclic systems. Sesquiterpenes are less volatile than monoterpenes in general [30]. Originally, it was thought that the MVA cytosolic pathway produced all sesquiterpenes. Recent research has revealed that some sesquiterpenes are derived from isoprene units obtained via the DXP pathway [31,32] or both biosynthetic pathways [33]. The movement of isoprenoid precursors from the plastids to the cytosol explains this [34].

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2.5 Triterpenes and steroids Triterpenes are made from two FPP molecules that are linked by tail-to-tail condensation to generate squalene via the MVA route. The cyclization of its metabolite 2,3-oxidosqualene, followed by rearrangements and methyl modifications, produces a variety of structures, most of which are tetracyclic or pentacyclic in nature. 2, 3Oxidosqualen is also a precursor of steroid hormones in plants. The triterpene cycloartenol is cyclized in this example, and the C27 cholesterol molecule is then transformed with the loss of three methyl groups. In both triterpenes and steroids, the oxygen of 2,3-oxidosqualene is frequently preserved as a hydroxyl group at C3. In contrast to animals, where cholesterol is the primary sterol, many plant sterols, such as campesterol and stigmasterol, are methylated or ethylated at the C24 of the side chain. Stem elongation, leaf expansion, seed germination, and xylene differentiation are just a few of the biological processes they control [35].

2.5.1 Saponins Triterpenic saponins are common in eudicotyledons, and triterpenoid saponins frequently contain pentacyclic a-amyrin (ursane), b-amyrin (oleanane), or lupan skeleton or tetracyclic dammaran backbone as an aglycone. This aglycone is linked to one to three carbohydrate chains that contain up to six sugar or uronic acid molecules [30,36]. The first sugar chain is connected to the triterpenic backbone’s hydroxy group at C3. If there are two or more carbohydrate chains, they are usually linked with hydroxyl or carboxy groups at C28 or C30. Spirostanols and furostanols are the two types of steroidal saponins. The cholesterol side chain is used to form a tetrahydrofuran ring in furostanols, and the hydroxyl group at C26 is glycosylated. When this sugar unit is separated, a second oxygen-containing heterocycle is formed, resulting in the formation of spirostanol. The structure of steroidal glycoalkaloids is similar to that of spirostanol saponins, except that oxygen in the six-membered heterocycle of the spiro function is replaced by nitrogen. Steroidal saponins, like triterpenic saponins, have a sugar chain attached to the C3 hydroxyl group [37].

2.5.2 Tetraterpenes Tetraterpenes are made up of only one type of compound, carotenoids. They are made by joining the tails of two GGPP molecules. Double bonds are inserted to form a large conjugated system with an alltrans configuration, which is responsible for carotenoids’ yellow, orange, and red colors. The tetraterpene chain cyclizes at one or both ends to form a six-membered ring. Xanthophylls are carotenoids with hydroxyl or epoxy functions [30]. Because carotenoids are part of the light-collecting complex and act as accessory pigments for chlorophyll, they perform important physiological functions in plants. Furthermore, when there is an excess of light energy, they remove triplet chlorophyll and singlet oxygen, protecting the plant from photo-oxidative damage. Carotenoids attract pollinators and seed dispersers as flower and fruit pigments [38].

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During the Renaissance and Reformation times, tools were found to investigate the chemistry of natural ingredients. Today we use the science of ethnobotany, which is the scientific study of the relationships between humans and plants, to understand the cultural concepts surrounding the perception of the chemistry of plants and natural products. However, natural product compounds can be organized in different ways: biological function, chemical structure, and biochemical synthesis pathways, as well as into three main groups, namely terpenoids, phenylpropanoids, and nitrogenous compounds [39]. Today, the majority of the world’s primary health care is still heavily reliant on herbal remedies. Kampo medicine is not unheard of in Japan. African and Asian countries, which are endowed with a wealth of traditional medicinal plants that can be used as active pharmaceutical ingredients, can be explored in order to address the challenges of modern medicine in health care. More than 4,000 of the approximately 6,400 plant species used in tropical Africa and Asia are medicinal plants. Native American Indians have a long history of using traditional medicines [27]. Since the memorial, many plants have been recorded as herbal plants and used in Egyptian medicine. Despite the fact that these traditional medicines have been around for thousands of years, they are still used today for their medicinal and health benefits, thanks to the presence of unidentified bioactive compounds in the plant [40]. Table 2.1 shows the distribution of major class of natural product.

2.5.3 The potential of the natural product Herbal formulas are commonly used in traditional therapies to treat a variety of health conditions such as body aches, swelling, and rheumatism. Herbal formulations are used in Chinese medicine for a variety of purposes, including external relief, digestive problems, blood regulation, and physiological disorders [41]. There are a variety of Chinese herbal teas available for a variety of health benefits. The majority of these traditional medicines are now commercially available as topical products or as food and drink. Natural products are becoming more popular in Western countries, according to studies. According to the report, natural products have been used by 80% of adults in the United States due to their potential health benefits [41]. Plants have been used as medicine for thousands of years. Before 2697 BC, the herbal plant is wonder for the treatment of diseases right from ages [42]. As knowledge of herbs used in Egyptian medicine, many plants were recorded on the Ebers papyrus (1550 BC) [40]. Despite the fact that these traditional medicines have been around for thousands of years, they are still used for health and medicinal purposes today. Plants used in traditional medicine around the world have piqued the interest of plant chemistry researchers. Researchers are currently studying medicinal plants in order to scientifically identify the active natural product. Although natural products are chemical compounds synthesized by living organisms, they are more commonly referred to as natural chemicals with medicinal properties. Compounds can be extracted from the tissues of terrestrial plants, marine organisms, or microorganisms. Leaves, flowers, twigs, barks, rhizomes, roots, seeds, and fruits are some of the plant parts that are commonly used to extract natural substances [43]. Active

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Aliphatic natural products

Terpenoids

Steroids

Amino acids and peptides

Alkaloids

Semiochemicals Lipids Polyketides

Monoterpenoids Sesquiterpenoids Diterpenoids

The sterols

Aminoacids Peptides Β-Lactams

Carbohydrates Oxygen heterocycles

Sesterterpenoids Triterpenoids

Simple aromatic natural products

Tetraterpenoids

Benzofuranoids Benzopyranoids Flavonoids Tannins Lignans Polycyclic aromatic natural products

Miscellaneous terpenoids Meroterpenoids

Alkaloids derived from ornithine Alkaloids derived from lysine Alkaloids derived from nicotinic acid Alkaloids of polyketide origin Alkaloids derived from anthranilic acid Alkaloids derived wholly or in part from phenylalanine or Tyrosine Isoquinoline alkaloids Alkaloids derived from tryptophan Monoterpenoid indole alkaloids Terpenoid alkaloids Steroidal alkaloids Imidazole alkaloids Oxazole alkaloids Thiazole alkaloids Pyrazine and quinoxaline alkaloids Pyrrole alkaloids Putrescine alkaloids Spermine and spermidine alkaloids Peptide alkaloids Purines Pteridines and analogues

Glycopeptides

Extraction of Natural Products from Agro-industrial Wastes

Table 2.1 Distribution of natural products.

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pharmaceutical ingredients (API) in plants are typically found in concentrations ranging from 0.3% to 3% [43]. Some diseases, such as cancer and HIV, are incurable with modern synthetic medicine [44]. The ongoing efforts of scientists all over the world to develop proper medicine have focused on the active ingredients of plants, herbs, and fruits as antiassents rather than drugs in their own right. Many studies on natural products have been conducted, with some indicating that certain natural products derived from plants, herbs, and fruits have anti-HIV and anticancer properties [44,45]. Several compounds have been isolated from natural sources, and the compounds themselves have anti-HIV properties [44]. The natural product has also shown promising results in crop protection. To meet the world’s growing population’s food needs, it is now common practice to use chemical pesticides for crop protection, particularly in large plantations. Consistent use of chemical pesticides over time will undoubtedly make the plant more resistant, which is why pesticide overdose has occasionally been used. These factors raise the prospect of health risks if the plant is consumed. Many nations, such as the United States, have supported and implemented new pesticide registration procedures, such as the Food Quality Protection Act, which has decreased the number of synthetic pesticides available in agriculture [46]. Today’s agronomic techniques favor green technologies and organic agriculture, with all herbicides and fertilizers being organic if used. Pesticides based on natural ingredients are now being researched to generate new pesticides to replace synthetic pesticides. Natural product research can help identify molecules that are significant in limiting the activities of bacteria, microorganisms, and termites, which can then be used as a starting point for the development of crop protection bioproducts [46] which relate with the discovery natural products as a source of new agent for the Control of diseases and ailments from plant as shown in Fig. 2.1.

2.6 A source of natural product Plants have been showed to be a source of new natural substances with potential as antioxidants [47], antimicrobials [48,49], antifungals [50,51], antiinflammatory [52,53], antiileishmanic [54], anticancer [55,45], insecticidal activities [56], and various other activities. Numerous studies have been conducted throughout the world to isolate and identify a variety of physicochemical agents such as amides, alkaloids, lignans, neolignans, propenylphenols, kawapirones, piperolides, chalcones, dihydrochalcones, flavones, flavonones, terpenes, and steroids [57]. Parmer’s [58] research revealed the presence of natural substances such as mevalonic acid, flavone, dihydroflavone, dihydrochalcone, and omethylflavonoids. Because secondary metabolites are largely constituted of tiny molecules, essential oil is a natural multicomponent system that is a mixture of volatile components produced by aromatic plants. Pure essential oils are made up of combinations of over 200 different ingredients. More than 3000 essential oils are recognized among the 100,000 secondary metabolites, with 300 of them being of economic interest and employed in the pharmaceutical, cosmetic, and food industries [59]. Natural product has been a sources of new medication over the nearly four decades as shown in Fig. 2.2.

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FIGURE 2.1 Contemporary approaches to the discovery natural products as a source of new agent for the control of diseases and ailments.

40 35 30 25 20 15 10 5

1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019

0

FIGURE 2.2 Natural product as a source of new medication over the nearly four decades.

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They are a delicate, fragrant, and volatile liquid obtained as secondary metabolites from diverse parts of plants and play a crucial function in ecology and biology. They’re vital for plant defense because they’re frequently antibacterial and antioxidant [60]. Depending on the manner of extraction, the chemical profile of essential oil products changes not only in terms of the number of molecules extracted, but also in terms of the stereochemical types of molecules extracted. Depending on the temperature, soil composition, plant organs, age, and stage of vegetation, the extraction product can vary in quality, quantity, and composition [61,62]. To acquire essential oils with consistent composition, they must be gathered under the same conditions from the same source, from plants cultivated in the same soil, in the same climate, and harvested in the same conditions and season [63]. The chemical composition of essential oil, as one of the sources of essential natural products, varies depending on the location and type of plant. It is a blend of terpenes and phenylpropane derivatives. They are classified as volatile fractions and nonvolatile residues. The essential oil, which accounts for 90%–95% of the oil, contains monoterpenes and sesquiterpenes, hydrocarbons and their oxygenated derivatives, as well as aliphatic aldehydes, alcohols, and esters, which are the volatile fractions of the essential oil. According to the Eslahi report [64], roughly 110% of essential oil comprises nonvolatile fractions such as hydrocarbons, fatty acids, sterols, carotenoids, waxes, and flavonoids. To stop bacterial growth and prevent putrefaction, the Ancient Egyptians used aromatic plants and essential oils in embalming. Essential oils have antibacterial properties and have been shown to be effective against a wide range of pathogenic bacterial strains, including Listeria monocytogenes, Salmonella typhimurium, Escherichia coli, Shigella dysenteria, Bacillus cereus, Staphylococcus aureus, Salmonella typhimurium, and many others [66–68]. Candida albicans (fungus) and Helicobacter pylori, a Gram-negative microaerophilic bacterium, can also be inhibited by the essential oil [69,70]. Essential oils are commonly utilized as flavorings in food and medicine. Some essential oils are utilized in the food business as natural additives or antibacterial agents to improve the shelf life of food. The fact that the essential oil contains natural chemicals with a variety of biological actions to protect food from pathogenic and perishable microbes makes this possible [71]. Essential oils have been used to prevent and treat a variety of ailments for at least 4000 years. Aromatherapy is a complementary medicine that was established as a result of the balancing qualities of essential oils. Carvacrol, a primary component of essential oils derived from oregano and thyme [71], is one of the best-known chemicals for this activity. Carvacrol is an antibacterial drug that works against most Gram-positive and Gram-negative bacteria, according to previous research. Other key components of the essential oil of the rosemary plant, such as -pinene and myrcene, have been found to contain both Gram-positive and Gram-negative bacteria [71–74]. Antioxidant, antiinflammatory, and antifungal properties are all present in essential oils. Thymol and carvacrol are the major components in vegetable essential oils that have significant antioxidant activity. These chemicals function as antioxidants in a variety of ways, including preventing chain initiation, acting as a reducing agent, scavenging radicals, and terminating peroxides [75].

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2.7 Conclusion Natural products include substances produced by plants or animals or chemical substances naturally present in nature that possess certain pharmacological properties. Primary metabolites, secondary metabolites and polymeric molecules are the three classes of natural products. Primary metabolites (e.g., citric acid, lactic acid, amino acids, etc.) are directly necessary for the growth, development, and survival of the organisms. Secondary products are basic N-containing heterocyclic compounds derived from higher plants, which frequently have significant physiological activity. They are found as a salt of formic, malic, tartaric, and citric, oxalic, and acetic acids in flowers, leaves, stems, bark, roots, and fruits. They form salts with acids and precipitate with phospho-tungstic acid, phospho molybdic acid, picric acid, and mercuri. They are active participants in plant metabolism rather than byproducts of detoxification. The primary metabolic pathways such as photosynthesis, Calvin cycle, citric acid cycle, glycolysis, and the pentose phosphate pathways all produce secondary metabolites but because their role was unknown plant metabolites were initially thought to be waste products. Plants’ defense and tolerance to pests, diseases, and biological and environmental stress are now heavily reliant on secondary metabolites. Secondary metabolites, as contrast to primary metabolites, are frequently found only in specific plant families and accumulate in specific tissues. These metabolites have antibacterial, antiinflammatory, and anticancer activities, as well as phytochemicallike flavors, fragrances, and colors. Plants’ medicinal value is conferred by secondary metabolites such as alkaloids, tannins, saponins, flavonoids, anthraquinones, glycosides, terpenes, essential oils, and resins. A review of scientific research revealed that secondary metabolites are found in plants that have a high commercialization potential and are important for medicinal purposes. Many plant species have antimicrobial, antifungal, antioxidant, insecticidal, allelopathic, and antitumor properties. Plants used in traditional medicine around the world have piqued the interest of plant chemistry researchers. Researchers are currently studying medicinal plants in order to scientifically identify the active natural product. Although natural products are chemical compounds synthesized by living organisms, they are more commonly referred to as natural chemicals with medicinal properties. Compounds can be extracted from the tissues of terrestrial plants, marine organisms, or microorganisms. Leaves, flowers, twigs, barks, rhizomes, roots, seeds, and fruits are some of the plant parts that are commonly used to extract natural substances. Many studies on natural products have been conducted, with some indicating that certain natural products derived from plants, herbs, and fruits have anti-HIV and anticancer properties.

References [1] Baltz RH. Gifted microbes for genome mining and natural product discovery. J Ind Microbiol Biotechnol 2017;44(4-5):573–88. [2] Buenz EJ, Verpoorte R, Bauer BA. The ethno pharmacologic contribution to bioprospecting natural products. Annu Rev Pharmacol Toxicol 2018;58:509–30.

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[27] Raymond C, George N. Natural products chemistry. Sources, separations, and structures. Boca Raton, FL: Taylor & Francis Group; 2015. [28] Sharkey TD, Wiberley AE, Donohue AR. Isoprene emission from plants: why and how. Ann Bot 2007;101(1):5–18. [29] Croteau RB, Davis EM, Ringer KL, Wildung MR. (−)-Menthol biosynthesis and molecular genetics. Naturwissenschaften 2005;92(12):562. [30] Dewick PM. Medicinal natural products: a biosynthetic approach 2002. [31] Dudareva N, Andersson S, Orlova I, Gatto N, Reichelt M, Rhodes D, et al. The nonmevalonate pathway supports both monoterpene and sesquiterpene formation in snapdragon flowers. Proc Nat Acad Sci USA, 102; 2005. p. 933–8. [32] Piel J, Donath J, Bandemer K, Boland W. Mevalonate-independent biosynthesis of terpenoid volatiles in plants: induced and constitutive emission of volatiles. Angew Chem Int Ed 1998;37(18):2478–81. [33] Adam KP, Zapp J. Biosynthesis of the isoprene units of chamomile sesquiterpenes. Phytochemistry 1998;48(6):953–9. [34] Bick JA, Lange BM. Metabolic cross talk between cytosolic and plastidial pathways of isoprenoid biosynthesis: unidirectional transport of intermediates across the chloroplast envelope membrane. Arch Biochem Biophys 2003;415(2):146–54. [35] Bishopp A, Mähönen AP, Helariutta Y. Signs of change: hormone receptors that regulate plant development. Development 2006;133(10):1857–69. [36] Hostettmann K, Marston A. Saponins. Cambridge University Press; 2005. [37] Güçlü-Üstünda˘g Ö, Mazza G. Saponins: properties, applications and processing. Crit Rev Food Sci Nutr 2007;47(3):231–58. [38] Howitt NM,CA, Pogson BJ. Carotenoid accumulation and function in seeds and non-green tissues. Plant Cell Environ 2006;29:435–45. [39] Bernardini S, Tiezzi A, Laghezza Masci V, Ovidi E. Natural products for human health: an historical overview of the drug discovery approaches. Nat Prod Res 2018;32(16):1926–50. [40] Aboelsoud NH. Herbal medicine in ancient Egypt. J Med Plant Res 2010;4(2):82–6. [41] Tosado, R. Natural products gaining in popularity: 80 percent of U.S adults use them for health benefits 2008. Retrieved October 19, 2021 from http://www.prweb.com/releases/2008/12/prweb1709304.htm. [42] Yang SZ. The Divine Farmer’s Materia Medica. Western Ave: Blue Poppy Press Inc; 1998. p. 1–84. [43] Hans-Jorg B, Stephan P. Extraction of natural products from plants—an introduction. 1st ed. Germany: Wiley-VCH Verlag & Co; 2011. p. 1–25. [44] Inder PS, Sandip BB, Bhutani KK. Anti-HIV natural products. Review article. Curr Sci 2005;89(2):269–90. [45] Gwendoline CLE, Chyi ML, Mawardi R, Khozirah S, Choon FJB. Pellitorine, a potential anto-cancer lead compound against HL60 and MCT-7 cell lines and microbial transformation of piperine from Piper nigrum. Molecules 2010;15:2398–404. [46] Franck ED, Charles LC, Stephen OD. Natural products in crop protection. Bioorg Med Chem 2009;17(12):4022–34. [47] Sruthi D, John Zachariah T. In vitro antioxidant activity and cytotoxicity of sequential extracts from selected black pepper (Piper nigrum L.) varieties and Piper species. Int Food Res J 2017;24(1):75–85. [48] Ramkumar KM, Vanitha P, Uma C, Suganya N, Bhakkiyalakshmi E, Sujatha J. Antidiabetic activity of alcoholic stem extract of Gymnema montanum in streptozotocin-induced diabetic rats. Food Chem Toxicol 2011;49(12):3390–4. [49] Amal AM, Sami IA, Farouk KEB. Antioxidant and antibacterial activities of crude extract and essential oils of Syzygium cumini leaves. PLoS One 2013;8(4):60–9.

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[50] Prakash B, Shukla R, Singh P, Kumar A, Mishra PK, Dubey NK. Efficacy of chemically characterized Piper betle L. essential oil against fungal and aflatoxin contamination of some edible commodities and its antioxidant activity. Int J Food Microbiol 2010;142:114–19. [51] Castillo F, Hernandez D, Gallegos G, Rodriguez R, Aguilar CN. Antifungal properties of bioactive compounds from plants. Fungicides for plants and animal diseases. Mexico: InTech; 2012. p. 81–106. [52] Sarvesh K, Shashwat M, Ashok KP, Erik VVE, Marc EB, William GSS, et al. Anti-inflammatory and antioxidant properties of Piper species: a perspective from screening to molecular mechanisms. Curr Topic Med Chem 2015;15:886–93. [53] Rintu D, Shinjini M, Kaustab M, Pramathadhip P, Umesh PS, Banerjee ER. Anti-oxidant and anti-inflammatory activities of different varieties of Piper leaf extracts (Piper betle L.). J Nutr Food Sci 2015;5:415. [54] Hardik S, Jalak K, Deepti J, Ghanashyam P. Evaluation of bonton active granules for anti-osteoporotic activity in ovariectomized rat. World J Pharm Sci 2014:181–7. [55] Jioji & Marcel, Tabudravu JN, Jaspars M. Anticancer activities of constituents of kava (Piper methysticum). South Pacif J Nat Appl Sci 2005;23(1):26–9. [56] Siddigui BS, Begun S, Gulzar T, Noor FF. An amide from fruits of Piper nigrum. Phytochemistry 1997;45:1617–19. [57] Hakimi WMN, Farediah A, Hasnah MS, Khong HY. Chemical composition and antibacterial activity of the leaf and stem oils of Piper porphyrophyllum (Lindl.), N.E. Br. EXCLI J 2012;11:399–406. [58] Parmar VS, Jain SC, Bisht KS, Jain R, Taraj P, Tha A, et al. Phytochemistry of the genus Piper. Phytochemistry 1997;46(4):597–673. [59] Freires I, Denny C, Benso B, de Alencar S, Rosalen P. Antibacterial activity of essential oils and their isolated constituents against cariogenic bacteria: a systematic review. Molecules 2015;20(4):7329–58. [60] Tohidi B, Rahimmalek M, Arzani A. Essential oil composition, total phenolic, flavonoid contents, and antioxidant activity of Thymus species collected from different regions of Iran. Food Chem 2017;220:153–61. [61] Angioni A, Barra A, Coroneo V, Dessi S, Cabras P. Chemical composition, seasonal variability, and antifungal activity of Lavandula stoechas L. ssp. Stoechas essential oils from stem/leaves and flowers. J Agric Food Chem 2006;54:4364–70. [62] Masotti V, Juteau F, Bessière JM, Viano J. Seasonal and phenological variations of the essential oil from the narrow endemic species Artemisiamolinieri and its biological activities. J Agric Food Chem 2003;51(6):7115–21. [63] Smith RL, Cohen SM, Doull J, Feron VJ, Goodman JI. A procedure for the safety evaluation of natural flavour complexes used as ingredients in food: Essential oils. Food Chem Toxicol 2005;43:345–63. [64] Eslahi, H, Nafiseh, F, Ali, RS. Chemical composition of essential oils 2017. https://onlinelibrary. willy.com/dio/pdf/10.1002/9781119149392.ch4. [65] Fornari T, Vicente G, Vázquez E, García-Risco MR, Reglero G. Isolation of essential oil from different plants and herbs by supercritical fluid extraction. J Chromatogr A 2012;1250:34–48. [66] Jirovetz L, Buchbauer G, Denkova Z. Antimicrobial testings and gas chromatograph analysis of pure oxygenated monoterpenes 1,8-cineo, α-terpineol, terpene-4-ol and camphor as well as target compounds in essential oil of pine (Pinus pinaster), Rosemary (Rosmarinus officinalis) and tee tree (Maelaleuca alternifolia). Sci Pharm 2005;73:27–39. [67] Simic A, Fernandes R, Brown R, Romanov P, Park W. Validation of VEGETATION, MODIS, and GOES+ SSM/I snow-cover products over Canada based on surface snow depth observations. Hydrol Processes 2004;18(6):1089–104. [68] Burt S. Essential oils: their antibacterial properties and potential applications in foods—a review. Int J Food Microbiol 2004;94(3):223–53.

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[69] Akor JS, Anjorin TS. Phytochemical and antimicrobial studies of Commiphora africana (A. Rich) Engl. root extracts. J Med Plant Res 2009;3(5):334–7. [70] Epifano F, Menghini L, Pagiotti R, Angelini P, Genovese S, Curini M. In vitro inhibitory activity of boropinic acid against Helicobacter pylori. Bioorg Med Chem Lett 2006;16(21):5523–5. [71] Tongnuanchan P, Benjakul S. Essential oils: extraction, bioactivities, and their uses for food preservation. J Food Sci 2014;79(7):R1231–49. [72] Elhassan IA, Osman NM. New Chemotype Rosmarinus officinalis L. (Rosemary) “R. officinalis ct. bornyl acetate. Am J Res Comm 2014;2(4):232–40. [73] Moghtader M, Salari H, Farahm A. Evaluation of the antifungal effects of rosemary oil and comparison with synthetic borneol and fungicide on the growth of Aspergillus flavus. J Ecol Nat Environ 2011;3(6):210–14. [74] Okoh OO, Sadimenko AP, Afolayan AJ. Comparative evaluation of the antibacterial activities of the essential oils of Rosmarinus officinalis L. obtained by hydrodistillation and solvent free microwave extraction methods. Food Chem 2010;120:308–12. [75] Guetat A, Al-Ghamdi FA, Osman AK. 1, 8-Cineole, α-pinene and verbenone chemotype of essential oil of species Rosmarinus officinalis L. from Saudi Arabia. Int J Herb Med 2014;2(2):137–41.

3

  

Ionic liquids with microwave-assisted extraction of natural products Irina Fierascu a,b, Sorin Marius Avramescu c, Elwira Sieniawska d and Radu Claudiu Fierascu a,e a NATIONAL

INSTITUTE FOR RESEARCH & DEVELOPMENT IN CHEMISTRY AND

PETROCHEMISTRY—ICECHIM, BUCHAREST, ROMANIA

b UNIVERSITY

OF AGRONOMIC

SCIENCES AND VETERINARY MEDICINE OF BUCHAREST, BUCHAREST, ROMANIA c FACULTY

OF CHEMISTRY, UNIVERSITY OF BUCHAREST, BUCHAREST, ROMANIA

d DEPARTMENT

OF PHARMACOGNOSY WITH MEDICINAL PLANT UNIT, MEDICAL

UNIVERSITY OF LUBLIN, LUBLIN, POLAND e DEPARTMENT OF SCIENCE AND ENGINEERING OF OXIDE MATERIALS AND NANOMATERIALS, UNIVERSITY “POLITEHNICA” OF BUCHAREST, BUCHAREST, ROMANIA

3.1 Introduction Following the principles of “green chemistry,” researchers developed new, modern and sustainable equipment and solvents. Consequently, the mixtures of substances emerged as new classes of extraction solvents designed to minimize or even eliminate harmful organic compounds or to replace them with more friendly alternatives [1]. Such a neoteric group of solvents are ionic liquids (ILs), which are commonly recognized as salts with a melting point below arbitrary temperature equal to 100°C. The most commonly encountered ILs are room-temperature ionic liquids (RTILs), representing organic salts with melting points below room temperature [2]. Their unique properties (low melting point) result from their structure, in which inorganic cations are replaced with asymmetric organic cations [3]. Since 1914, when Paul Walden synthesized the first ionic liquid (ethyl ammonium nitrate) with a room temperature melting point, and from 1934 (the apparition date of the first patent on the topic), the researchers developed thousands of combinations, designing the solvent properties for numerous specific applications [5]. Due to their advantageous properties and possibility to develop a tailored solvent, ILs can be used in a wide range of applications. From environmental protection and catalysis, through analytical extraction methodologies for the isolation of plant secondary metabolites, ILs compensate the limitations of different solvents used in an usual manner. Introduced below, Tables 3.1 and 3.2 list the abbreviations used in the chapter, whereas Table 3.3 presents the examples of different ILs, their properties and applications. Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach. DOI: https://doi.org/10.1016/B978-0-12-823349-8.00012-5 c 2023 Elsevier Inc. All rights reserved. Copyright 

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36

ILs

Acronym

1-butyl-3-methylimidazolium [Bmim][Cl] chloride 1-butyl-3-methylimidazolium [Bmim]Br bromide 1-butyl-3-methylimidazolium [Bmim][BF4 ] tetrafluoroborate 1-decyl-3-methylimidazolium [C10 mim]Br bromide 1-benzyl-3-methylimidazolium [Bemim]Cl chloride 1-octyl-3-methylimidazolium [Omim][NTf2 ], bis(trifluoromethanesulfonyl)imide 1-hexyl-3-methylimidazolium [C6 mim][CF3 SO3 ] trifluoromethanesulfonate 1-butyl-2,3-dimethylimidazolium [C4 dmim][Cl] chloride 1-octyl-3-methylimidazolium [Omim] [OAc] acetate 1-octyl-3-methylimidazolium [OMIM][Br] Bromide 1-Hexyl-3-methylimidazolium [C6 mim][BF4 ] Tetrafluoroborate 1-ethylpyridinium bromide [C2 py]Br Tetraethylammonium germanium [Et4 N][GeCl3 ] trichloride

Cation name

Acronym

Anion name

Acronym

1-butyl-3methylimidazolium 1-butyl-3methylimidazolium 1-butyl-3methylimidazolium 1-decyl-3methylimidazolium 1-benzyl-3methylimidazolium 1-octyl-3methylimidazolium 1-hexyl-3methylimidazolium 1-butyl-2,3dimethylimidazolium 1-octyl-3methylimidazolium 1-octyl-3methylimidazolium 1-hexyl-3methylimidazolium 1-ethylpyridinium tetraethylammonium

Bmim

Chloride

Cl

Bmim

Bromide

Br

Bmim

Tetrafluoroborate

BF4

C10 mim

Bromide

Br

Bemim

Chloride

Cl

Omim

NTf2

C6 mim

bis(trifluoromethanesulfonyl)imide Trifluoromethanesulfonate

CF3 SO3

C4 dmim

Chloride

Cl

Omim

Acetate

OAc

Omim

Bromide

Br

C6 mim

Tetrafluoroborate

BF4

C2 py Et4 N

Bromide Germanium trichloride

Br GeCl3

(continued on next page)

Extraction of Natural Products from Agro-industrial Wastes

Table 3.1 Abbreviations used in the chapter for ILs.

[Et4 N][SnCl3 ]

tetraethylammonium

[EtNH3 ][NO3 ] [Omim][BF4 ]

[C2 mim]Br [Bmim][N(CN)2 ] [C4 C1 im]Im [HO3 S(CH2 )4 mim]HSO4 [C10 mim]NO3 [C12 mim]NO3

Et4 N

Tin trichloride

SnCl3

ethyl ammonium EtNH3 1-octyl-3Omim methylimidazoliumchloride

Nitrate Tetrafluoroborate

NO3 BF4

1-ethyl-3methylimidazolium 1-butyl-3methylimidazolium 1-butyl-3methylimidazolium 3-methyl-1-(4-sulfonylbutyl) imidazolium 1-decyl-3methylimidazolium 1-dodecyl-3methylimidazolium

C2 mim

Bromide

Br

Bmim

Dicyanamide

N(CN)2

[C4 C1 im]

Imidazolide

Im

HO3 S(CH2 )4 mim

Hydrogen sulfate

HSO4

C10 mim

Nitrate

NO3

C12 mim

Nitrate

NO3

Chapter 3 r Ionic liquids with microwave-assisted extraction of natural products

Tetraethylammonium tin trichloride ethylammonium nitrate 1-octyl-3methylimidazoliumchloride tetrafluoroborate 1-ethyl-3-methylimidazolium bromide 1-butyl-3-methylimidazolium dicyanamide 1-butyl-3-methylimidazolium imidazolide 3-methyl-1-(4-sulfonylbutyl) imidazolium hydrogensulfate 1-decyl-3-methylimidazolium nitrate 1-dodecyl-3-methylimidazolium nitrate

37

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Extraction of Natural Products from Agro-industrial Wastes

Table 3.2 Other abbreviation used in the chapter. Abbreviation

Full name

C2 mim C6 mim C8 mim DMHEEAP DMCEAP ILs VB3PILs PILs MAE IMUSEH MALSE BMSHE VMAE

1-ethyl-3-methylimidazolium 1-hexyl-3-methylimidazolium 1-octyl-3-methylimidazolium N,N-dimethyl-N-(2-hydroxyethoxyethyl)ammonium propionate N,N-dimethyl(cyanoethyl)ammonium propionate Ionic liquids vitamin B3-based protic ionic liquids Protic ionic liquids Microwave-assisted extraction Microwave–ultrasonic synergistic simultaneous extraction and hydrolysis Microwave-assisted liquid-solid extraction Brönsted acidic ionic liquid-based microwave-assisted simultaneous hydrolysis and extraction Vacuum microwave-assisted extraction

Table 3.3 Examples of different ILs: their properties and applications. ILs

Properties

Application

1-butyl-3-methylimidazolium chloride ([Bmim][Cl])

Low vapor pressures, stability at high temperatures, solvation for a wide variety of compounds and gases

1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) Ionic liquids built with tetraalkylammonium cations and halide (Br−), dicyanamide (Dca− ), thiocyanato (SCN- ) and bis(trifluoromethysulfonyl)imide (Tf2 N− ) 1-hexyl-3-methylimidazolium trifluoromethanesulfonate ([C6mim][CF3 SO3 ]) 1-butyl-2,3-dimethylimidazolium chloride ([C4dmim][Cl])

Affinity toward CO2 and easy desorption Negligible vapor pressure, avoiding solvent loss by volatilization

Gas storage and handling [5] applications such as separating hydrogen from ammonia borane in hydrogen storage Carbon dioxide capture (CO2 ) [6]

1-butyl-3-methylimidazolium chloride ([Bmim]Cl) 1-alkyl-3-methylimidazolium chlorides, alkyl is: methyl, ethyl, propyl, butyl or hexyl Functionalized ILs in mesoporous silicon

Reference

Solvent extraction process of gold from aqueous solutions

[7]

Powerful solvents of cellulose

Dissolution of lignin

[8]

Instability of most imidazolium-based ILs under basic condition Capability to form hydrogen bonds with cellulose at high temperatures Negligible vapor pressure, high viscosity, good stability, reusability without properties loss Low volatilization

Catalyzed depolymerization of lignin

[9]

Pretreatment of lignocellulosic biomass

[10]

Silk Fibroin Nanoparticles

[11]

Ionic liquid-organicfunctionalized ordered mesoporous silica

[12]

Chapter 3 r Ionic liquids with microwave-assisted extraction of natural products

39

3.2 Ionic liquids: general considerations, classification, and properties The detailed history of ILs was described in several interesting review papers, which we suggest for further reading [13–15]; however, several names of important contributors to the ILs development should be mentioned here, also. First ionic liquid was synthesized in 1914 by Paul Walden being studied the correlation between its molecular size and the conductivity [16]. His discovery passed unnoticed for 40 years, until Hurley and Weir discovered that the mixture of [C2 py]Br and AlCl3 was liquid at room temperature [17]. In 1972, Parshall used tetraethylammonium germanium trichloride and tetraethylammonium tin trichloride ([Et4 N][GeCl3 ] and [Et4 N][SnCl3 ]) as solvents for platinum-catalyzed hydrogenation reactions. Other names related to ILs are of Warren Ford who explored the low viscosity of tetraalkylammonium tetraalkylborides, and Robinson and Osteryoung, who studied the electrochemistry of two iron (II) diimine complexes, ferrocene and hexamethylbenzene at room temperature [18–20]. In the 1980s, Evans and collaborators used for the first time ethyl ammonium nitrate as a non-aqueous solvent for biochemical systems [21]. This resulted in huge exploration on this field and until the year of 2000 many groups had been working on different technologically important applications of ILs, such as electrochemistry, solvents for different chemical reactions, catalyzed dimerization of alkenes in ethyl aluminum chloride or replacement of synthetic oils [22–25]. At the beginning of 2000s ILs became commercially available from Solvent Innovation GmbH (SI), at a good quality, in high quantities and at accessible prices [14]. The interest towards the development of new potential applications on the ILs area increased exponentially. From that moment, ILs were used on a large scale in biomass processing to obtain bioactive compounds, or in the production of biomassderived products, such as cellulose from wood [26]. Several types of ILs are used in our days as solvents in different extraction processes, being mainly associated with the microwave-assisted extraction (MAE), applied in order to obtain different target compounds. For example, dual-chain ionic liquids can be used for the MAE of flavonoids [27], whereas vitamin B3-based protic ionic liquids found application as green solvents for the MAE of astilbin [28]. Also, very recently, in 2020, more sophisticated ILs were developed in the field of natural products, in order to increase the quality and safety of food. This is the case, for example, of the magnetic ionic liquid, which can be used for the determination of biogenic amines [29] or as catalyst for choline hydroxide ionic liquid biodiesel production [30]. ILs are highly tuneable organic salts usually used because of their low temperature melting points (Tm 200°C) [31]. Several authors proposed the theory that there is over a million permutations of ILs that could be synthesized [4,32], but all of them have a common denominator: they possess a cation core, cation substituents, anion core, and anion substituents [33] (Fig. 3.1). The most common anions and cations [34,35] are presented in Fig. 3.2. For such a large number of possible combinations, various classifications have been proposed by different authors. According to Kuzmina et al., ILs can be divided into 3 important groups: heterocyclic amines (pyridinium, imidazolium, etc.), quaternary cations (phosphonium and ammonium-based cores), respectively superbases [36]. According to Hajipour and Rafiee, ILs can be classified into eleven groups: neutral, acidic, basic, functionalized, protic, chiral,

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Extraction of Natural Products from Agro-industrial Wastes

FIGURE 3.1 Schematic design of ILs, exemplified on the structure of 1-Ethyl-3-methylimidazolium diethyl phosphate (left) and 1-Butyl-3-methylimidazolium dicyanamide (right). The different colors represent the different sections of a typical IL.

FIGURE 3.2 The most common cations and anions in ILs.

supported, bio-ionic, polymerized and energetic ionic liquids, and ionic liquids with amphoteric anions [37]. Another possibility to classify ILs is according their cations and anions [38], but the simplest classification is dividing them into acidic, basic and neutral ionic liquids [39]. According to Buszewska-Forajta’s classification, the cation can be imidazolium, pyridinium, piperidinium, quinolinium, morpholinium, pyrrolidinium and their derivatives and the anion can be trifluoromethylsulfate, bis(trifluoromethylsulfonyl)imide, dicyanamide, hexafluorophosphate or tetrafluoroborate. Another category of ILs useful in biomass conversion are polymerized ILs, providing an exceptional flexibility for designing interfacial reactions [40]. ILs properties are related to their chemical character and physical characteristics. Low melting temperatures and the resistance to crystallization from melt favor the use of ILs as solvents for extraction. The substitution of large, non-polar, hydrophobic alkyl chains of the charged cation

Chapter 3 r Ionic liquids with microwave-assisted extraction of natural products

41

core disperses the charge and raises steric hindrance to the counter ion, exposing to thermal conditions conducting to polymorphs (as observed for several [BMIM+] ILs) [41]. By changing the structure of an IL, the viscosities can be higher, compared with those of common organic solvents [39]. Acidic ionic liquids (AILs), Lewis acidic ionic liquids (LAILs) and Bronsted acidic ionic liquids (BAILs) possess high acidic properties. This enables better dissolution and isolation of target compounds from the biomass [42]. Therefore, such ILs can be used in the area of biomass processing [43] or as biomass pre-treatment solvents [43].

3.3 Ionic liquids as solvents for microwave extraction Plants represent rich sources of target compounds, which, after extraction and purification, can be considered active molecules for many applications, such as pharma, food, agriculture, etc. Nowadays, the interest of many researchers focuses on finding new modalities based on the equipment progress and leading to obtain pure compounds with increased yields, low cost, ecofriendly methods and low reagent consumption. The tremendous interest is also observed for scaling up laboratory methods to obtain bioactive compounds from natural sources. Alongside methods based on pressure or ultrasounds, microwave-assisted extraction (MAE) is a modern extraction technique [45]. It is applied for the extraction of active compounds; however, quality and quantity of extracted molecules is influenced by different factors, such as: extraction time and power, effect of temperature, solvent composition, solvent-feed ratio, pH, particle size, and sample moisture [46]. The controlled selection of MAE appropriate parameters gives a possibility to obtain enhanced extraction yields of such plant secondary metabolites, like polyphenolics, vitamins, or terpenoids [47]. Importantly, for a wide range of vegetal material and extracted compounds it is almost impossible to provide generalized extraction conditions. Optimization of “solvent parameter” can be performed in different MAE systems such as: r Closed MAE system operating under nitrogen atmosphere (NPMAE) to lower the degradation of bioactive compounds [48,49]; the application of the inert gases, such as nitrogen or argon removes oxygen from the reaction system and decreases the decomposition of the compounds, which can occur at elevated temperatures in the air atmosphere [50,51]; r Simultaneous MAE system, called dynamic MAE, removing the risk of contamination or loss of bioactive compounds and reducing their thermal degradation [52]; r Negative pressure cavitation (NPC) system suitable for extraction of sugars, flavonoids, phenols and alkaloids without damaging their biological properties and significantly decreasing the extraction time [53]; r Ultrasonic microwave-assisted extraction (UMAE) system, enhancing mass transfer needed to damage cell integrity and liberate bioactive compounds, resulting in superior extraction yields [54]; r Microwave-assisted subcritical and supercritical fluid extraction system, operating in low temperatures and increasing extraction yields of both organic (especially oil and fats) and inorganic compounds, without damaging their properties [55,56];

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Extraction of Natural Products from Agro-industrial Wastes

r Microwave-assisted enzymatic extraction (MAEE) system, inducing fragmentation of the cell matrix through microwave supported rotation of dipoles [57]; r Microwave hydro diffusion and gravity extraction system, suitable for the extraction of essential oils from aromatic plants [58]. Ionic liquids, which are a suitable alternative to classical solvents, increase the performance of microwave extraction through facilitation of microwave energy absorption [59]; however, their composition should also be optimized. Hydrogen bonding, hydrophobicity of ILs, π –π stacking between ILs and target bioactive compounds, and steric hindrance effect can affect the extraction procedure [60]. Nevertheless, due to their adaptable properties, ILs are suitable solvents for extraction of different types of bioactive molecules [61,62]. According to literature data, the application of ionic liquids can lead to the enhancement of the extraction ability and yield, as well as to shorter extraction times, when compared to alternative conventional solvents [63–66]. An additional advantage regarding the application of ILs is represented by the possibility to use room temperature ionic liquids (RTILs), such as [C6 mim]Br, [Bmim]Br, [Bmim]BF4 , [C6 min]BF4 and [Bmim]Cl [52] in the cases of easily degradable compounds. RTILs accelerate the extraction process and reduce the risk of overexposure to microwave heating [47]. Also, these solvents are able to provide very good results in the extraction of vegetal material with thick and resistant cell walls [67]. The tandem ionic liquids – MAE systems can also eliminate hazardous solvents, such as hydrochloric acid solutions [68]. Table 3.4 presents some examples of ILs applied in different MAE systems.

3.3.1 ILs and MAE for simultaneous extraction of different classes of compounds ILs can be successfully applied for simultaneous MAE of different classes of plant metabolites. For example, Guo et al. obtained gingerols and shogaols from ginger with the application of ILs for MAE. They obtained increased yields (0.716%) in comparison to classical methanol extraction (0.595%) and methanol MAE (0.673%) [70]. Hou et al. used 1-Butyl-3-methylimidazolium bromide solution to obtain procyanidins (oligomeric and polymeric) and essential oil from pinecones of Pinus koraiensis. Using LiCl and mixture of cellulase and pectinase as extraction additives, the authors obtained increased yields of target compounds (13.02, 32.19, and 7.76 mg/g for oligomeric, polymeric procyanidins, and essential oil, respectively). What is more, they proved possibility to recycle ILs, indicating lower process costs as potentially relevant benefit to industrial production [69]. From the economic point of view, ILs can also be used as costeffective pre-treatment solvents, what was shown for sweet sorghum bagasse, a raw material for bacterial nanocellulose production [83]. The disruption of the intermolecular hydrogen bonds can be further obtained by addition of different salts to ILs mixtures. This leads not only to tissue softening, but also increases solubility of bioactive compounds [84]. Another possibility for simultaneous extraction procedure (pectin and naringin from pomelo peels) is the application of a functionalized ionic liquids (Brönsted acidic ionic liquids), which possesses the properties of both non-acidic ionic liquids and mineral acids [85]. Comparing

Table 3.4 ILs application for microwave extraction of phytocomponents. ILs

Extraction parameters

MAE MAE

P:140–190 W, t: 5-60 s [28] P: 600 W, t: 6 min, T: 70°C, solid-liquid ratio [61] 1:10 [C4C1im]Im - 0.5 M, liquid–solid ratio [62] 24 mL/g, t: 25 min, P: 396 W

Rhizoma Smilacis Glabrae Andrographis paniculate (Burm.f.) Nees Paeonia rockii (S.G. Haw & Lauener) T. Hong & J.J. Li) seed oil Haematococcus pluvialis (Flotow, 1844) Pinus koraiensis Siebold & Zucc. Zingiber officinale Roscoe

Astilbin Diterpenoid lactone-andrographolide Trans-resveratrol

VB3PILs [Bmim]Cl

Astaxanthin

PILs

Gingerols and shogaols

[C10 mim]Br

Verbascoside Lipids

MAE

Rehmannia root Chlorella vulgaris Beijerinck 1890 Curcuma longa L.

[Bemim]Cl [Omim][NTf2 ]; [Omim] [OAc] [OMIM][Br]

BMSHE

Eucalyptus globulus Labill.

VMAE

Sorbus tianschanica Rupr.

MAE

Peperomia pellucida L.

UMAE

Abutilon theophrasti Medik., Rutin and quercetin 1787 Cajanus cajan (L.) Millsp. Flavonoid glycosides

IMUSEH

MALSE MAE MAE

MAE MAE

MAE

[C4 C1 im]Im

Procyanidins and essential oil [Bmim]Br

Curcuminoids Ellagic acid, gallic acid, and essential oil Rutin, hyperoside, and hesperidin Polyphenols

[HO3 S(CH2 )4 mim]HSO4 [C6 mim][BF4 ] [Bmim]BF4 [Bmim]Br [Bmim]Br

Reference

t: 50 s

[67]

P: 581.49 W, t: 15.95 min liquid–solid ratio 11.91 mL/g Ils concentration - 0.80 M; T: 75°C; t: 30 min; P: 400 W, solid–liquid ratio 0.1:10 g/mL. 0.3 mol L–1 of [Bemim]Cl, P: 210 W, t:10 s P:700W, T-60°C; t:5 min

[69]

T - 55°C, t - 8 min, solid-liquid ratio of 0.5/30 (g/mL) ILs concentration - 1.0 M, liquid–solid ratio 30 mL/g, t: 20 min, P: 85 W Vacuum pressure: 0.08 MPa, t:19 min, P: 420 W t: 18.5 min, P: 26.47% W 0.79 mol/L [bmim]BF4 , liquid–solid ratio 10.72 mL/g T: 60°C, t: 12 min, liquid-solid ratio 32 mL/g, P: 534 W, ultrasonic power of 50 W T: 60°C, liquid-solid ratio 20:1 mL/g, t: 13 min

[70]

[60] [71] [72] [73] [74] [75] [76] [77]

(continued on next page)

Chapter 3 r Ionic liquids with microwave-assisted extraction of natural products

Extraction Obtained bioactive method Vegetal material extracted compounds

43

44

Extraction Obtained bioactive method Vegetal material extracted compounds VMAE MAE

MAE MAE

MAE

Populus alba × Populus berolinensis Uncaria tomentosa (Willd. ex Schult.) DC.; Uncaria guianensis (Aubl.) J.F. Gmel. Paeonia x suffruticosa Andrews Schinus terebinthifolius Raddi

ILs

Extraction parameters

Reference

Salicin, Hyperin, and Rutin

[Bmim]BF4

[78]

Hynchophylline, pteropodine, isomitraphylline, and isopteropodine Paeoniflorin

[Bmim]Br

Vacuum pressure: 0.08 MPa t: 20 min, P: 400 W, liquid/solid ratio 25 mL/g ILs concentration: 0,5M; t: 45 s, P: 900 W

[80]

[Bmim]Br

ILs concentration: 1,25 M; liquid–solid ratio 20 mL/g, t: 25 min, P: 700 W t: 10 min, T: 60 ºC, [Bmim]Br: H2 O - 1:1

[81]

DMHEEAP; DMCEAP

t: 1-5 min, solid-liquid ratio: 1: 30 - 2: 5;

[82]

3-oxotirucalla-7,24Z-dien27-oic acid, 3a-hydroxytirucalla-7,24Zdien-27-oic acid, 3a-acetoxytirucalla-7,24Zdien-27-oic acid, gallic acid, and ethyl gallate, Ligusticum chuanxiong Hort. Lactone (senkyunolide I, senkyunolide H, and Z-ligustilide)

[Bmim]Br

[79]

Extraction of Natural Products from Agro-industrial Wastes

Table 3.4 ILs application for microwave extraction of phytocomponents—cont’d

Chapter 3 r Ionic liquids with microwave-assisted extraction of natural products

45

to classical ILs, functionalized ILs are more efficient in pectin extraction due to the controlled pH factor. Under the acidic conditions, insoluble pectin can be hydrolyzed into soluble pectin, dissolved and hence released from plant material, enabling easier extraction of other compounds like naringin [85,86]. Brönsted acidic ionic liquids were also successfully used for catalytic hydrolysis of hydrolysable tannins and essential oil from Eucalyptus globulus Labill. leaves [73].

3.3.2 ILs and MAE for targeted extraction of individual classes of compounds The usefulness of ILs for the MAE of targeted compounds was recently proved, underlining the link between their extraction properties and the chemical structure. ILs with longer alkyl chains present less polar behavior and extraction efficiency of apolar compounds is increased. On the contrary, ILs containing anions (e.g., ToS– , Cl– , and Br– ) are miscible with water and have better affinity to polar molecules [85]. Also, the anion type affects extraction efficiency, Br– being over Cl– and toluene sulfonate as efficient anions [60]. Krishnan et al. used short alkyl chain ILs with different anions for lipid extraction from microalgae [71]. The addition of water to the extraction medium reduced viscosity and density of the mixture and further removed the need to dewater the microalgae before cellular disruption [71]. Liang et al. [72] investigated several different types of ionic liquids, with different anions (BF4– , Br– ), and carbon chain lengths (C-4 to C-8), for the extraction of curcuminoids from Curcuma longa L. [Omim][BF4 ] appeared to be less efficient because of its poor water solubility, but the efficiency of the extraction increased with length of the alkyl chain. The length of alkyl chain was also important during vacuum microwave-assisted extraction of rutin, hyperoside and hesperidin from Sorbus tianschanica Rupr. leaves. The extension of [C2 mim]+ , [Bmim]+ , [C6 mim]+ , and [C8 mim]+ alkyl chain length from ethyl to hexyl increased the extraction yields. Such a behavior represents a compromise between poor cation miscibility with water in case of ILs with longer alkyl chain and higher ability to solubilize targeted active ingredients by ILs with longer alkyl chain [74]. Usually, higher lipophilicity of targeted compounds requires more lipophilic ILs with increasing alkyl chain length [87]. However, the increase of alkyl chain length cannot be unlimited. Long alkyl chain can cause a plateau in the extraction yield due to the formation of micelles and increased steric clash [74]. The mentioned relationship between ILs hydrophobicity and the affinity to extracted molecules was extensively studied for polyphenols. Some authors even proposed the order of hydrophobicity of ILs, [C2 mim]Br < [Bmim]Br < [C6 mim]Br < [C4 mim][N(CN)2 ] < [Bmim][BF4 ], useful for polyphenols extraction [75,88]. Tetrafluoroborate-based ILs were not recommended being water-unstable because they can undergo hydrolysis in aqueous solutions [89]. Besides hydrophobicity of ILs, again the anions, and their hydrogen bonding properties impact MAE of polyphenols [75]. In addition to plant metabolites discussed above, also the other classes of compounds were successfully obtained using ILs in combination with MAE like flavonoids [76–78], alkaloids [79], terpenoids [79,81], or lactones [82].

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Extraction of Natural Products from Agro-industrial Wastes

4 Concluding remarks and future perspectives As presented above, the tandem ILs/microwave-assisted extraction can be considered to be in the development stage. Validation of the multitude of ILs applicable for the extraction of a wide range of phytocomponents of potential interest, inevitably will lead to an explosive development on this field in the coming years. The application of ILs in this area was initially driven by the concepts of “green chemistry.” At first, these solvents were considered a next generation of environmentally friendly chemicals, mainly as a consequence of their low vapor pressure. However, other important properties (such as good water miscibility, solubility or stability) rise a serious concern, not only because they are proven to be toxic for aquatic organisms, but also poorly biodegradable and environmentally persistent pollutants [90]. Generally, the toxicity of ILs is related to their cation component. It increases with the alkyl chain length for the imidazolium, pyridinium and ammonium ILs, and respectively with the number of nitrogen atoms in the aromatic cation ring. The decrease in toxicity can be correlated with the increase in ring methylation and the number of negatively charged atoms on the cation for ammonium, pyridinium, imidazolium, triazolium and tetrazolium ILs [91]. Fluorinated ILs were evaluated to have low ecotoxicity, but they cannot be classified as environmentally acceptable “due to resistance to biotic and abiotic degradation” [92]. What is more, several ILs were also proven to be toxic for Danio rerio (zebrafish). The highest harmfulness was recorded for 1-decyl-3-methylimidazolium nitrate ([C10 mim]NO3 ) and 1-dodecyl-3methylimidazolium nitrate ([C12 mim]NO3 ) with median lethal concentrations (LC50 ) of 4.5, and 3.7 mg/L respectively, in 96 h acute toxicity bioassays [93]. The topic of ILs toxicity is appealing, especially because of their proposed applications in food and pharma industry, where food grade solvents are required. Extensive research on the ILs uncertain safety was summarized in multiple review papers [92,94,95] and as a result, led to the proposal of new compounds, with lower toxicity [96] and enhanced biodegradability [96,97]. This could represent a very promising direction of research driving the development of ILs with an authentic environmentally-friendly character and possible applications for microwave extraction of plant metabolites.

Acknowledgments Irina Fierascu and Radu Claudiu Fierascu gratefully acknowledge the financial support obtained through the grants of the Romanian National Authority for Scientific Research and Innovation, CNCS/CCCDI – UEFISCDI, project BIOHORTINOV, project code PN-III-P1-1.2-PCCDI-2017-0332, project number 6 PCCDI/2018, and project GreenCatOx, project code PN-III-P2-2.1-PED-2019-3166, within PNCDI III. The support of the Ministry of Research, Innovation and Digitization through Program 1 - Development of the national research and development system, Subprogram 1.2 -Institutional performance- Projects to finance excellence in RDI, Contract no. 15PFE / 2021 is also gratefully acknowledged.

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[66] Zeng H, Wang Y, Kong J, Nie C, Yuan Y. Ionic liquid-based microwave-assisted extraction of rutin from Chinese medicinal plants. Talanta 2010;83:582–90. [67] Fan Y, Niu Z, Xu C, Yang L, Chen F, Zhang H. Biocompatible protic ionic liquids-based microwave-assisted liquid-solid extraction of astaxanthin from Haematococcus pluvialis. Ind Crops Prod 2019;141:111809. [68] Sarada R, Vidhyavathi R, Usha D, Ravishankar GA. An efficient method for extraction of astaxanthin from green alga Haematococcus pluvialis. J Agric Food Chem 2006;54:7585–8. [69] Hou K, Bao M, Wang L, Zhang H, Yang L, Zhao H, et al. Aqueous enzymatic pretreatment ionic liquid–lithium salt based microwave–assisted extraction of essential oil and procyanidins from pinecones of Pinus koraiensis. J Clean Prod 2019;236:117581. [70] Guo JB, Fan Y, Zhang WJ, Wu H, Du LM, Chang YX. Extraction of gingerols and shogaols from ginger (Zingiber officinale Roscoe) through microwave technique using ionic liquids. J Food Compos Anal 2017;62:35–42. [71] Krishnan S, Ghani NA, Aminuddin NF, Quraishi KS, Azman NS, Cravotto G, et al. Microwave-assisted lipid extraction from Chlorella vulgaris in water with 0.5%–2.5% of imidazolium based ionic liquid as additive. Renew Energy 2020;149:244–52. [72] Liang H, Wang W, Xu J, Zhang Q, Shen Z, Zeng Z, et al. Optimization of ionic liquid-based microwave-assisted extraction technique for curcuminoids from Curcuma longa L. Food Bioprod Proc 2017;104:57–65. [73] Liu Z, Chen Z, Han F, Kang X, Gu H, Yang L. Microwave-assisted method for simultaneous hydrolysis and extraction in obtaining ellagic acid, gallic acid and essential oil from Eucalyptus globulus leaves using Brönsted acidic ionic liquid [HO3 S(CH2 )4 mim]HSO4 . Ind Crops Prod 2016;81:152–61. [74] Gu H, Chen F, Zhang Q, Zang J. Application of ionic liquids in vacuum microwave-assisted extraction followed by macroporous resin isolation of three flavonoids rutin, hyperoside and hesperidin from Sorbus tianschanica leaves. J Chromatogr B 2016;1014:45–55. [75] Ahmad I, Yanuar A, Mulia K, Mun’im A. Optimization of ionic liquid-based microwave-assisted extraction of polyphenolic content from Peperomia pellucida (L) kunth using response surface methodology. Asian Pac J Trop Biomed 2017;7:660–5. [76] Zhao C, Lu Z, Li C, He X, Li Z, Shi K, et al. Optimization of ionic liquid based simultaneous ultrasonic- and microwave-assisted extraction of rutin and quercetin from leaves of velvet leaf (Abutilon theophrasti) by response surface methodology. Sci World J 2014;2014:283024. [77] Wei W, Fu YJ, Zu YG, Wang W, Luo M, Zhao CJ, et al. Ionic liquid-based microwave-assisted extraction for the determination of flavonoid glycosides in pigeon pea leaves by high-performance liquid chromatography-diode array detector with pentafluorophenyl column. J Sep Sci 2012;35:2875–83. [78] Chen F, Mo K, Liu Z, Yang F, Hou K, Li S, et al. Ionic liquid-based vacuum microwave-assisted extraction followed by macroporous resin enrichment for the separation of the three glycosides salicin, hyperin and rutin from populus bark. Molecules 2014;19:9689 –11. [79] Chang CW, Yeh YY, Chang LC, Hsu MC, Wu YT. Rapid determination of oxindole alkaloids in cat’s claw by HPLC using ionic liquid-based microwave-assisted extraction and silica monolithic column. Biomed Chromatogr 2017;31:e3925. [80] Chen F, Mo K, Zhang Q, Fei S, Zu Y, Yang L. A novel approach for distillation of paeonol and simultaneous extraction of paeoniflorin by microwave irradiation using an ionic liquid solution as the reaction medium. Sep Purif Technol 2017;183:73–82. [81] Morais TR, Coutinho APR, Camilo FF, Martins TS, Sartorelli P, Massaoka MH, et al. Application of an ionic liquid in the microwave assisted extraction of cytotoxic metabolites from fruits of Schinus terebinthifolius Raddi (Anacardiaceae). J Braz Chem Soc 2017;28:492–7. [82] Yansheng C, Zhida Z, Changping L, Qingshan L, Peifang Y, Welz-Biermann U. Microwave-assisted extraction of lactones from Ligusticum chuanxiong Hort. Using protic ionic liquids. Green Chem 2011;13:666–70.

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[83] Sun YK, Sun GY, Jia M, Yang J, Liu ZS, Huang YP, et al. Cost-effective imprinting to minimize consumption of template in room-temperature ionic liquid for fast purification of chlorogenic acid from the extract of E. ulmoides leaves. Anal Bioanal Chem 2019;411:1261–71. [84] Zhang H, Wu J, Zhang J, He J. 1-allyl-3-methylimidazolium chloride room temperature ionic liquid: a new and powerful nonderivatizing solvent for cellulose. Macromolecules 2005;38:8272–7. [85] Liu Z, Qiao L, Gu H, Yang F, Yang L. Development of Brönsted acidic ionic liquid based microwave assisted method for simultaneous extraction of pectin and naringin from pomelo peels. Sep Purif Technol 2017;172:326–37. [86] Huang G, Shi J, Zhang K, Huang X. Application of ionic liquids in the microwave-assisted extraction of pectin from lemon peels. J Anal Method Chem 2012;2012:302059. [87] Yang L, Wang H, Zu YG, Zhao C, Zhang L, Chen X, et al. Ultrasound-assisted extraction of the three terpenoid indole alkaloids vindoline, catharanthine and vinblastine from Catharanthus roseus using ionic liquid aqueous solutions. Chem Eng J 2011;172:705–12. [88] Tan Z, Yi Y, Wang H, Zhou W, Wang C, McPhee DJ. Extraction, preconcentration and isolation of flavonoids from Apocynum venetum L. leaves using ionic liquid-based ultrasonic-assisted extraction coupled with an aqueous biphasic system. Molecules 2016;21:262. [89] Freire MG, Neves CMSS, Marrucho IM, Coutinho JAP, Fernandes AM. Hydrolysis of tetrafluoroborate and hexafluorophosphate counter ions in imidazolium-based ionic liquids. J Phys Chem A 2010;114:3744–9. [90] Kudłak B, Owczarek K, Namie´snik J. Selected issues related to the toxicity of ionic liquids and deep eutectic solvents—a review. Environ Sci Pollut Res 2015;22:11975–92. [91] Couling DJ, Bernot RJ, Docherty KM, Dixon JNK, Maginn EJ. Assessing the factors responsible for ionic liquid toxicity to aquatic organisms via quantitative structure–property relationship modelling. Green Chem 2006;8:82–90. [92] Vieira NSM, Stolte S, Araújo JMM, Rebelo LPN, Pereiro AB, Markiewicz M. Acute aquatic toxicity and biodegradability of fluorinated ionic liquids. ACS Sustain Chem Eng 2019;7:3733–41. [93] Zhang C, Zhu L, Wang J, Wang J, Zhou T, Xu Y, et al. The acute toxic effects of imidazolium-based ionic liquids with different alkyl-chain lengths and anions on zebrafish (Danio rerio). Ecotoxicol Environ Saf 2017;140:235–40. [94] Hartmann DO, Pereira CS. Toxicity of ionic liquids: past, present, and future. In: Xu X, Guo Z, Cheong LZ Ionic, editors. Liquids in lipid processing and analysis: opportunities and challenges. London: AOCS Press; 2016. p. 403. [95] Thuy Pham TP, Cho CW, Yun YS. Environmental fate and toxicity of ionic liquids: a review. Water Res 2010;44:352–72. [96] El Blidi L, Saleh J, Ben Ghanem O, El-Harbawi M, Lévêque JM, Hadj-Kali MK. Synthesis, characterization, and antimicrobial toxicity study of dicyanamide-based ionic liquids and their application to liquid-liquid extraction. J Chem Eng Data 2020;65:34–42. [97] Markiewicz M, Maszkowska J, Nardello-Rataj V, Stolte S. Readily biodegradable and low-toxic biocompatible ionic liquids for cellulose processing. RSC Adv 2016;6:87325–31.

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Pressurized liquid extraction of natural products Sorin Marius Avramescu a,b, Irina Fierascu c, Radu Claudiu Fierascu c and Mihaela Cudalbeanu b a DEPARTMENT

OF ORGANIC CHEMISTRY, BIOCHEMISTRY AND CATALYSIS, FACULTY OF

CHEMISTRY, UNIVERSITY OF BUCHAREST, BUCHAREST, ROMANIA

b RESEARCH

CENTER

FOR ENVIRONMENTAL PROTECTION AND WASTE MANAGEMENT, UNIVERSITY OF BUCHAREST, BUCHAREST, ROMANIA c NATIONAL INSTITUTE FOR RESEARCH & DEVELOPMENT IN CHEMISTRY AND PETROCHEMISTRY—ICECHIM, BUCHAREST, ROMANIA

4.1 Introduction The holistic approach to using medicinal plants and other crops as an important source of natural compounds is the ultimate alternative to developing new pharmaceuticals, improving the existent ones, and replacing the synthetic route of producing valuable medicine [1,2]. Several essential aspects concur to fulfill this endeavor successfully: r Numerous plants containing a large range of natural compounds are found in natural ecosystems or are already adapted for large-scale cultivation; r A vast amount of data from traditional medicine offer valuable support for developing new drugs; r Development of omics tools (genomics, proteomics, metabolomics, metagenomics) and dereplication strategies as a tool for a better understanding of biological processes and to find solutions for high challenges encountered in this field; r An unprecedented evolution of analytical and separation techniques which assure a comprehensive view on therapeutic plants potential. Extraction represents the core of the natural compound recovery from the vegetal matrix. In most of these processes, particular forms of energy waves or pulses (electromagnetic, acoustic, electrical) are ultimately transformed into thermal energy, which enhances the yields of extraction, leading to higher amounts in desired compounds (Fig. 4.1). Therefore, to obtain a liquid with a complete or partial desired chemical profile, an extensive range of methods were developed and tailored to match the solid vegetal characteristics and the properties of target compounds. Regarding the timeline of extraction methods, their development lies in two main categories: classical and modern. The classical methods (maceration, percolation, decoction, Soxhlet, Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach. DOI: https://doi.org/10.1016/B978-0-12-823349-8.00019-8 c 2023 Elsevier Inc. All rights reserved. Copyright 

53

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Extraction of Natural Products from Agro-industrial Wastes

Ultrasount assisted extraction (UAE)

Pressurized liquid extraction (PLE)

Supercritical fluid extraction (SFE)

Instant controlled pressure drop extraction (DIC)

Pulsed Electric Field Extraction

EXTRACTION METHODS

High hydrostatic pressure extraction (HHPE) Enzyme-assisted extraction

Mecrowaveassisted extraction (MAE)

Phytonic extraction

FIGURE 4.1 Modern extraction methods are used for the advances recovery of natural compounds from vegetal matrices.

FIGURE 4.2 Green solvents which become an alternative for the sustainable extraction of natural compounds.

enfleurage) continuously enhance or provide a reliable comparison tool. Improvement of classical methods and development of new ones is also facilitated by using new solvents with an accent on “green” features (Fig. 4.2). Extraction performance is primarily affected by the choice of well-known operational parameters: temperature, pressure, suitable size reduction of vegetal material, solvent nature,

Chapter 4 r Pressurized liquid extraction of natural products

55

solvent/solid ratio, extraction time. Due to their complexity, extraction processes need optimization by a good design of experiments, generally by response surface methodology (RSM). Some techniques use a large variety of pressure values from negative to positive. Hence, this chapter presents the principles and characteristics of some emergent methods where pressure is the main parameter and significantly improves the extraction efficiency.

4.1.1 Pressurized liquid extraction (PLE) Pressurized liquid extraction (PLE) [3–12] represents a mixture of techniques differentiated mainly by values of operating parameters (sub- or supercritical) and solvent used. The approach is to use solvents with different polarities to extract an extensive range of natural compounds. CO2 supercritical extraction (SFE-CO2 ) [13–17] is a genuinely eco-friendly method due to its main attributes: it is a nontoxic or reactive solvent and operates at low temperatures; therefore, the integrity of phytonutrients remain intact. However, CO2 used alone is applicable mainly for nonpolar compounds, including essential oils, phytosterols, and fatty acids. Other compounds can be used as co-solvents (ethanol, ethyl lactate, methanol), leading to a lesser green process. Negative aspects are the high capital costs, it is difficult to operate/optimize the installation, and the scale-up is challenging. Other solvents potentially used in supercritical fluid extraction (methane, ethylene, propylene, ammonia) have lower performance or are not environmentally suitable. Alternative pressure liquid extraction approaches operate below critical parameters; nevertheless, they are very efficient in recovering an extensive range of natural compounds with medium and higher polarity. These techniques bear different names according to the nature of solvent utilized: r Solvents based PLE, also known as pressurized liquid extraction (PLE)/accelerated solvent extraction (ASE)/pressurized hot solvent extraction (PHSE)/pressurized fluid extraction (PFE) r Water-based PLE also called subcritical water extraction (SWE)/pressurized hot water extraction (PHWE)/pressurized low polarity water extraction (PLPW)/superheated water extraction (SHWE) r Phytonic process [18] These techniques originated from Dionex Corporation, which designed a device based on the PLE principle branded as Accelerated Solvent Extraction (ASE) [19–24]. The label incorporates this device main feature, meaning that the extraction process occurs very fast compared with other conventional methods like Soxhlet. In the green extraction paradigm, the superiority of this approach over classical processes is incontestable (Table 4.1) yet, the main advantages are short extraction time and low amount of solvents required. In some applications, the eco-footprint of pressure extraction was 33 times lower comparing with the Soxhlet method. The initial purpose of this equipment was for sample preparation required in complex analytical evaluation using advanced techniques like GC, GC-MS, HPLC. The sample preparation step before analytical runs is a difficult task and represents the primary consumer of resources.

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Table 4.1 Comparison of performances and compliances with green chemistry principles of PLE and Soxhlet methods (Adapted with permission from Ref. [5]). Parameters

Soxhlet

PLE (ASE)

Raw material required (g) Solvent amount used (ml) Energy consumption (kWh)∗ Time consumption in the process (h) By-products (amount of waste generated) (g) Target compound recovery (%)

10 300 N/A 9.5 ∼8 87.7

3 50 N/A 1 ∼0.7 100

∗

Energy consumption was not evaluated in the study, while according to authors is much lower for PLE considering the shorter processing time.

Due to its essential advantages, the ASE process is currently implemented in numerous standardized methods for determinations of pesticides, natural products, environmental contaminants, consumer products. Also, PLE is easy to scale up, and the cost of manufacturing decrease significantly compared with classical methods for higher reactors volume. The extraction of antioxidants from jabuticaba skins in 0.3 m3 extractor produce 2.14- and 1.67-fold more anthocyanin and total phenols comparing to atmospheric pressure extraction, while the cost of manufacturing (COM) was about 40-fold lower [25]. Extraction process efficiency is strongly dependent on the vegetal matrix and the interaction/position of the target compound inside the solid particles. The process itself occurs at a molecular level in several stages: r The vegetal sample is soaked in solvent, and all pores are more or less filled with liquid (depending on the solvent type, solid characteristics, pressure, and temperature); r Solvation power of the liquid produces desorption or breaking the chemical bonds of a target compound from a solid matrix; r Diffusion of all desorbed compounds from inner pores to the bulk solution. Regardless of the vegetal material or solvent used, the PLE setup is relatively simple and is configurable in three distinct modes: static (Fig. 4.3A), dynamic, and static-dynamic (Fig. 4.3B). These devices consist of solvent reservoirs, a pump, a pressurized gas container, an extraction cell inserted in an oven to assure desired temperature, a valve working in a dynamic or static mode, and a vessel for extract collection. Although the relative simplicity of the experimental setup, this type of process needs detailed modeling and optimization of operational parameters (Fig. 4.4).

4.1.2 Influence of operational parameters Temperature—Temperature represents an essential parameter since can have both positive and negative influence on the extraction processes. Beneficial characteristics are: r most compounds are very soluble at higher temperatures, r the viscosity of the solvents decrease; therefore, the boundary layer thickness decrease

Chapter 4 r Pressurized liquid extraction of natural products

57

FIGURE 4.3 General PLE setup. (A) static approach: (1) solvent reservoir, (2) pump, (3) gas tank, (4) three-way purge valve, (5) three-way relief valve, (6) oven, (7) extraction cell, (8) static valve, (9) collection vessel. (B) static/dynamic approach: (1) solvent reservoir, (2) pump, (3) two-way static/dynamic valve, (4) oven, (5) extraction cell, (6) condenser, (7) relief valve, (8) collection vessel.

FIGURE 4.4 Operational factors that require optimization for higher PLE efficiency.

r diffusion rates increase and therefore mass transfer increase r the dielectric constant of solvents can change and, as a consequence, their polarity is changing water being a good example [26–28] (Fig. 4.5) r solvent surface tension decrease. Detrimental aspects refer mainly to the sensitivity of a large number of natural compounds at higher temperatures. Most importantly, the optimization step is difficult to achieve since the extraction yield increases with temperature up to some point and, after this value, drops rapidly. This behavior depends on solvents used, thus the need for detailed modeling and application of response surface methodology as a tool for process optimization. Table 4.2 presents high differences between obtained yields using solvents with various dielectric constants at several temperatures and 100 bars.

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FIGURE 4.5 Variation of water dielectric constant with the temperature at 20 MPa.

Table 4.2 Extraction yields (%) from L. ochroleuca using PLE in various operational conditions (Adapted with permission from Ref. [7]). Temperature (°C)

Hexane

Ethyl acetate

Ethanol

Ethanol : Water (1:1) (v/v)

80 120 160

8.39 ± 1.19 9.02 ± 0.45 7.425 ± 1.54

5.25 ± 2.74 7.42 ± 1.73 5.29 ± 1.02

12.21 ± 0.33 15.54 ± 2.50 11.55 ± 2.41

37.48 ± 12.12 47.16 ± 2.67 51.91 ± 4.25

Pressure—Pressure is mostly a “silent parameter” that has less significance than temperature and even other variables but with an important impact in most cases. The main advantage of using high pressure in PLE processes is that the solvents penetrate deeply into the vegetal material. A highly synergetic effect results when appropriate temperature and pressure are applied. More importantly, adequate pressure maintains the solvent in liquid form when conditions are below the critical temperature point. Also, in most PLE processes, when pressure rises, the yield increases accordingly and, after some point, the yield remains constant on a plateau. This phenomenon occurs due to a compensating effect between increasing solvating power of solvents at higher densities and, at the same time, a decrease of diffusion coefficients with a detrimental effect on target compound recovery [22,29,30]. Also, molecules with larger molecular mass (proteins or lipids) are efficiently extracted at higher pressures. About 36% more protein was obtained from brewer’s spent grain using PLE comparing with UAE [7,31]. In this technique, the pressure maintained by an inert gas (usually nitrogen) assures the flushing of remained solvent after a large part of the extract was evacuated. Solvents—In this method, the selection of solvents types and mixtures of them represent the main challenge [23] as there are an extensive range of liquids to be used: alcohols (methanol, ethanol, and isopropanol), alkanes (cyclohexane, hexane and heptane), water (at different temperatures). It is essential to avoid harmful solvents (halogenated compounds, tetrahydrofuran)

Chapter 4 r Pressurized liquid extraction of natural products

59

Table 4.3 Extraction temperature for several natural compounds found in the different vegetal matrix. Compound

Temperature (°C)

Quercitrin Phenolic compounds Spiraeoside and isoquercitrin Isoxanthohumol Camphor, borneol, and borneol acetate Quercetin Isorhamnetin, kaempferol, apigenin

110 140 150 150 160 170 190

or solvents with an auto-ignition interval of 40°C–200°C (CS2 , diethyl ether). Methanol and water are suitable for this method solely or in mixtures with other polar or nonpolar liquids. Extraction mode—Extraction mode has a considerable influence on the overall yield and the chemical composition. The static procedure consists of maintaining the solvent and the solid at high pressure and temperature for a certain period in several cycles to attain the desired yield (Fig. 4.4A). Dynamic setup implies the insertion of the solid into the extraction cell, adding the solvent, attaining the desired operational parameters, and releasing the solvent at a specific flow rate through the solid bed (Fig. 4.4B). In static mode, several cycles are mandatory due to the large concentration of compounds in the solid sample or the lower solvation capacity of the liquid used. The mass transfer is optimal in dynamic mode, but the solvent consumption is too high. Nevertheless, in either mode, the process gives greater yields than other methods. Staticdynamic is preferable since both situations cumulate their advantages and represent a better approach [32]. Additives—PLE is improved by using several solids as dispersants or desiccants: alumina, quartz, diatomaceous earth, sand, glass beads, cellulose, sodium sulfate. These solids increase the contact between solvent and vegetal material by preventing the sample compression and removing residual humidity, which otherwise can hinder the process through competition with extraction solvent [30,33–35]. Pressurized hot-water extraction (PHWE)—All extraction processes tend to become greener, and PLE is not making an exception. For that, the main criterion is to avoid organic solvents as much as possible. Water is an eco-friendly solvent and working at different temperatures ensures a selective extraction of target compounds (Table 4.3). Moreover, the process is amenable to scale-up. Still, the main drawbacks are potential corrosion of water at superior temperatures and the requirement of Triton X-100 (or substitutes) for micelle-mediated process in the case of thermosensitive components [36,37].

4.1.3 Phytonic process In this application patented by Advanced Photonics Limited (Manchester, UK), extraction is based on HCF-134a or 1,1,1,2 tetrafluoroethane. This solvent is primarily used in numerous countries for refrigeration or medical applications to replace chlorofluorocarbons [38]. The substitution was necessary since HCF-134a has 18 times lower ODF capacity (ozone layer depletion)

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Extraction of Natural Products from Agro-industrial Wastes

FIGURE 4.6 Schematic presentation of phytonic process: (1) extractor vessel containing plant material, (2) extract collector/flush drum, (3) dehydration column, (4) compressor, (5) solvent tank, (6) condenser. (Adapted with permission from R.C. Costello & Assoc., Inc.)

than CFC-12. However, it is not entirely an ecological solution because it has a GWP (global warming potential) of 1300 reported to CO2 and 13 years lifetime. Concerning plant extraction, this approach presents several advantages comparing with other PLE methods: r Lower temperature and pressure are required. This process is essentially a reversed refrigerator and works at 5–10 bars and 15°C–50°C. The mild operational parameters assure a low energy consumption avoiding the thermal degradation of sensitive compounds. Three fractions were collected in an application for ginger oil extraction by applying three temperature values: 15°C, 25°C, and 40°C. Hence, depending on the vegetal matrix and operating parameters photonic process is selective for numerous target compounds. r Closed circuits allow a higher recovery of volatile compounds and complete recycling of solvent. r The corrosion problem is circumvented since this solvent is inert, the pH is neutral, and the oxygen is absent. Therefore hydrolysis or oxidation reactions are eliminated. Also, the solvent is nonflammable and nontoxic. Residual biomass management does not involve disposal issues. The process flow is presented in Fig. 4.6. The plant material and the HCF-134a are inserted in the extractor (1) at the desired temperature and pressure. The extract is collected in another

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vessel (2) from where the fluorinated solvent is vaporized and evacuated into the purification column (3). After purification, the solvent is liquefied using a compressor (4), stored into the solvent tank (5), and recirculated in the extraction process. The phytonic process has numerous applications: production of antibiotics, pharmaceuticalgrade extracts, pharmacologically active intermediates, extraction of essential oil, and flavors. A particular case is the extraction of artemisinin [39–41] from Artemisia Annua L., which is a very effective and affordable antimalaria therapeutic agent. Since discovering the artemisinin antimalaria potential, the demand for this compound has increased exponentially, reaching 799M treatments in 2020 and comprising about 49% of the antimalarial treatments market [42]. The concentration of artemisinin in extracts depends strongly on the solvent used and reaches higher values when using HCF-134a (20%–30%) comparing with hexane (10%–15%), toluene (10%–15%), and ethanol ( delicious > American variety. Ferrer et al. [78] extracted the pectin from the passion fruit peel and studied pectin content through acid hydrolysis process in an environment of pH 3.0, 90°C–95°C temperature for 90 minutes. Ripening increases the pectin extraction in fruits, e.g., the ripen passion fruit peel showed the maximum pectin content while less ripe peels showed better gelling characteristics. Rehman and Salariya [79] studied the comparative characteristics of pectin extracted from Feutral, Musambi, Malta and Kinnow and observed that the temperature, pH and time considerably affected the pectin extraction. The pectin yield of Feutral was highest, followed by Mosambi, Malta and Kinnow varieties. Pectin can also be extracted from apple pomace as confirmed by the study and also highest yield was reported at 100°C after an extraction time of 180 minutes [80]. The factors, i.e., pH, time, and temperature also determine the yield and quality of pectin that is supported by the study of

Chapter 15 r Extraction of pectin from agro-industrial waste 255

Hussain et al. [81] confirming the highest pectin yield from orange peel (16.10%) at processing for 120 minutes at 80°C temperature and 2.5 pH. Similarly, in another study, Langrish et al. [82] studied the parameters like pH and solvent, the mode of extraction (Microwave and Soxhlet extraction method) affecting the pectin extraction from orange peel and found microwave extraction technique for 15 minutes effective in increasing the yield. Emaga et al. [53] reported that the chemical composition of pectin was responsible for the effect of pH on pectin yield. In banana peel, lower pH helps to enhance the pectin yield while decreasing the galacturonic acid content. Moreover, pH affects the macromolecular as well as chemical characteristics of pectin extracted from cacao pod husk with an extraction time of 3 hours, 95°C temperature at pH 2.5 in citric acid resulting in the maximum pectin extraction [44]. The temperature used in the process of extraction usually affects molecular weight and yield with no significant effect on the degree of esterification that was depicted from the studies of Methacanon et al. [83] on pectin of pomelo (Citrus maxima). Saba banana peel was used for the extraction of pectin in 0.5 N HCL at different pH depicting the maximum yield at pH 4 [68]. Moreover, maximum pectin extraction from durian rinds was reported at pH 2.8 through an extraction time of 45 minutes.

15.6 Conclusion Present world witnesses wastes and by-products from agriculture to the consumer level in huge quantities. The aforementioned wastes are treasures of high valued compounds such as pectin that could be used in various fields. The rising levels of agro-industrial wastes need advanced and innovative approaches for the extraction of high-added value compounds. Apart from holding an eminent role in food industries pectin finds its participation in industries such as cosmetic and pharmaceutical where it acts as a gelling, thickening, and stabilizing agent, besides helping in drug delivery and gene delivery. The present chapter focused on the structure of pectin and some recent studies on pectin extraction from agro-industrial waste and some important quality attributes. Tremendous work has been done on the recovery and extraction of pectin involving some novel techniques from agro-industrial waste. However, there is an immense need for the researchers to focus on some innovative methodologies for better recovery of pectin that may result in better and proper utilization of waste. With this concept, extraction of these valued compounds from agro-industrial waste through green and feasible separation may be attractive considering economic and socio-environmental contexts.

Acknowledgment Awarding the Senior Research Fellowship to the first author (Arshied Manzoor) by Indian Council of Medical Research, New Delhi, India is duly acknowledged.

References [1] Mohnen D. Pectin structure and biosynthesis. Curr Opin Plant Biol 2008;11(3):266–77. [2] Xie L, Li X, Guo Y. Ultrafiltration behaviors of pectin-containing solution extracted from citrus peel on a ZrO2 ceramic membrane pilot unit. Korean J Chem Eng 2008;25(1):149–53.

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16

  

Extraction of cellulosic fibers from date palm by-products Lobna A. Elseify a, Mohamad Midani a,b, Tamer Hamouda c, Ramzi Khiari d,e,f and Ahmed H. Hassanin g,h a DEPARTMENT

EGYPT

OF MATERIALS ENGINEERING, GERMAN UNIVERSITY IN CAIRO, CAIRO, b WILSON

COLLEGE OF TEXTILES, NC STATE UNIVERSITY, RALEIGH, NC,

UNITED STATES c TEXTILE RESEARCH DIVISION, NATIONAL RESEARCH CENTER, CAIRO, EGYPT

d RESEARCH

UNITY OF APPLIED CHEMISTRY & ENVIRONMENT, UNIVERSITY OF

MONASTIR, MONASTIR, TUNISIA e DEPARTMENT OF TEXTILE, HIGHER INSTITUTE OF TECHNOLOGICAL STUDIES OF KSAR HELLAL, MONASTIR, TUNISIA f CNRS, UNIVERSITY OF GRENOBLE ALPES, GRENOBLE, FRANCE

g MATERIALS

SCIENCE AND ENGINEERING

DEPARTMENT, EGYPT-JAPAN UNIVERSITY OF SCIENCE AND TECHNOLOGY (E-JUST), NEW BORG EL-ARAB CITY, EGYPT

h DEPARTMENT

OF TEXTILES ENGINEERING,

ALEXANDRIA UNIVERSITY, ALEXANDRIA, EGYPT

16.1 Introduction Natural fibers, which are obtained from natural sources, have two types; cellulose fibers and protein fibers. Protein fibers are obtained from animals resources, such as silk, wool and hair, and cellulosic fibers which are obtained from plants, such as flax, jute, sisal, date palm and cotton [1]. Date palm (Phoenix Dactylifera L.) is one of the abundant sources of cellulosic fibers where fibers could be extracted from four different parts; midribs, spadix stems, leaflets, and mesh as shown in Fig. 16.1. Date palm, as a source of natural cellulosic fibers, was chosen for investigation due to its wide availability, there are more than 85 million date palms located in the MENA region. Moreover, according to a study made by El-Mously in 2005 a single female date palm tree produces annually a dry weight of 9.75 kg of midribs, 7 kg of spadix stems, 8 kg of leaflets, and, 1.25 kg of mesh [2]. Many research were performed to investigate the possibility of extracting fibers from different parts of the date palm [3–24]. Nowadays there is a renewed interest in replacing manmade fibers with bio-based materials in composites manufacturing. The strength of the reinforcing fibers is one of the main properties that determine the adequacy of their use. Hence, obtaining long strong bio-based fibers that could be processed in order to be used in different applications is very important and one of the emerging research topics. Date palm fibers were used in different applications in the literature. They were used as a reinforcement to composites either in a thermoplastic, thermoset, Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach. DOI: https://doi.org/10.1016/B978-0-12-823349-8.00009-5 c 2023 Elsevier Inc. All rights reserved. Copyright 

261

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Extraction of Natural Products from Agro-industrial Wastes

FIGURE 16.1 Date palm parts from which fibers can be extracted.

or bio-based matrices [25–32]. Date palm fibers were used as a reinforcement in particleboards [33–36] and also in papermaking industry [21,6,9]. Moreover, date palm fibers were used in other applications like cement, concrete, asphalt, and gypsum reinforcement, and also in insulating panels [19,22,37–41]. However, the literature wasn’t informative and there were so many ambiguities, and discrepancies between the work of different researchers; they used different terminologies referring to the same thing. Moreover, there is a lack of research in this area and it is considered a new field of research. Furthermore, the extraction processes used in the literature were incomplete, fibers weren’t efficiently extracted from the source and this is supported by the fact that the fibers were coarse ground fibers with a large amount of lignin and hemicellulose sticking on the surface. Also, the fibers were more of particles than fibers due to their very short length which is less than 5 mm [42,43]. Due to the above-mentioned limitations and the large availability of byproducts of annual pruning, especially the midribs, the objective of this research is to extract long fibrillated date palm cellulosic fibers from the date palm midribs and to investigate the effect of the alkaline treatment on the mechanical properties of the extracted fibers.

16.2 Materials and methods 16.2.1 Materials The midribs were obtained from a female Barhi cultivar date palm located in El-Sharkeya governorate in Egypt. The midribs were obtained from the same date palm at the same time to ensure consistency and to eliminate the influence of the cultivation factors. The fibers extraction was achieved by alkaline chemical treatment using highly purified sodium hydroxide NaOH at different concentration. The alkaline treatment was followed by

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Table 16.1 Experimental design. Factors

Levels

No. of levels

Time (hr.) Concentration (%) Temperature (°C)

1, 2, 3 1, 3, 5 25, 75, 100 Total runs

3 3 3 3 × 3 × 3 = 27

neutralization process using 5% glacial acetic acid solution. Sodium hydroxide was chosen since it’s widely used to treat similar natural fibers sources, wide availability, low cost, and high efficiency.

16.2.2 Fibers extraction The samples were prepared by a 4-step process; midribs preparation, alkaline treatment, mechanical separation and neutralization. The midribs were cut into 30 cm long pieces; afterward, the chemical treatment was performed by immersing the midribs into a tank containing NaOH solution of different concentrations and at different temperatures depending on the experimental plan. Upon completion of the alkaline treatment, the midribs were then squeezed using a commercial rolling machine. Then finally, the samples were thoroughly washed with water then neutralized by immersion in 5% glacial acetic acid solution. Three factors were identified as the most influencing factors in the alkaline treatment; NaOH %, treatment duration, and treatment temperature. After analyzing all the possible NaOH alkaline treatment conditions and how often they were used in the literature, it was found that the use of 1% NaOH at 100°C for 1 hour was the most frequently used combination in addition to the use of 5% NaOH at 90°C for 3 hours [43]. The experimental design was formulated while taking into consideration that some of the conditions used in the literature are not economical to apply on an industrial scale; like using high NaOH concentration for long time. Moreover, increasing NaOH % would make the process less eco-friendly and uneconomical. Consequently, the experimental design was made to cover wide range of treatment conditions such that the three factors have three levels each. Therefore, the NaOH concentration varied between 1%, 3%, or 5%. The duration was either 1 hr, 2 hr, or 3 hr. Finally, the temperature was either 25, 75, or 100°C. Hence, the total number of samples is 27 different samples in addition to one untreated control sample that acted as a reference. The bath ratio (liquor ratio) was 40. The experimental design is shown in Table 16.1. Also, the samples ID and treatment conditions are shown in Table 16.2.

16.2.3 Testing and evaluation 16.2.3.1 Cross-sectional area Cross-sectional area was measured using the cork method where the fibers are pulled inside a cork by means of a needle and a thread as shown in Fig. 16.2A. A typical image of a fiber bundle

264

Treatment parameters

Fibers properties (mm2 )

Sample ID

Temp (°C)

NaOH (%)

Duration (hr)

Area

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

100 75 25 100 75 25 100 75 25 100 75 25 100 75 25 100 75 25 100 75 25 100 75 25 100 75 25 -

1% 1% 1% 3% 3% 3% 5% 5% 5% 1% 1% 1% 3% 3% 3% 5% 5% 5% 1% 1% 1% 3% 3% 3% 5% 5% 5% -

1 hr 1 hr 1 hr 1 hr 1 hr 1 hr 1 hr 1 hr 1 hr 2 hr 2 hr 2 hr 2 hr 2 hr 2 hr 2 hr 2 hr 2 hr 3 hr 3 hr 3 hr 3 hr 3 hr 3 hr 3 hr 3 hr 3 hr -

0.06097 0.06537 0.08177 0.06174 0.12868 0.13778 0.04782 0.05238 0.07274 0.06419 0.06044 0.10377 0.06782 0.05709 0.13536 0.06317 0.06043 0.08905 0.04628 0.06646 0.11114 0.0687 0.084388 0.08334 0.045534 0.057552 0.072778 0.202498

CV (%)

σ (MPa)

CV (%)

E (GPa)

CV (%)

65.80 73.59 125.7 53.67 123.65 91.24 53.16 52.44 54.12 74.15 62.69 62.10 50.46 57.12 61.94 61.14 48.31 68.14 49.13 55.02 56.85 55.73 52.21 69.88 72.61 63.77 50.64 83.80

452.79 408.45 222.87 256.52 120.84 104.98 162.72 284.57 263.32 134.94 312.47 152.93 184.48 175.73 193.14 114.01 125.64 302.86 181.13 321.01 163.58 224.11 142.23 300.94 164.24 112.19 391.54 118.44

33.93 44.26 37.33 37.97 18.79 36.08 36.08 30.00 10.79 16.26 83.99 44.34 36.70 36.08 54.35 21.45 30.58 18.51 33.43 29.09 24.03 14.99 34.20 62.10 46.79 32.15 40.24 37.91

10.49 10.02 6.60 5.21 3.08 3.32 5.00 7.51 6.94 3.31 7.08 4.33 4.06 4.70 4.38 1.59 4.04 6.35 5.11 7.57 6.23 4.85 3.36 5.16 1.93 4.10 8.98 3.04

37.90 35.89 31.85 27.31 18.31 30.51 25.37 21.77 15.43 20.24 93.72 37.05 45.19 29.96 37.44 40.48 36.98 22.86 39.76 27.48 21.52 18.21 49.29 37.06 31.48 51.04 31.97 24.49

Extraction of Natural Products from Agro-industrial Wastes

Table 16.2 Samples ID and date palm fibers physical and mechanical properties.

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FIGURE 16.2 (A) Embedded fibers using cork method and (B) typical cross-sectional view of embedded fibers bundle observed using optical microscope.

FIGURE 16.3 Optical Microscope images of traced fibers for area calculations.

embedded in cork viewed using optical microscope is shown in Fig. 16.2B. The cross-sectional area was calculated by tracing the fibers cross-section area using an image analysis software and the average area was calculated for each sample. Nearly an average of 98 fibers was measured per sample. Fig. 16.3 shows optical microscope images of fibers after tracing to calculate the crosssectional area.

16.2.3.2 Mechanical properties The mechanical properties of the fibers were determined by performing single fiber tensile test (SFTT) according to the standard test ASTM D 3822 – 01. The standard test method was used to determine the dry and wet strength of the fiber as well as the modulus of elasticity. The fiber

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FIGURE 16.4 SFTT (A) schematic diagram of the cardboard frame used for testing, real testing frame for (B) dry and (C) wet SFTT, and, (D) SFTT frame mounted between pneumatic grips and a close up look showing place of cut.

surface was examined first using a stereo microscope to ensure that the fibers are free of any surface defects and also to ensure that only a single fiber will be tested. A single fiber was mounted between 2 frames then bonded together using waterproof Cyanoacrylate adhesive. The frame’s dimensions are 4 × 5 cm and the window centered inside is of dimensions 2.5 × 1 cm allowing 10 mm gauge length as shown in Fig. 16.4A. Fig. 16.4B is a real dry SFTT testing frame while Fig. 16.4D shows the frame after being secured inside the pneumatic grips having pressure between 7-8 MPa. The tensile test was conducted at strain rate 0.5 mm/min with zero initial load. The load cell of the tensile tester was equal to 100 N. For the dry tensile test, the frames were made of cardboard; while for the wet test the frames were made of thermoplastic sheets. For wet tensile strength testing, the fibers were soaked in distilled water for 15 ± 1 minutes. Afterward, the fibers were removed and tested within 2 minutes using same test parameters as the dry strength. A real wet SFTT testing frame is shown in Fig. 16.4C. For both the dry and wet SFTT 10 specimens were tested per sample.

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16.2.4 Statistical analysis To determine the effect of the independent parameters (NaOH %, treatment duration, and treatment temperature) on the dependent parameters (cross-sectional area, tensile strength, and modulus of elasticity) the results were statistically analyzed using IBM SPSS software. The statistical tools used were main effects, univariate analysis of variance (ANOVA), Duncan post hoc. The ANOVA was used to determine if the independent parameters had a significant effect on the dependent parameters or not. Moreover, Duncan post hoc test was used to confirm the ANOVA results and to show the exact location of significance among the parameter three levels.

16.3 Results and discussion 16.3.1 Cross-sectional area The average cross-sectional areas of the 28 different samples were calculated and their results are listed in Table 16.2. The date palm midrib is composed of fiber vascular bundles embedded in a lignin matrix. These vascular bundles contain two large hollow lumens in addition to other considerable amount of hollow content. Furthermore, those vascular bundles are composed of much smaller elemental micro-fibrils held together by hemicellulose. When the fibers are treated with caustic soda, this causes an initial dissolution of the amorphous constituents such as lignin and hemicellulose resulting in a reduced cross section area, further treatment result in swelling of the cellulose and a significant increase in the cross-sectional area. Both the dissolution and swelling are essential steps for the caustic soda reaction and both are strongly dependent on treatment temperature and caustic soda concentration [44]. As the treatment continues, the swollen vascular bundles are broken down into smaller longitudinal bundles, resulting in a significant reduction in area due to effective removal of the large hollow content in the lumens as shown in Fig. 16.5. Further treatment will result in further fibrillation of the longitudinal bundles accompanied by reduction in area and then finally degradation of the fibrils. The extent of treatment can be achieved by increasing any of the 3 treatment parameters. The main effects of the treatment parameters on the cross-sectional area of fibers are shown in Fig. 16.6. Fig. 16.6A shows that as the temperature increases the cross-sectional area significantly decreases. This reduction in the cross-sectional area is due to the removal of the amorphous constituents, breaking down of vascular bundles and further fibrillation. However, it can be noticed that due to the strong effect of the temperature and broad range (25°C–100°C), it failed to detect the minor increase in cross sectional area by swelling. Fig. 16.6B shows that as the caustic soda concentration increases the cross-sectional area initially decreased with respect to the untreated sample, due to the removal of lignin and other impurities from the fiber surface. As the concentration further increase the fiber is swollen indicating a slight increase in area at 3% concentration, followed by another reduction in area at 5% concentration, due to the breakdown of the vascular bundles and further fibrillation. The

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FIGURE 16.5 Midrib vascular bundle (A) before complete dissolution, (B) after dissolution, swelling and breaking down into longitudinal bundles.

FIGURE 16.6 Main effects of (A) treatment temperature, (B) NaOH concentration, and (C) treatment duration on the cross-sectional area compared to control sample C.

effect of the caustic soda concentrations is less pronounced at such narrow concentration range (1%–5%) compared to the temperature. Fig. 16.6C shows that as the treatment duration increases the cross-sectional area decreases and this could be due to the prolonged duration of the treatment, which indicated that even with the least duration of 1 hour the fibers have already been broken down into longitudinal bundles, however further prolonged duration up to 3 hours wasn’t capable of causing significant fibrillation. As far as the cross-section area of the fiber is concerned, the ANOVA analysis showed that the three factors had a significant effect on fiber cross-sectional area. Yet, the most pronounced

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FIGURE 16.7 Date palm fibers’ cross-sectional area treated with (A) 1%, (B) 3%, and (C) 5% NaOH.

effect is the temperature, followed by the caustic soda concentration and finally the duration [45]. It could be noticed that the alkaline treatment regardless of its severity had caused the reduction of the area by more than 50% when compared to the control sample C (Ac = 0.202498 mm2 ), while the sample with the smallest area (A25 = 0.0455 mm2 ) had a 77.5% reduction. The individual results of all 27 samples are plotted in Fig. 16.7. It could be concluded that the highest fibrillation was obtained when the fibers were treated with very severe conditions either at 100°C for 1 or 3 hours, or at 75°C for 2 hours. Moreover, it was noticed that room temperature as a treating temperature succeeded in breaking down the vascular bundles but failed to significantly fibrillate and reduce the cross-sectional area of the fibers.

16.3.2 Tensile strength The tensile strength of the date palm midrib fiber was tested in dry and wet conditions. The change in tensile strength of the date palm fiber under different treatment conditions is due to the change in cross sectional area and load sharing efficiency, not due to polymorphic transformation or changes in crystallinity index as indicated by the XRD results in the work of Elseify et al. (2020) [46]. When the lignocellulosic fibers are treated with caustic soda, they undergo a gradual delignification process, during which the lignin macromolecules are broken into smaller molecules so that they can be dissolved into the solution [47]. This is usually associated with the gradual extraction of the hemicellulose from the fiber cell walls [48]. The removal of lignin and hemicellulose cause the cellulose fibrils to separate and significantly reduce the load sharing efficiency between the fibrils within the same fiber bundle as shown in Fig. 16.8. This in turn causes the fibrils to resist the tensile loads individually rather than collectively during the tensile testing, resulting in a reduced breaking load of the test specimen [49].

16.3.3.1 Dry tensile strength The tensile strength was calculated by dividing the average breaking load by the average crosssectional area of each sample. Fig. 16.9 shows a typical load-extension curve of date palm midribs fibers.

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FIGURE 16.8 Longitudinal view of date palm fiber after (A) delignification, (B) hemicellulose extraction, and (C) separation of fibrils.

FIGURE 16.9 Typical load-extension curve of date palm midribs fibers.

The main effects of the treatment parameters on the tensile strength were plotted with respect to the control sample as shown in Fig. 16.10. Fig. 16.10A shows the main effect of the treatment temperature on the tensile strength of the fibers compared to the untreated control sample. There was a significant increase in strength from the untreated to the samples treated at 25°C; however, further increase in temperature didn’t have any significant effect on the strength according to the ANOVA test. This initial increase in strength can be mainly attributed to significant removal of the amorphous constituents, in addition to, breaking the vascular bundles into longitudinal bundles with smaller cross-sectional area and elimination of the hollow content. In Fig. 16.10B, the main effect of increasing the concentration of NaOH on the tensile strength is represented. Similarly, there was an initial significant increase in strength of the fibers treated at 1% compared to the untreated sample, due to the better packing and removal of amorphous constituents. Further increase in the concentration to 3% NaOH resulted in a significant drop in the fiber strength, due to the fiber swelling and associated increase in cross sectional area. Finally, increasing the concentration to 5% NaOH showed an insignificant increase in strength, this could be due to the two opposing effects; fibrillation and reduced load sharing efficiency.

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FIGURE 16.10 Main effects of (A) treatment temperature, (B) NaOH concentration, and (C) treatment duration on the tensile strength compared to control sample C.

While, the fibrillation reduce the cross sectional are and in turn increase the strength, yet the reduction in load sharing efficiency due to the separation of fibrils results in a reduction in strength which balance out the increase due to area reduction, hence no significant change in strength from 3% to 5% was indicated. This was further confirmed by the univariate analysis of variances that showed that there was a significant effect of the NaOH concentration on the fiber strength, and by performing a post hoc Duncan test, it indicated that samples treated with 3% and 5% belong to the same subset while sample treated with 1% NaOH belongs to a different subset. Finally, Fig. 16.10C shows the main effect of the treatment duration on the tensile strength of the extracted fibers. The effect of the treatment duration was very similar to the effect of NaOH concentration, which indicated a significant increase in strength from the untreated sample to the samples treated at 1 hour, followed by a significant reduction in strength for the 2-hour samples; however, the re-increase in strength for the 3-hour samples was significant in this case. This can be due to the same reasons mentioned above. After analyzing the dry tensile strength results of all 28 samples in Fig. 16.11, it was noticed that the extent of the alkaline treatment can be reached by increasing any of the 3 parameters; however, the most pronounced effect on the dry fiber strength is the caustic soda concentration, followed by the treatment duration, and then the treatment temperature. Moreover, at lower treatment levels, such as, low soda concentration, room temperature or short treatment duration, the cross-sectional area is effectively reduced due to removal of non-load bearing amorphous constituents and hollow content, hence higher load bearing capacity and strength. On contrary, at higher treatment levels, such as, 5% NaOH, 100°C and 3 hours, the load sharing efficiency is reduced and in turn the strength is reduced. Therefore, treating the fibers at 100°C should only be accompanied by the use of low NaOH % for short durations. The 75°C as a treating temperature showed good results but only when used

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FIGURE 16.11 Dry tensile strength of date palm fibers treated with (A) 1%, (B) 3%, and (C) 5% NaOH.

FIGURE 16.12 Main effects of (A) treatment temperature, (B) NaOH concentration, and (C) treatment duration on the modulus of elasticity compared to control sample C.

with low NaOH % for long durations. As for the 25°C as treating temperature, only high tensile strength fibers were obtained when they were treated using 5% NaOH for 3 hours.

16.3.3.2 Modulus of elasticity Modulus of elasticity was calculated by dividing the average dry tensile strength of each sample by its average failure strain. The main effects of the treatment parameters on the modulus of elasticity are shown in Fig. 16.12. After analyzing all the modulus of elasticity results, it was noticed the effect of the treatment parameters on the modulus of elasticity was quite similar to that of the dry tensile strength of fibers. The high values were obtained when fibers were treated at high temperature while using low NaOH % and vice versa. It was noticed that the 3% NaOH had a very negative effect on the modulus of elasticity and this could be due to the swelling of

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Table 16.3 Sample ID, severity level and dry and wet strength of fibers. Sample ID

Severity level

Dry strength (MPa)

CV (%)

Wet strength (MPa)

CV (%)

28 9 1 25

Untreated Mild Medium Severe

118.44 263.32 452.79 164.24

37.91 10.79 33.93 46.789

135.74 146.79 123.85 27.45

34.04 40.58 79.75 93.89

FIGURE 16.13 (A) Comparison between dry and wet strength of fibers (B) main effect of moisture content on the tensile strength.

fibers when 3% NaOH was used. As for the treatment durations, the best results were observed when the fibers were treated for 1 hour at high temperatures; either 75°C or 100°C. Moreover, the 3 hours duration could be used but at room temperature. The use of 2 hours should be limited along with 3% NaOH. The modulus of elasticity results were noticed to be below the expected values, this could be due in part to error in the strain measurement. The strain readings were obtained from the overhead movement of the grips which were exaggerated, resulting in higher failure strain results and consequently reduction in the modulus of elasticity values.

16.3.3.3 Wet tensile strength Wet single fiber tensile test (WSFTT) was performed for 4 selected samples with 4 different severity levels and different dry strength values. The selected samples were 1, 9, 25, and 28 (control sample). The wet strength was calculated following the same steps of the dry strength and the results are listed in Table 16.3. Fig. 16.13A shows the difference between fiber strength in the dry and the wet states of all 4 samples. It can be seen from Fig. 16.13A that soaking the fibers in water has caused deterioration in the fiber strength except for the untreated control

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FIGURE 16.14 Effect of the treatment severity on the percent reduction in tensile strength.

sample #28 that showed a slight increase. Fig. 16.13B shows the main effect of the moisture content on the tensile strength of fibers. When comparing the dry and wet strength of fibers it was clear that there is a significant reduction in strength by more than 56%. This reduction in the fiber tensile strength in the wet state is mainly due to the fiber swelling (increased area) and significant reduction in the load sharing efficiency in the wet state. Since, the load sharing is dependent on both the presence of binder and the inter-fiber friction, and in the wet state not only the binder is removed, but also the inter-fiber friction is significantly reduced. Fig. 16.14 shows the effect of the treatment severity on the percent reduction in tensile strength. In case of the untreated sample it had a slight increase of strength in the wet state due to the better packing [50]. The sample treated at mild conditions displayed a 44.2% reduction in strength, as for the medium conditions it showed a reduction of 76%, and finally the sample treated at severe condition showed 83%.

16.4 Optimum conditions It was noticed that increasing the extent of alkaline treatment resulted in higher fibrillation and removal of the amorphous constituents; however, this was at the expense of the strength reduction (dry and wet). Therefore, the question remained; what is the optimum treatment condition that will result in fine, long, pure, strong date palm fibers? Accordingly, an experimental optimization of the alkaline treatment process was made to determine the best samples from the strength and area point of views separately and simultaneously. By analyzing all 27 samples it was clear that there is no one sample that has the lowest cross section area and highest dry strength. Hence, the optimum treating conditions will differ based on which property is more favored based on the final application. The highest dry tensile strength values were obtained when the fibers were treated with low concentrations of sodium hydroxide at high temperature and vice versa. The best samples were the ones treated at 100°C + 1% NaOH + 1 hr (σ 1 = 452.79 MPa) and the one treated at 75°C + 1% NaOH + 1 hr (σ 2 = 408.45 MPa). Also, the sample treated at 25°C + 5% NaOH + 3 hr had high

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FIGURE 16.15 Comparison between tensile strength of fibers extracted in this work with (A) the literature and (B) other natural fibers.

dry tensile strength (σ 27 = 391.54 MPa) when compared to the other samples treated at room temperature or even the other samples. Whereas the most fibrillated fibers were obtained when the fibers were treated at the highest temperature using the highest NaOH concentration for the longest duration, i.e., 100°C using 5% NaOH for 3 hours and (A25 = 0.045534 mm2 ). However, in some applications, high strength and small cross-sectional areas are both required. Therefore, the sample with the best all-around properties was #11. The fibers were treated at 75°C using 1% NaOH for 2 hours and the dry tensile strength was nearly 312.47 MPa and the cross-sectional area was equal to 0.05978 mm2 . After analyzing the WSFTT results it can also be concluded that if the fibers will be used in applications where they will be kept in dry conditions, as in the case of being embedded in a polymer matrix, then the optimum samples will be as mentioned earlier. However, if the fibers will be prone to water absorption, then the least severe (mild) sample should be used to avoid the reduction in fiber strength. As for comparing the tensile strength of the fibers extracted and the literature, Fig. 16.15A shows that the extracted fibers are nearly five times stronger than midrib date palm fibers reported in the literature. Moreover, date palm midrib fibers have very promising mechanical properties when compared to other competing natural fibers. Fig. 16.15B shows a comparison between the tensile strength of date palm and other natural fibers. It can be noticed that date palm midrib fibers have comparable strength to other natural fibers such as flax, hemp and sisal [51].

16.5 Conclusions Date palm fibers were extracted from the midribs using alkaline treatment. 27 samples were extracted in addition to the untreated sample by varying the treatment parameters; NaOH concentration, treatment duration, and treatment temperature. The alkaline treatment had a

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significant effect on the properties of the date palm fibers, this was mainly due to the effective removal of the non-load bearing amorphous constituents and hollow content. The treatment effectively fibrillated the midrib fibers by reducing the cross-sectional area by more than 77.5%. Moreover, the fibers dry tensile strength was enhanced by 74%. The ANOVA showed that the treatment parameters and their interactions had a significant effect on the fibers cross-sectional area and their mechanical properties. The optimum conditions from the strength point of view were found to be at 100°C for 1 hr using 1% NaOH. On the other hand, the optimum condition from the area point of view was at 100°C using 5% NaOH for 3 hours. Whereas, the sample that had high mechanical properties and low area results was treated at 75°C while using 1% NaOH for 3 hours treatment duration. Moreover, the WSFTT showed a significant reduction in the wet strength of the fibers when compared with the dry strength values. Therefore, to maintain the high strength of date palm midrib fibers, they should be used in dry conditions. However, if the fibers will be used in application where they will be prone to moisture, then the fibers treated with the least treatment severity should be used. Comparing the properties of fibers extracted in this research showed that date palm fibers had properties similar to other natural fibers and even sometimes higher. Therefore, this work had succeeded in extracting long fibrillated textile-grade cellulosic fibers form the midribs of date palm using alkaline treatment, the fibers have the potential to replace other natural fibers like sisal or hemp in different applications like the reinforcement of composites or in ropes industry. As recommendations for future work, it’s important to investigate the potential of treating the fibers with other methods that could have less environmental impact such as biological or enzymatic treatment.

Acknowledgments The work in this research is fully funded by inTEXive Consulting. The authors would like to greatly acknowledge the efforts of research assistant Asmaa Mansour from Alexandria University for her help in the SFTT. The authors would also like to acknowledge the support of Dr. Lamia A. Shihata from the German University in Cairo.

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Recent developments in extraction of keratin from industrial wastes Fayyaz Salih Hussain and Najma Memon NATIONAL CENTRE OF EXCELLENCE IN ANALYTICAL CHEMISTRY, UNIVERSITY OF SINDH, JAMSHORO, PAKISTAN

17.1 Introduction The industrial revolution has led to an exponential growth of economic development but simultaneously caused severe damage to environment. Uncontrolled expansions of industrial units throughout the world has overcome the basic needs of population but also produced enormous waste material from all the segments of industrialization, which ranges from small cottage to heavy industries. Waste products are generated in the form of chemicals, processing waste and discarded material. Untreated waste material from those industries continuously polluted all spheres of environment, i.e., hydrosphere, lithosphere and atmosphere, when this wastes cross the assimilation capacity of the environment, it created pollution. Control of industrial waste is a first-rate challenge, especially in developing countries. Large quantities of industrial wastes are being dumped on the soil floor, resulting in eco-unfavorable consequences and due the excessive cost of treatment, little or no attention is being given to proper disposal of built-up waste [1]. Keratin waste are considered as the environmental pollutants and generated mostly from the poultry farms, slaughterhouses and leather industries [1,2]. The poultry farms, slaughterhouses, leather industries and wool industries are constantly producing a million tons of keratin waste [3]. It has been estimated that 1.6 billion pounds wool has been discarded annually. Leather industries throw away extensive amount of waste products and are considered as polluting industries with negative environmental impact [4]. The main countries producing keratin waste include the United State of America, China, India and Brazil. These countries generate millions of tons of protein containing keratinous waste which is mainly generated from poultry slaughterhouses and wool textile industries [5]. Keratin protein is the major component of the keratin waste [6] and belongs to the scleroprotein group [7]. Keratin is a Greek work used for horn, “κ ερατ ´ ο.” Now it is used for the protein covering structure and layers produces by chordates which includes birds, mammals, fish, amphibians and reptiles. The outermost dead layer of hair, wool and epidermis claws, horn, claws, feathers scales and hooves are mainly composed of keratin. This proteinous material is resistant to peptidase, a protein degrading enzyme and Extraction of Natural Products from Agro-industrial Wastes: A Green and Sustainable Approach. DOI: https://doi.org/10.1016/B978-0-12-823349-8.00010-1 c 2023 Elsevier Inc. All rights reserved. Copyright 

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FIGURE 17.1 Picture of various sources of keratin.

it is water insoluble [2]. Keratin protein is greatly resistant to the action of physical, chemical and biological agents [8]. The poultry feathers and other keratin-containing waste is dumped, land filled and incinerated throughout the world [9,10]. These activities cause soil, water and air pollution. Discarded feather furthermore causes different human diseases including chlorosis and fowl cholera [11]. The concept of utilization of waste materials as a component of the circular economy has introduced alternatives to maximize reuse and recycling of waste materials for wastewater treatment.

17.2 Sources of keratin protein Keratin is the part of living organism and can be obtain from their body part. Main sources of keratin are wool, feathers, stratum corneum, scales and woof (Fig. 17.1). Feathers, the byproduct of poultry industry contains more than 90% keratin where wool and hair are the byproduct of leather industry, also contain abundant proteins. Human hair contains more than 80% of keratin.

17.3 Structure keratin Keratin is complex biological material comprised of a cysteine rich protein and composed of 19 different amino acids which are linked and form a leather like filamented structure of polypeptide chains [3]. It serves as a protective layer for epidermal appendages like claws, beak, nails, wool, hairs, feathers and horns. There is huge variation in the properties of keratin. They are classified into two groups based on their function, structure and regulations. These are hard keratin and soft keratin. Hard structure of keratin is due to higher amount of sulfur which is crosslinked and form filaments which are embedded in cysteine rich protein showed a compact and hard structure. While soft keratins formed a bundles loosely packed of filaments [4]. Keratin can also be classified in to two main categories as; alpha keratin (α- keratin) and beta keratin (β-keratin). α- keratin is associated with hairs, wool nails, hooves stratum corneum as well as horn. It is found mostly in the epithelial portion of almost all vertebrates. Whereas β-keratin is associated with avian claws, beaks, scales, reptilian, cuticle hair and feathers. It is normally present in reptile and birds as a structural protein. β-keratin contains 4%–20% cysteine

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FIGURE 17.2 Structure of keratin shows different interaction within keratin polypeptide chain including hydrophobic interaction, hydrogen bonding and disulfide bonding.

and it is rich in glycine, serine, alanine, proline and very low level of histidine tryptophan and lysine [5,6]. In the α- keratin the arrangement of polypeptide chains are as alpha helices, whereas in beta keratin these chains are arrange as pleated beta sheets. It formed a coiled coil structure [7]. Theses chains are different in sequence and number of amino acids, charge, size and polarity [8,9]. Composition and characteristics of various types of keratin is shown in Table 17.1. Keratin contained high level of inter as well as intra molecular disulfide bonds, and these bonds are formed by the connection of two sulfhydryl between two amino acids, i.e. two cysteine that’s why they are generally insoluble in many solvent like alkaline, water, organic solvents and dilute acids [7] (Table 17.2).

17.4 Extraction of keratin The structure of keratin is stabilized due to covalent interaction like disulfide bonds and wide range of non-covalent interaction like hydrogen bonds, electrostatic forces and hydrophobic forces, for dissolution these interaction must be disturbed [11]. The keratin does not behave like other proteins therefore simple methods for dissolution of proteins are normally not suitable for its solubilization. However under very controlled conditions and presence of oxidizing/reducing agents, low pH, it become chemically reactive and more water soluble due to sulfur-sulfur bond

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Table 17.1 Amino acid composition (residues per 100 residues) of representative α- and β-keratin materials [10]. Amino acid

Whole wool (representing a-keratin)

Whole feather rachis (representing b-keratin)

Alanine Arginine Aspartic acid Half cystine Glutamic acid Glycine Histidine Isoleucine Leucine Methionine Phenylalanine Proline Serine Threonine Tyrosine Valine Tryptophan

5.5 6.6 6.5 11.4 11.3 8.8 0.8 3.4 7.8 0.5 2.5 6.0 9.6 6.1 4.1 5.9 –

8.7 3.8 5.6 7.8 6.9 13.7 0.2 3.2 8.3 0.1 3.1 9.8 14.1 4.1 1.4 7.8 0.7

Table 17.2 Characteristic features of α-keratin and β-keratin. Characteristics

α-keratin

β-keratin

Distribution Structure Diameter (nm) Stiffness Bonding Molecular mass (kDa)

Hairs, wool, hooves, nails and horns Intermediate filament 8–10 High Hydrogen bonding (intramolecular) 40–68

Feathers, reptilian epidermis, claws avian beaks Amorphous 3–4 Lower Hydrogen bonding (intermolecular) 10–22

(–S–S), carboxylic acid and amino moieties [12]. The solubility of keratin in water increases in high temperature, acidic pH and the presence of reducing agent i.e. Na2 S or Na2 SO3 as a result of reduction, breaking of cross linked disulfide bonds take place into thiol (-SH) beside the protonation of -NH2 and different other groups carry positive charge thus the solubilization can easily occurs. After protonation, the exposed and unfolded functional groups contained positive charge with great reactivity thus after chemical modification the protein of keratin become pseudo cationic polymer. This biopolymer can be developed and modified into different forms from films, gels, nanoparticles, beads, sponges. These materials have unique properties of nontoxic, environmentally friendly and biodegradability. Thus these polymers have great importance in the field of food science, green chemistry, cosmetic industry as well as pharmaceutical industry [13,14]. Generally, reduction processes are used for the extraction of keratin

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from different materials because of its high efficiency. Reducing agents mainly disassociate the hydrogen bonds, disulfide bonds, salt linkages and allow protease access to peptide backbone and dissolve the protein [11,15,16]. Feathers are the most abundant keratinous waste in millions of tons every year from poultry processing. Feathers contain more than 95-98% keratin protein which is mainly β-keratin [17]. Wool is also a major contributor to keratin waste. Wool contains approximately 95% of keratin [18]. Various methods have been used for dissolution of the keratin from keratinous materials thereby minimizing environmental pollution and to generate useful resources from keratinous waste in different aspects. Many oxidative and reductive agents are used to dissociate the keratin such as peroxide and thiols has a very harmful effect on ecosystem. These methods were applied on animals’ hoofs, horns and on feathers and even on human hair. Most of the researchers used Shindai method for the extraction of keratin from feathers in reduction condition [19–23]. Methods other than reduction/oxidation are also used to extract the keratin from biowaste including alkali extraction, microwave irradiation, ionic liquids, sulfitolysis and steam explosion etc. The structure of keratin is disturbed, and primary chain is damaged in hydrolysis method. In an alkaline method, huge amount of alkali is used for hydrolysis and acids are used for neutralization. One of the most reported methods for extraction of keratin from wool is implication of thiols (mercaptoethanol) as a reducing agent to break down the disulfide bonds. But the disadvantage of this method is mercaptoethanol is toxic to ecosystem as well it is expensive. Mercaptoethanol is replaced by sodium sulfide for extraction of keratin from wool by sulfitolysis method need large amount of urea as protein denaturant. Sulfitolysis method breaks (R–S–S–R), the disulfide bonds and form cysteine (R–S–H, this can change the physical and chemical properties of extracted keratin. In literature different oxidation methods for the extraction of keratin has been reported [24]. Peracetic acids and formic acids have been widely used to form as sulfonic acid. Disadvantage of this method is time consuming. Ionic liquid methods are newer and relatively green solvent that attract the attention of researchers for the extraction of keratin from wool [25] but extraction process required nitrogen and temperature controlled environment. The obtained keratin is water insoluble [26].

17.4.1 Reduction method for the extraction of keratin The stability of keratin is mainly because of disulfide bonds present in the peptide chain. This disulfide linkage can be reduced by using different reducing agents having thiol group and under different control conditions including pH, temperature as well as pressure (Fig. 17.3). Reduction of keratin is decades old method found in the 1930’s [27]. In reduction method, the reducing agent attack on the disulfide bonds and formed a thiol group (-SH). At different pH, concentration and temperature thioglycolic acid and sodium thioglycolate are used as a reducing agent. Thioglycolate and mercaptoethanol are used to reduce keratin, at pH 5 both showed the similar reduction capacities at a low thiol concentration, but at neutral pH and high concentration of thiol the complete reduction observed, it has been suggested if the concentration of mercaptoethanol is increased by 4M, than approximately 96% reduction can be observed. Mercaptoethanol is more effective reducing agent as compare to potassium thioglycolate [28]. Literature showed that toluene-thiol has a greatest reduction capability as compare to other thiol groups nearly

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FIGURE 17.3 Extraction procedure of keratin from wool by using L-cysteine and urea.

93%. Other reducing agents like phosphines are also used for breaking of disulfide linkages and form thiol groups in keratin. Sweetman and Maclaren [29] had studied different phosphine as a reducing agent to for the dissolution of disulfide groups in keratin obtained from wool including tri-diethylaminomethyl-phosphine and tri-hydroxymethyl-phosphine, among them tein-butylphosphine is found very effective and selective reducing agent can reduce keratin upt0 95% within one hour. Goddard and Michaelis [30] also suggest that wool keratin can be reduced by sodium thioglycolate to kerateine, that can be further oxide to form meta keratin, soluble in alkali. Author has reported that wool keratin can be reduced at pH higher than 10.5. Nakamura, Arimoto [31] has extracted the keratin from human hair by using urea and thiourea in presence of the reductant that can effectively reduce proteins from cortex of human hair. The thiourea 2.4 M, urea 15 M, 15% DTT, 25 mM Tris at pH 8.5 temperature 50°C for 48 hours gave 67% yield. Jin, Wang [32] also reported the keratin extraction from human hair by using reduction method. The author used urea, 2-mercaptonethanol and SDS and modified 100% thiols at pH 9-10, temperature 70°C and time 48 hours, the resulted keratin was S-Carboxymethyl keratin with lower amino acids. Savige [33] used thiols at a very low pH 2 and moderate temperature 50°C–60°C reduce wool keratin up to 50% in 24 h. Wang, Li [15] has reported the dissolution of keratin from wool by using L-cysteine as a reducing agent and urea as protein denaturing agent. The dissolution was achieved about 72% at 5 h time and 75°C temperature. Schrooyen, Dijkstra [20] have reported the extraction of keratin from feather by using 2-mercaptoethanol, 5M urea and SDS. The pH was maintained between 7 and 9 and temperature 40°C, approximately 75% of keratin was extracted within 30 min. Martelli, Moore [34] has improved extraction process by increasing SDS

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concentration. A 35g Feather was treated with 30g of SDS,189g of urea, 9.5 g tris-(hydroxymethyl) aminomethane and 46 mL of 2-mercaptoethanol. In a nitrogen environment temperature was adjust up to 50°C and pH was maintained at 9.0. The extraction yield was found 80%. Wang, Zhang [35] has reported the extraction of keratin by using SDS, sodium sulfite and sodium hydroxide, at the optimized condition i.e. sodium sulfite 30 g/L, SDS 10 g/L sodium hydroxide 6 g/L reaction temperature was optimized 30°C and time 3h leads to dissolution of more than 99% and the extraction can be more than 60%. Pourjavaheri, Pour [36] have reported extraction of keratin from chicken feathers by using L-cysteine and compared with sodium sulfide, the keratin extracted from both methods have a same molecular mas i.e. ca. 11 kg/mol. But the extracted yield was found 88% with sodium sulfide and 66% with environment friendly Lcysteine. The reaction temperature was optimized at 40°C, pH 10.5 and the reaction time 6 hours. Table 17.3 shows more methods using urea and l-cysteine.

17.4.2 Effect of different reducing, surfactant, pH, and denaturing agents In early studies wool was solubilized using reduction methods. Thiols have been used as a reducing agent since 1930, since then mostly thioglycolic acid and sodium thioglycolate were used with different concentration and pH was adjusted to maximize the extraction yield and obtained desired product. Many researchers have been investigating the effect of pH and concentration of reducing agent on the extraction yield. Goddard and Michaelis [30] and Patterson, Geiger [50] have reported that the keratin can be reduced at pH higher than 10.0. Some researchers have reported that considerable amount of keratin reduction in acidic pH. Savige [33] has observed the extraction of protein approximately 47% at a very low pH 2 by using thiols. Beside of all hazards, mercaptoethanol is strong reducing agent in case of keratin extraction. High concentration of mercaptoethanol, i.e., 4 M can reduce wool cystine up to 96%. Mercaptoethanol and thioglycolate was used to reduce wool keratin by O’donnell and Thompson [51] observed that both mercaptoethanol and thioglycolate have shown similar reduction capacity. But if the concentration of thiol increased the reduction process will be driven to its end. Thiourea and urea both have been used as a denaturing agent to increase the extraction of keratin. At higher concentration urea weakens the bonds presents in polypeptide chain. It has been observed that combination of urea and thiourea with higher concentration 2-8 M, 2-mercaptoethanol at basic pH can increase the protein recovered amount in supernatant were about 8-27% from its original level, in the absence of urea this action was not found. With the removal of 2-mercaptoethanol, the protein recovered amount reduced up to 5%. This indicate that reductant is also necessary for good extraction [31]. Urea can easily breakdown the hydrophobic bonds present in the polypeptide chain of protein hence it is facilitating the extraction of keratin from its matrix. It has been observed that at harsh conditions i.e. higher pH or at higher temperature the structure of keratin is damaged as a result the biochemical and physical properties of keratin can be lost and at some stage formation of lanthionine can take place [52]. Several authors have reported that the surfactant can improve the extraction yield as well as it can stabilize the extracted keratin in aqueous medium. Many authors have reported SDS can increase the extraction yield.

288

Condition/specification Source

Extraction solvent

Temperature (°C) pH

Time (h) Yield (%) Reference

Feathers bovine horn Feathers Wool Wool Human Hair Wool Feathers Wool Bovine hoof Feathers Feathers Wool Feathers Wool Wool Human hair

L-cysteine, Urea 8 M and NaOH Thioglycolic acid 5%, thiourea 2.5M and 25 mM Tris-HCl Mercaptoethanol 125 mM, 200 mM EDTA and Tris 200mM Thioglycolic Acid 0.2 M, Urea8 M Tris (2-carboxyethyl) phosphine and Na2 S2 O5 Thiourea 2.4 M, Urea 15 M DTT 15%, Tris 25 mM Thioglycolic acid 0.2 M, Urea 10 M 2-mercaptoethanol 750 ml, urea 8 M, EDTA, SDS, tris, 200 mM Mercaptoethanol 5%, SDS 7 2%, Mercaptoethanol 0.7 M, Urea 7.0 M and SDS Sodium sulfide 500 Mm, Sodium sulfide 0.92 M Urea 7M, SDS, and 2-mercapthoethanol 2-mercaptoethanol, sodium m-bisulfite, sodium bisulfite or DTT DTT 0.2 M, urea 8 M 0.2 M Tris– HCl and EDTA 3 mM Urea M 10 fold of L-cysteine (based on wool fibers) and NaOH 50 NaOH and sodium dodecyl sulfate beta-mercaptoethanol 2% and EDTA 0.01 M.

70 50 40 50 80 50 40 40 50 60 65 80.1 60 50 20 70 90

12 72 30 min 3 5 48 2

10.5 9.5 8 11 8.5 11 7–9 7 7 3.5

24 12 1-6 9.5 – 12 2 9 19 10.5 24 8.5 10 min

60 – 75 70 80 67 91 75 60 44 80.2 86.5- 91 53 94% 60 63 47.3

[16] [37] [38] [26] [39] [31] [40] [41] [21] [42] [43] [44] [45] [46] [47] [48] [49]

Extraction of Natural Products from Agro-industrial Wastes

Table 17.3 Reduction methods for the extraction of keratin from different sources.

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289

Researchers’ findings suggested that neutral surfactant and cationic surfactant are less effective as compare to anionic surfactant such as SDS which is more effective. Some amount of surfactant is retained extraction of keratin as a residue after final extracted keratin but this residue did not show any negative impact on extraction of keratin nor any scientific observation is available about cell toxicity or any negative impact on digestibility of the keratin by the trypsin [20].

17.4.3 Sulfitolysis methods for the extraction of keratin In the reduction methods, hazardous chemicals are used, and the methods are comparatively mostly expensive. In case of sulfitolysis (breakdown of sulfo), these methods are inexpensive where odor free regents are used and chemically benign. The sulfitolysis it basically the main process of the keratinolysis [53]. In sulfitolysis (breakdown of sulfo) and proteolysis (attack of proteolytic) by the keratinolytic proteases is basically based on complex nature of the keratin. In methods, the dissolution is simple which uses SO3 to break sulfur groups and prevention of further disulfide bond formation. It attack to a specific cysteine and cystine in protein hence the other important amino acids are preserved. In the sulfitolysis, the sulfo functionalities render derivatives which are highly soluble in water. Mercaptoethanol has been chosen for the good yield and better extraction of keratin and maintained their structure for years. But it is not environmentally friendly and has very toxic effects on environment as well as unpleasant smell and high cost made it undesirable for commercial use. So to break down the sulfide bonds and to extraction of keratin from any source, sodium sulfite can be a better and alternative choice. The major sulfite compounds like sodium sulfite, bisulfite and disulfite can be used to extract keratin employing sulfitolysis process [26]. Bisulfide is a predominant in the lower pH, while sulfite is predominant pH above than 7. Sulfitolysis of the cystine at pH greater than 9 is the reversible displacement reaction. The formation S-sulfonate anion and thiol are forming with bissulfite at pH blow than 9. Normally when rinsing in water the sulfitolysis reactions readily reverse but in an acidic condition this reversal is very slow [54]. Keratin through sulftolysis can be extracted in single or various steps. This is due to the sulfo group normally renders cysteine residue unreactive. It can be process like keratoses, there is less data available on extraction of keratin by oxidative sulftolysis so the characterization data is limited [55]. Further, all disulfide bonds can be dissociated in the presence of SDS and urea. By increasing the temperature, adding high concentration of urea or increase concentration of bisulfite can increase the extent of keratin extraction. Happey and Wormell [56] have reported first time extraction of keratin by using sodium sulfite. In their paper they recognized that the extraction of keratin by using sodium sulfide is done by breaking of cross linkages between cystine in polypeptide chain. Each sulfide bond is converted into one thiol group and one sulfite. Usually the thiol group is oxide into new disulfide bridge in presence of any oxidizing agent. Many catalysts have been used as strong oxidizing agents i.e. solid-state copper, is used due to specificity of particular thiol group in cysteine. Until unless all sulfite are consumed or all cysteine are converted, the process of sulfitolysis is continuous. The main advantage of sulfitolysis is that without hydrolysis, all the disulfide bonds can be broken by introducing negative charge on cysteine, hence solubility increased. Some researchers used urea to breakdown the hydrogen bonding as well as disturb

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secondary structure of keratin. SDS has been used as a surfactant to prevent aggregation and stabilized protein. The sulfitolysis process need dialysis procedure after dissolution [57]. The extraction of keratin by sulfitolysis method, the hydrogen bonds, ionic bonds, disulfide bonds and hydrophobic bonds are broken with NaOH, urea, SDS and sodium metabisulfite respectively [58] (Table 17.4).

17.4.4 Alkali methods for the extraction of keratin Hydrolysis of keratin by alkali solutions is one of the old and most widely used method for the extraction of keratin from wool. Strong alkali solution like NaOH or KOH can easily solubilize the wool. Alkali basically speed up hydrolysis process by peptization up to the pH 9.0, i.e., quelling (swelling of keratin complex) at pH higher than 9.2, and condition like contact time, temperature and the concentration speed up the hydrolysis. Higher concentration of alkali solution leads to dissociate the sulfur nucleus hence cysteine residue degradation take place, peptide chain and side chain amide bonds damaged and lanthionine is formed by the degradation of cysteine which can decrease the solubility of wool. Higher alkali concentration dissociates hydrogen from carboxylic and sulfate group. In case of potash or soda the hydrolysis goes to the completion and the formation of soluble sulfides, sodium salt or amino acids take place. Hydrolysis of wool with 0.1 N NaOH and boiling leads to destruction of serine, cystine, arginine, cysteine and threonine on other side tryptophan is not destroyed [69–71]. ´ Banach [72] have used waste feather and dissolve it by using calcium hydroxide Staron, Ca(OH)2. A two-stage hydrolysis was carried out by sterilizing material followed by digestion of protein. A 0.05–0.75 g of calcium hydroxide was added to feather and incubated for the 1–4 h at the temperature about 90°C–110°C. Author concluded that the amount of calcium hydroxide is main contributor in hydrolysis process. The greater amount of calcium hydroxide can lower hydrolysis process of keratin specially obtained from feathers. The optimized conditions for heights yield 89% when amount of calcium hydroxide 0.75 g, water 2 g, temperature 90°C and 4h time. Due to its mild conditions like pressure, temperature and short duration, author claim this process is economically and environmentally feasible. Tsuda and Nomura [73] extracted the keratin from wool as well as feathers by using sodium hydroxide. Feathers were incubated in sodium hydroxide solution having concentration 10 g/L for 10 min at 120°C, after dissolution the solution was neutralized with acid and dialyzed. In case of hairs, sodium lauryl sulfate (2%) solution was used to soaked for 5 min, after socking and washing the hair was treated with ammonium hydroxide (0.9%) and hydrogen peroxide (3.6%) at 10 pH for 30 min and the temperature was adjusted at 40°C. The authors compared the molecular weight and amino acid composition of both hairs and feathers. It showed that wool contained less hydrophobic amino acid as compared to feathers. And the glycine/proline ratio is higher in keratin extracted from feather and compare to wool. It is the indication of presence of higher β-sheet in keratin obtained from feather as compared to the wool. During the hydrolysis process the molecular weight has loss that the intact sources but both hydrolyzed retain completely secondary structure. Shavandi, Bekhit [45] investigates the physio-chemical properties of extracted keratin from the Merino

Condition/specification Source

Extraction solvent

Temperature (°C)

pH

Time (h)

Yield (%)

Reference

Wool Wool Feathers Wool Wool Wool Wool Wool Human hair Feathers

Sodium sulfite 30 g/L, sodium hydroxide 6 g/L, SDS 10 g/L Na2 S2 O5 0.5 M, urea 8 M NaOH 5N Na2 S 0.2 M, urea 8 M and SDS Sodium disulfite Na2 S2 O5 150g., urea 8 M. SDS 75 g. NaHS O3 0.5 mol/L, LiBr 0.1 mol/L and SDS 0.02 mol/L Sodium metabisulfite 0.5 M, urea 8 M and NaOH 5 M Sodium metabisulfite 0.5 M, urea 8 M, NaOH 5M Sodium metabisulfite 0.5 M, SDS 0.1 M and urea 8 M. Sodium metabisulfite 5% w/v, urea 5 M, thiourea 2.6 M and NaOH. 1 g feather in 10 ml of a solution containing 0.125 mol/L Na2S2O5, 0.05 mol/L SDS, and 2.0 mol/l urea. 15 g fibers 300 mL of a solution containing urea 8M and Na2S2O5 0.5M adjusted pH with NaOH 5N. 0.5% SDS 20 g, was 400 mL 25 mM Tris, 2.6 M thiourea, 5 M urea, and 5% 2- mercaptoethanol and 0.25 M sodium hydroxide. Na2 HPO4 6.0 g/L, KH2 PO4 3.0 g/L, NaCl 5.0 g/L and MgSO4 0.1 g/L Sodium Metabisulfite 0.5 M Urea 8 M and NaOH Sodium metabisulfite 0.5 M, Urea 8 M, NaOH and SDS

90 65 65 100 90 65 65 65 50 80

– 6.5 6.5 7-9 12 6.5 7 – 5 9

3 2 5 30 min 4 2 2.5 12 7 15-45 min

60 – 87 – 50 38 32 76 – 74

[35] [59] [58] [60] [61] [62] [63] [64] [12] [65]

65

6.5

2

–

[66]

50

8.5

72

–

[67]

37 60 65

8 6.5 6.5

48 5 2

83 41 14

[68] [45] [62]

Wool Human hair Black feather Wool Brown Alpaca

Chapter 17 r Recent developments in extraction of keratin from industrial wastes

Table 17.4 Sulfitolysis methods for the extraction of keratin from different sources.

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wool. They studied five different methods including alkali hydrolysis. For hydrolysis using NaOH, 10 g of the wool was treated with 2% NaOH for three hours at 80°C. As compared to other methods, the extraction of keratin through alkali process yield approximately 25% and protein while the protein yield up to 63%. This decrease in yield was probably because of degradation of amino acid contants and extensive hydrolysis of polypeptides and huge amount might be lost during the dialysis process. Although this method is cheap but the yield is low as compared to other methods. Al-Souti, Gallardo [74] have investigated the effect of autoclaving, on addition of NaOH on protein content of chicken feathers. The author performs different experiment by varying the ratio of NaOH, autoclave and time. It was concluded by the authors that the pepsin digestibility and protein content of feathers when treated for 2, 12 and 24 h with NaOH, digested most of the chicken feathers. The reaction time for 2 hours gives highest pepsin digestibility as compared to 12 and 24 h treatment, while the protein content was found lower as compare to the raw and control feathers. 87.47% protein content showed by the raw feather as compared to insoluble control chicken feathers. The use of sodium sulfide can reduce NaOH amount used for the extraction of keratin. Harris and Smith [75] reported that by adding sodium sulfide 1% to the solution of 0.065 N NaOH can degrade wool more rapidly in a short period of time i.e. 30 min as compare to alone NaOH. By adding sodium sulfide, it was observed that sulfur content in the residual was more when compared with NaOH treatment. Mokrejs, Svoboda [76] have studied the two-stage alkaline enzymatic hydrolysis of poultry feathers by using KOH. The feather a ratio of 1:50 were mixed in 0.1% or .03% potassium hydroxide and incubated for the 24 h at 70°C. In second stage the proteolytic enzyme is added up to 1%–5% for 4–8 h at 50°C–70°C at pH 9.0. This results in more than 91% degradation. Extraction through alkaline hydrolysis has some drawbacks such as difficulty in handling because of temperature and pressure, cost of alkali because high volume is used and recovery issues. Beside all, many authors reveals that the 2.5% NaOH with other chemical treatment can increase the extraction yield up to 94% [46] (Table 17.5). It has been observed that that the solubility of keratin by alkali method directly depends on the concentration of alkali solution, higher concentration increased the strength of wool. The strength of the wool fiber can be 30% as compare to original fiber, if the NaOH concentration will be increased up to 30%. During the alkaline processes harsh chemical conditions effects the final product hence at industrial scale, use of this of keratin is limited. Cystine is the major constituent of keratin and in any extraction method precautions should be taken to preserve major portion of cystine. The addition of alkali solution to the keratinous material will leads to loss of sulfur as well as dissociation of cystine take place. Cystine is very sensitive towards any alkali solution and it decomposes into pyruvic acid and producing amino acrylic acid. Yield and amino acid content from alkali methods are very low. Many authors are in favor that the alkaline method is good for extraction of keratin from feathers.

17.4.5 Ionic liquid methods for the extraction of keratin Research on ionic liquid is flourishing day by day. In March 2003 first time the potential of ionic liquid for developing new technologies specially for chemical industry was begun to be

Condition/specification Source Feathers Feathers Wool

Extraction solvent

Sodium hydroxide 1.78% and sodium bisulfite 0.5% Alkali-enzymatic hydrolysis NaOH and KOH both are used. Potassium hydroxide and sodium hydroxide (14:1) Concentration 0.5 to 3% (w/v). Feathers Sodium hydroxide 50%, Urea 8 M, L-cysteine Feathers NaOH 0.4%,Steam 1.4–2.0 MPa Wool Sodium hydroxide 2% Human hair NaOH 6 g/L. Human hair NaOH 0.1 M, Na2 SO3 0.75 M, urea 8 M sodium dodecyl sulfate 0.02 M Wool Sodium hydroxide 0.5 N Feathers Sodium hydroxide 0.1 N Wool KOH–0.5 mol/L and NaOH 0.5 mol/L heated in a microwave oven (800 W) containing wool Feathers 1 M NaOH feathers/bath 1 g/25 mL Wool Thioglycollate O.1 M or by Feathers Various conditions i.e. NaOH (0.01–0.1 M) and microwave-alkaline pretreatment (0.01–0.05 M. Both autoclave alkaline NaOH 0.068 M 0.05 M NaOH than 80% more than 70% protein recovery Wool NaOH 15% and water 1:20

Temperature (°C) pH

Time (h)

Yield (%) Reference

87 70-80 120

12-13 111 min – 4 – 30 min

68 76 100

[77] [78] [79]

70 25 80 80 80

10.5 4.5 7.0 –

12 0.5–5 min and 1 h 3 3 5

60 65 25 75 55

[16] [80] [45] [81] [82]

65 90 –

13.9

3 1 1

– 90 60

[83] [84] [85]

– 50

– 12.6

24 40 min 1–10 min

54 65

[86] [87] [88]

–

105 80

12

2 min 10 min. 3

80 79

[89]

Chapter 17 r Recent developments in extraction of keratin from industrial wastes

Table 17.5 Alkaline methods for the extraction of keratin from different sources.

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FIGURE 17.4 Common strategy for extraction of keratin by using ionic liquids.

recognized and the first process at industrial level by using ionic liquids was announced. The ionic liquids are entirely composed of ions, i.e. the solution of NaCl in water is a molecular solvent but the molten NaCl is considered as an ionic liquid. Ionic liquids are basically molten salts composed of inorganic/organic anions or bulky cations. Due to its thermal stability high melting and boiling points, higher ion conductivity, recyclability high salvation, non-flammable, low vapor pressure and chemically stable. They possess unique physio-chemical properties. Ionic liquid is also considered as a green solvent and widely used for different application like solvent, ion conductive media and catalysts [90]. Swatloski, Spear [91] has reported the dissolution of cellulose in ionic liquids, the cellulose was regenerated, and it has been observed that there was no significant change in dispersibility and degree of polymerization in cellulose. These findings received attentions of researchers to study the ionic solvent for the different natural polymeric materials. Ionic liquid can destroy strong interactions i.e. hydrogen bonding hence it increases the dissolution of polymers. Different ionic liquids have been studied for the dissolution of different natural polymers, the ionic liquid with imidazole has shown a promising result in case of wool keratin, lignocellulose and protein extraction. Due to its low price and easy availability, it’s good for industrial application. Several studies have been conducted for the dissolution of wool keratin including imidazole with ionic liquid [92–100]. The proposed mechanism of dissolution of wool for extraction of keratin by ionic liquids is the breaking of lipids layers which covered the wool surface. The solubility of feathers depends mainly on the polarity of ionic liquids, hence when the polarity of ionic liquids increased, the extraction yield also increased. For the extraction of keratin from feathers or wool, the parent material is immersed in ionic liquid for certain period and required temperature. Ionic liquid can be reused and recycled, they have a very low vapor pressure so they can be recovered and reuseable. Keratin is regenerated by using water as a coagulation bath. Temperature plays an important role in dissolution process (Fig. 17.4). It improves mobility of ions as well as lower-down the viscosity. But higher temperature denatures

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the protein i.e. keratin by shorten the peptide chain as well as low molecular weight product, hence the usage of the final product become limited. So, the higher temperature is not feasible when we need to extract a good quality product rich in amino acids. It has been reported that the cysteine content of keratin was lowered from 8.9 to 0.9 if the temperature was increased from 120°C to 180°C [25]. Ji and Chen [101] studied the extraction of keratin from chicken feathers by using ionic liquid. He used [Bmin]Cl with Na2 SO3 for unfolding the disulfide bonds in feather keratin by forming RSSO3 Na. The water was also added to decrease viscosity and increase solubility of Na2 SO3 . Water improved the extraction of feathers keratin. The keratin was separated easily from ionic liquid phase after addition of some water as solid precipitation owing the immiscibility of keratin with water and miscibility of ionic liquid with water. Precipitated keratin can be easily separated by filtration while ionic liquid can be distilled and Na2 SO3 was recycled. The maximum extraction was observed at 10% weight Na2 SO3 in liquid, 20% weight of water while the ratio of liquid/feather was 20% by weight, the optimized temperature was set at 90°C for 60 min. The extraction of keratin was found 75.1% while dissolution rate was 96%. Several studies have been reported the effect of temperature on dissolution and extraction of keratin. In case of wool, the good solubility of wool was observed at 130°C. Higher temperature provided energy to unfold the disulfide as well as hydrogen bonds. The structure of cations also played an important role in dissolution of wool keratin. Zheng, Nie [102] have studied the different ionic liquids for the extraction of keratin from wool, the study suggest that imidazolium based ionic liquids has a better capability to dissolve the keratin from wool. The study reveal that 8% by weight wool was completely dissolve in [Bmin]Cl in 5 h, [N2221 ] DMP in 3 h and in [Emin]DMP in 1.5 h. and while dissolution of keratin was not found in 24 hours in [BPy]Cl, [N4444 ]Cl and [P4444 ]. The author also investigated the imidazole based cations effects on the length of chain and observed that with the same condition i.e. temperature, time and weight of wool to ionic liquid, with the anion Cl- the chain length of imidazole ring increased from C2 -C8, indicated that with the same conditions the [Cn min]Cl: n = 2, 4, 6, 8 showed the similar polarity, dissolution capacity and spatial structural change thus it is concluded that the chain length of imidazole cations has very minute effect on the dissolution capability of ionic liquids. The hydroxyl group plays an important role in cleavage the hydrogen bonding in wool keratin. Imidazole with hydroxyl group is functioned to increased H-bonding sites. The author observed that the keratin obtained from wool is insoluble in [EtOHmin]FeCl4 or [EtOHmin]Cl, because of possibly formation of hydrogen bonds between [EtOHmin]FeCl4 or [EtOHmin]Cl with hydroxyl, hence reducing the cleave capacity of hydrogen bonding in keratin. For the wool keratin the dissolution capability of the ionic liquid has follows order of [Bmim]FeCl4 < [Bmim]SCN < [Cn mim]Cl (n = 2, 4, 6, 8) < [N2221 ]DMP < [Emim]DMP < [Bmim]OAc. Experiments also reveals that keratin was not dissolved in [BPy]Cl, [N4444 ]Cl, [P4444 ]Cl, [EtOHmim]FeCl4 or [EtOHmim]Cl. Thus anions and cations only played a synergistic effects in the dissolution of keratin from wool. Several studies reports that ionic liquid with imidazolium cations have significant capability to dissolve keratin at higher grade, while ionic liquids with tetrabutylphophonium and tetrabutylammonium do not success this task. One of the promising anion for the dissolution of keratin are formate, acetate, chloride and phosphate. Some researchers stated that the dissolution of keratin in an ionic liquid is depend on anion on

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Table 17.6 Ionic liquid methods for the extraction of keratin from different sources. Condition/specification Source

Extraction solvent

Temperature (°C)

pH

Time (h)

Yield (%)

Reference

Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Feathers Feathers Feathers Feathers Feathers Feathers Feathers Feathers Feathers Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Wool Camel hair

[Emim]DEP [Emim]DEP [Emim]DEP [Emim]DEP [Emim]DEP [Emim]DEP Emim]Cl [Bmim]Cl [Bmim]OAc [Emim]OAc [Emim][Br] [Amim]Cl [Bmim]Cl Choline thioglycolate [Bmim]NO3 [Bmim]HSO4 [Bmim]Cl [Amim]Cl [Hmim]CF3 SO3 [Bmim]Br [Bmim]Cl [Bmim]Cl [Bmim]Cl [Emim]Ac [Emim]DEP [Amim]Cl [Emim]Cl [Bmim]Cl HOEtmimCl [Bmim]DCA [Bmim]SCN BmpyrrCl BpyCl [Bmim]Cl BMIM]Cl

1:10 1:10 1:10 1:10 1:10 1:10 1:10 1:10 1:10 1:10 1:10 1: 2 1: 2 1: 2 1: 2 1: 2 1: 2 1: 2 1: 2 1: 2 1: 6 1: 6 1: 6 – – – – – – – – – – – 15% (w/w)

140 120 120 100 120 120 120 120 120 130 130 130 130 130 90 90 90 90 90 90 150 180 120 120 120 120 120 120 120 120 120 180 180 180 130

2 1 3 2 2 30 min 30 min 30 min 30 min 30 min 30 min 10 10 10 1 1 1 1 1 1 30 min 30 min 30 min – – – – – – – – – – – 10

11.36 40.62 20.56 – 30.63 70.02 73.86 78.54 16.82 15.89 – 60 60.0 55 4.2 4.1 4.8 4.8 0.2 4.2 35 18 57 38 22 13 14 11 3 1.5 10, in most cases) make cellulose fibers a superb reinforcement material for polymer composites. Water & air filtration: Cellulose fibers are used in water purification facilities as they can filter impurities like dirt, sand particles, bacteria (like E. Coli) and metallic impurities quite effectively [126]. On the other hand, better tensile properties, large surface area, oil absorption capability, temperature stability are some of the properties for which cellulose fibers are used in air filters [127]. Oil & dye absorption: As we have discussed in sections 4.1.4 and 4.1.5, cellulose fibers extracted from maize straw and banana peel are good as oil and dye absorbers. They are used as sorbents in industries to clean up oil or dye spills. Insulation: Cellulose fibers are traditionally used as insulator material (in electrical cables, transformers, pipes, buildings, etc.) due to their low thermal and electrical conductivity.

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19.5.2 Applications of cellulose nanoparticles Cellulose nanoparticles find their application as a reinforcement material in composites. Cellulose-based Bio or Nanocomposite is a relatively new research field that has gained increasing attention for its exceptional properties in holds. Some of these research have reached the level of practical use in recent years. Acoustic diaphragm: Nanocellulose has two unique properties, low dynamic loss and high sonic velocity, which make them an interesting material to make acoustic diaphragm. Ultrathin nanocellulose diaphragm can produce warm and delicate sounds like papers while producing the same sound velocity as titanium and aluminum diaphragm [128]. SONY is already using this technology in their headphones for a long time [129]. Digital display: Nanocellulose’s paper-like appearance, contrast, better reflectivity, biodegradability has put them into the leading role to make the basic structure of dynamic display technology (e.g. electronic paper) [130]. It is also being used as a reinforcement material in optically transparent plastics to make bendable displays. They can also remain transparent even at higher fiber content [131]. Flexible Organic Light Emitting Diode (FOLED) has been made by Legnani et al. which is biodegradable and uses a nanocellulose membrane as substrate [132]. Pharmaceutical sector: Cellulose is being used in the pharmaceutical sector for a very long time. Their biocompatibility, excellent compaction properties and large surface area enable them to bind large amounts of drugs and that is why they are being used as a drug delivery excipient. By microparticle inclusion and proper tablet coating, it is possible to control the release rate and disintegration of these tablets [133]. Biomedical sector: Nanobiocellulose membranes have been developed which are elastic in nature, hold no microbial activity and have good water absorption capability. They are being used to make healing bandages [128]. Polyvinyl Alcohol (PVA)/Nanocellulose Composite is a promising material in Cardiovascular Tissue Engineering. This material has almost identical mechanical properties to that of aorta and heart valve leaflets [134]. The potentiality of nanocellulose to be used as a scaffold for tissue engineering of the artificial cornea has been explored by Huia et al. and the result is satisfying [135]. Another study was carried out by Amorim et al. to investigate the possibility of using nanocellulose for nasal reconstruction. They found that nanocellulosic blankets had good biocompatibility and do not change over time when used as an implant to reconstruct nose bone [136]. Moreover, the use of Nanocellulose in stem cell-based therapy has also drawn the attention of researchers [137]. On the other hand, cellulose-derived materials such as, cellulose acetate (which can be produced by the electrospinning method) are being utilized in cell culture, tissue engineering, biosensors and making antimicrobial mats [138]. Food industries: Unique nanostructure and excellent chemical and physical properties of Cellulose Nanocrystals (CNCs) play an important role in food industries. They are used in the packaging sector, as flavor carriers, suspension stabilizers, low-calorie replacements for carbohydrate additives, etc. Also, CNCs are ideal candidates for the food delivery system as they can protect the nutrients and other important ingredients of food products very efficiently [139].

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Water purification: Due to their chemical inertness, versatile surface chemistry, high surface area and high strength, nanocellulose is used to make ultra-filtrating membranes to purify water. They have been proved to be efficient to remove heavy metal particles, oil, microbes, dye and organic molecules [140].

19.6 Concluding remarks With the increasing population and the development in the agricultural sector around the world, the production of food is increasing rapidly; creating an enormous amount of agro-industrial wastes. These wastes which contain a large quantity of value-added products are discarded without any proper treatment and end up polluting our surroundings. They have the potential to contribute to the economy of a country. But the lack of proper knowledge and management making them a barrier to the path of the country’s sustainable development. Specially extracting cellulose from these agro-industrial wastes can solve both economic and waste problems. Cellulose is the most abundant biopolymer in nature, having exceptional mechanical and chemical properties. Moreover, it is environmentally friendly and biocompatible. Extensive research on cellulose, cellulose-based products and their application is being carried out by the scientific community; making it one of the most fascinating bioresources of this century. Agroindustrial waste is widely considered to extract cellulose in different forms like cellulose fibers, micro/nanocellulose and cellulose nanocrystals. Their properties largely depend on the source and preparation technique. The extraction of cellulose from agro-industrial wastes has been shortly described in this chapter. Cellulose fiber extraction from wastes is mainly chemical analysis-oriented, which involves processes like dewaxing, alkaline or acidic treatment, chlorite treatment, bleaching of the waste. Though a greener environment-friendly approach is always appreciated. On the other hand, cellulose micro/nanofiber is produced via mechanical treatment such as grinding, HPH, cryocrushing, HIU, microfluidization, etc. However, these mechanical procedures actually take place after the pretreatment of the wastes which provides purer products and reduces energy consumption. The preparation technique of cellulose nanocrystals follows the acid hydrolysis procedure before mechanical treatment. The morphology of the CNCs mainly depends on hydrolysis conditions and acid medium. Men have been using cellulose fibers for a very long time. Fibers are commonly utilized in textile, insulation, water purification and reinforcement. In recent years, the nanoworld of cellulose has opened the door to more possibilities. They are now being considered to be used in biomedical, electronic, food and pharmaceutical sectors. Extracting cellulose (especially cellulose nanoparticles) from wastes can be a challenge for agro-based industries sometimes. But considering the market value of cellulose and the environmental impact of wastes, extracting cellulose from them can be exceedingly beneficial for the environment and economy of a country.

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Index A Accelerated solvent extraction (ASE), 55, 98, 187 Acid, 200 ionic liquids, 40 sodium chlorite treatment, 326 value, 235 Agricultural residues, 2 Agri-food industry, 131, 132f Agro-industrial wastes, 114, 134, 134t, 143, 144, 145, 164, 171, 225, 250, 323 agricultural residues, 2 benefits, recycle and reuse, 4 bioactive compounds, 6 bioconversion, 4 bioenergy and biorefineries, 8 challenges and future outlook, 226 enzyme, 6 enzyme production, 4 fertilizers in aquaculture, 9 future perspective, 11 industrially important enzymes, 6 industrial wastes, 3 lignin, 221 polysaccharides, 4 problems, 3 separation of natural products, 8 solid state fermentation, 7 types and sources, 2 value-added applications, 10 Alkali extraction, 200 Alkaline peroxide treatment, 326 Alkaline pulping method, 224 Alkaloid, 20 amaryllidaceae, 22 benzyl isoquinoline, 21 calystegines, 21 ipecac, 22 monoterpene indole, 22 purine, 20

pyrrolizidine, 21 quinolizidine, 21 tropane, 21 Alpha amylase, 4 Amaryllidaceae alkaloid, 22 Amino acid composition, 284t Amyloglycosidase (AMG), 5 ANOVA analysis, 268 Anthocyanins chemical structure, 112f Anticardiovascular diseases, 183 Antiobesity effect, 160 Antioxidants, 144, 148 activity, 151 Aquaculture, agro-industrial wastes, 9 Aqueous extraction, 199 Aqueous two-phase solvents extraction (APTE), 63 Aromatherapy, 29 Artificial antioxidants butylated hydroxyanisole, 144 butylated hydroxytoluene, 144 propyl gallate, 144 tert-butylhydroquinone, 144 B Bast fibers, 322 Benzyl isoquinoline alkaloid, 21 β−fructofuranosidase, 5 Bioactive compounds, 144, 145 extraction, 145, 150t Bio chemical compound extraction, 148, 149 Bioenergy and biorefineries, 8 Biological oxygen demand (BOD), 2 Bisulfide, 289 Bleaching pretreatment process, 338 Brick formation, 11 Bronsted acidic ionic liquids (BAIL), 40 Buszewska-Forajta’s classification, 39

349

350

Index

C Calystegines, 21 Camptothecin, 22 hemiterpenes, 23 lignans and lignins, 22 monoterpenes, 23 polyketides, 23 sesquiterpenes, 23 Carotenoids, 157, 158, 179 antioxidant, 160 extraction process, 166f food industry, 164 structural classification, 158f Carvacrol, 29 Cavitation phenomenon, 169 Cellulose, 320 chemical properties, 321 extraction scheme, 330f extraction techniques, 324 fiber extraction, 324 fibers, 339 mechanical properties, 321 microfibrils, 336 nanofibrils, 336 nanoparticles, 340 origin, 321f structure, 320, 321f waste sources, 323 Chemical oxygen demand (COD), 2 Citric acid production, 10 Citrus wax, 237 Coconut production agro-industrial waste, 304 agro-industrial waste challenges and opportunities, 305 agro-industry residual potential, 304 biorefineries utilization, 304 economic potential, 303 Cold pressing, 308 Column chromatography (CC), 104 Compositing, 10 Conventional extraction method, 187 techniques, 166 Conventional extraction methods, 308

Cost of manufacturing (COM), 55 Crocetin, 159 Cryocrushing, 335 D Debauched pyrolysis, 222 Deodorization process, 237 Dielectric constant, 188t Diode array detector (DAD), 102 Distillation methods, 309 Dry tensile strength, 269 E Electromagnetic waves, 170 Enhanced carotenoid, 163 Enzymatic extractions, 200 Enzyme-assisted extraction (EAE), 138, 186 Enzyme-based process, 198 Essential oils, 29, 306, 310 chemical composition, 307 extraction, 307 Extraction methods, 146 Extraction processes, 134 microwave-assisted extraction, 135 pressurized liquid extraction, 134 subcritical water extraction, 135 supercritical fluid extraction, 136 ultrasound-assisted extraction, 135 Extract lipid compounds free fatty acids, 138 phytosterols, 138 policosanols, 138 tocopherols, 138 F Farnesyl diphosphate (FPP), 23 Fatty acids, 240 agro-industrial waste, 236 characteristics, 234 iodine value, 235t structures, 234t, 236, 239f Ferulic acid, 11 Fibers extraction, 263 Flavonoids, 111

Index

cellulosic skin, husk or leaves waste, 119 classes, 112f extraction, 117 ligneous barks, 124 ligneous shells, 122 pomace, 123 uses, 113 Food flavoring and preservative compounds, 11 Food fortification processes, 157 Food phenolic tert-butylhydroquinone, 144 Formic acids, 285 Fourier transform infrared (FTIR) spectroscopy, 104, 235 Free radicals, 144 Fruit by-products, 133f Fruit fibers, 322 G Gallic acid, 148 Gallic acid equivalents (GAE), 116 Gas chromatography (GC), 102 Gas chromatography-mass spectrophotometry (GCMS), 311 Geranyl diphosphate (GPP), 23 Glucoamylase, 5 Grinder system, 335f H Hemiterpenes, 23 High hydrostatic pressure extraction (HHPE), 69 High-intensity ultrasonication, 336 High methoxyl pectins (HMP), 246 High-performance liquid chromatography (HPLC), 102 High-performance thin layer chromatography (HPTLC), 103 High pressure homogenizer, 332 temperature extraction, 149 Hot air drying, 163 Hydrolysis lignin, 221 I Industrial wastes, 3, 281

Instant controlled pressure drop, 63 high hydrostatic pressure extraction, 69 hydrodistillation/steam distillation, 64 process additional benefits, 67 Intercellular signaling, 161 Invertase, 5 Ionic liquids (IL) classification and properties, 39 future perspectives, 46 and MAE, 42, 45 microwave extraction, 43 for microwave extraction, 41 Ipecac alkaloid, 22 K Keratin, 282, 297 alkali methods, 290, 293t extraction, 283 extraction procedure, 286f ionic liquid methods, 292, 296t reduction method, 285 reduction methods, 288t sources of, 282 strategy for extraction, 294f structure, 282, 283f sulfitolysis methods, 289, 291t Kraft lignin method, 222 L Leaf fibers, 322 Lewis acidic ionic liquids (LAIL), 40 Ligneous barks, 124 Lignins, 22, 217 advantages, 220t extraction, 222 extraction processes., 223f limitations, 220t source, 219, 221f Lignocellulose biomass derivatives, 218 Lignocellulosic by-products, 132f Lipase, 6 Lowmethoxyl pectins (LMP), 246 Lycopene, 158, 179, 180t, 186, 189, 192, 193 anticarcinogenic property, 184t extraction, 185

351

352

Index

microencapsulation and storage stability, 192 prevention of skin damage, 184 protective effect, 183t role in human health, 181 sources, 180 structure, 181 M Maceration technique, 94, 148 Maize straw (MS), 329 Mercaptoethanol, 285, 289 Microcapsules, 190 Microencapsulation techniques, 191 Microfluidizer, 333, 334f Microwave-assisted enzymatic extraction (MAEE) system, 39, 42, 97, 135, 148, 170, 188 closed, 41 method, 149, 199f process, 170 simultaneous, 41 technology, 148 Microwaves, 188 Moderate electrical field processing (MEF), 171 Molecular affinity, 166 Monoterpene indole alkaloid, 22 Monoterpenes, 23 Multistep heat treatment, 163 N Nanobiocellulose membranes, 340 Natural deep eutectic solvents (NDES), 63 Natural dyes, 204, 205, 205t, 210 dye-sensitized solar cells, 210 medicinal purpose, 209 Natural fibers, 261 mechanical properties, 265 Natural products, 19, 131 accelerated solvent extraction, 98 chromatographic techniques, 102 column chromatography, 104 combined processes, 63 distillation methods, 99 distribution, 26t extraction methods, 93

gas chromatography, 102 high-performance liquid chromatography, 102 high-performance thin layer chromatography, 103 maceration, 94 microwave-assisted extraction, 97 negative pressure cavitation extraction, 61 operational parameters, 56, 61 percolation, 95 phytonic process, 59 primary metabolites, 19 process improvements, 62 sample preparation, 92 secondary metabolites, 19 separation methods, 101 source, 27 soxhlet extraction, 95 supercritical fluid extraction, 98 thin layer chromatography, 103 ultrasound-assisted extraction, 97 Negative pressure cavitation extraction (NPCE), 61 system, 41 Nonconventional extraction techniques, 167 advantages, 168t disadvantages, 168t Nonthermal processing technique, 189 Norbelladin, 22 Nuclear magnetic resonance (NMR) spectroscopy, 105 O Obesity disorder, 160 Oil cakes, 3 Organic wastes, 1 Organosolv lignin, 221, 223 treatment, 223 P Pectin, 243, 244, 252 classification, 245 colloidal properties, 247 extraction, 254 flowchart, 251f gelation properties, 248

Index

properties, 247 rheological properties, 249 sources and extraction, 249, 250t structure, 245, 246f yield, 254t Peracetic acids, 285 Percolation, 95 Phenolic compounds, 131, 148 Photosensitivity disorders, 161 Photosensitizers protoporphyrin, 161 Phytase, 6 Phytochemicals, 100 alkaloids presence, 100 carbohydrates presence, 101 diterpenes presence, 101 flavonoids presence, 100 phenols presence, 101 phytosterols presence, 100 proteins and amino acids, 101 Pigment production, 10 Polar molecules, 189 Pollution, 1 agricultural and forestry, 1 industrial activities, 1 Polyelectrolyte complex (PEC), 245 Polyketides, 23 Pomace, 123 Pressurized fluid extraction (PFE), 55 Pressurized hot solvent extraction (PHSE), 55 Pressurized hot water extraction (PHWE), 55, 59 Pressurized liquid extraction (PLE), 55, 134, 151, 170 technology, 151 Pressurized low polarity water extraction (PLPW), 55 Proanthocyanidins, 145 Processing techniques, 162 Protease, 6 Protein-glutamine-γ -glutamyl transferase, 6 Pulsed electric field processing (PEF), 150, 171 assisted extraction, 172, 189 technology, 150 Purine alkaloid, 20 Pyrolytic lignin, 222 Pyrrolizidine alkaloid, 21

353

Q Quinolizidine alkaloid, 21 R Room-temperature ionic liquids (RTIL), 35 S Saccharomyces cerevisiae, 5 Saponins, 24 Scanning electron microscopy, 146 Secondary metabolites, 20 Seed fibers, 322 Sesquiterpenes, 23 Solid state fermentation, 207 Solid state fermentation (SSF), 7 Solvent extraction, 309 Soxhlet extraction technique, 95, 189 Spray drying technique, 191, 200 Spray dyers, 201f Stalk fibers, 322 Steam explosion method, 223 Steroids, 24 Structure elucidation, 104 Fourier transform infrared spectroscopy, 104 nuclear magnetic resonance spectroscopy, 105 UV–visible spectroscopy, 104 Subcritical water extraction (SWE), 55, 135 Sugarcane bagasse (SCB), 325 Supercritical CO2 extraction, 80 bioactive compounds, 81 controlled puffing in extrusion, 84 environmental applications, 85 food processing, 84 hexane removal, 85 Supercritical fluid extraction (SFE), 79, 98, 136, 149, 167, 185, 200 fluid extraction, 185 schematic representation, 137f Super critical method of separation, 201f Superheated water extraction, 55 Supramolecular solvents (SUPRAS), 122 T Tetrahydrofuran, 226

354

Index

Tetraterpene molecules, 159 Tetraterpenes, 24 Thermal processing, 162 Thin layer chromatography (TLC), 103 Transglutaminase, 6 Triterpenes, 24 natural product, 25 saponins, 24 tetraterpenes, 24 Trolox equivalent antioxidant capacity (TEAC), 121 Tropane alkaloid, 21

V Vitamin A, 159 Volatile compounds, 314

U Ultrasonic microwave-assisted extraction (UMAE) system, 199, 41, 198 Ultrasonic waves, 186 Ultrasound-assisted extraction (UAE), 61, 97, 135, 169, 186

X Xanthophylls, 158

process, 147 protective finishing, 208 technique, 146

W Walnut husk, 203 Waste products, 281 Wet single fiber tensile test (WSFTT), 273 Wheat straw (WS), 328