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Biopolymer-Based Food Packaging: Innovations
and Technology Applications
ffirs.indd 1 21-03-2022 08:41:47

Biopolymer-Based Food Packaging: Innovations
and Technology Applications
Edited by
Santosh Kumar
Central Institute of Technology Kokrajhar
Kokrajhar, India
Avik Mukherjee
Central Institute of Technology Kokrajhar
Kokrajhar, India
Joydeep Dutta
KTH Royal Institute of Technology
Stockholm, Sweden
ffirs.indd 3 21-03-2022 08:41:47

This edition first published 2022
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Library of Congress Cataloging-in-Publication Data
Names: Kumar, Santosh, 1980- editor. | Mukherjee, Avik, editor. | Dutta, Joydeep (Professor of functional
materials), editor.
Title: Biopolymer-based food packaging : innovations and technology applications / edited by
Santosh Kumar, Avik Mukherjee, Joydeep Dutta.
Description: Hoboken, NJ : John Wiley & Sons, [2022] | Includes bibliographical references and index.
Identifiers: LCCN 2021045228 (print) | LCCN 2021045229 (ebook) | ISBN 9781119702252 (hardback) |
ISBN 9781119702320 (pdf) | ISBN 9781119702337 (epub) | ISBN 9781119702313 (ebook)
Subjects: LCSH: Food--Packaging. | Biopolymers.
Classification: LCC TP374 .B575 2022 (print) | LCC TP374 (ebook) | DDC 664/.09--dc23/eng/20211109
LC record available at https://lccn.loc.gov/2021045228
LC ebook record available at https://lccn.loc.gov/2021045229
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Cover design by Wiley
Set in 9.5/12.5pt STIXTwoText by Integra Software Services Pvt. Ltd, Pondicherry, India
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v
Contents
List of Contributors xv
Preface xix
1 An Overview of Natural Biopolymers in Food Packaging 1

Santosh Kumar, Indra Bhusan Basumatary, Avik Mukherjee, and Joydeep Dutta
1.1 Introduction 1
1.2 History and Background 4
1.3 Classification 6
1.3.1 Polysaccharide-Based Biopolymers 6
1.3.2 Protein-Based Biopolymers 11
1.3.3 Lipid-Based Biopolymers 13
1.3.4 Biopolymers Synthesized from Bio-derived Monomers 14
1.4 Advantages and Disadvantages 15
1.5 Properties and Applications 16
1.6 Conclusion and Perspectives 17
References 21
2 Biopolymers: The Chemistry of Food and Packaging 29

Rajib Majumder, Arpita Das, Avik Mukherjee, and Santosh Kumar
2.1 Introduction 30
2.2 Biopolymers, Packaging Surfaces, and the Chemistry of Foods 31
2.2.1 Biopolymers 31
2.2.2.1 Starch and Derivatives 32
2.2.2.2 Cellulose and Derivatives 33
2.2.2.3 Chitin and Derivatives 33
2.2.2.4 Alginate and Pectin 34
2.2.2.5 Xanthan Gum 34
2.2.3.1 Gelatin 35
2.2.3.2 Collagen 35
2.2.3.3 Soy Protein 36
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vi Contents
2.2.3.4 Whey Protein 36

2.2.4 Aliphatic Polyester-Based Biopolymers 36
2.3 Properties 37
2.3.1 Physicochemical Properties 37
2.3.1.1 Density 42
2.3.1.2 Crystallinity 42
2.3.1.3 Melting Temperature (Tm) 43
2.3.1.4 Glass Transition Temperature (Tg) 44
2.3.1.5 Film-Forming Property 44
2.3.1.6 Solubility 44
2.3.1.7 Transparency 45
2.3.1.8 Thermal Stability 45
2.3.2 Mechanical Properties 45
2.3.3 Barrier Properties 46
2.3.4 Bio-activities 47
2.3.5 Biodegradability 49
2.4 Interactions Between Food and Packaging 50
2.4.1 Migration 50
2.4.2 Permeation 50
2.4.3 Sorption 51
2.5 Surface Properties of Packages and Food 52
2.5.1 Hydrophilicity and Hydrophobicity 52
2.5.2 Contact Angle 52
2.5.3 Wettability 53
2.6 Conclusion and Future Perspectives 53
References 54
3 Technologies for Biopolymer-Based Films and Coatings 66

Anjali Khuntia, N. Sai Prasanna, and Jayeeta Mitra
3.1 Introduction 67
3.2 Fabrication Techniques for Films 68
3.2.1 Solvent Casting or Wet Process 68
3.2.1.1 Film-Forming Solution (FFS) 69
3.2.1.2 Film Casting or Film Coating 71
3.2.1.3 Film Drying 71
3.2.2 Extrusion or Dry Process 71
3.2.3 Electrohydrodynamic Technique 76
3.2.4 Comparison and Application of Different Fabrication Techniques 76
3.3 Coating Methods 76
3.3.1 Dipping 77
3.3.2 Brushing 77
3.3.3 Spraying 77
3.3.4 Electrospraying 78
3.3.5 Layer-by-Layer (LBL) Electrostatic Deposition 78
3.3.6 Vacuum Impregnation (VI) 79
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Contents vii
3.4 Properties 79
3.4.1 Physical Properties 79
3.4.1.1 Thickness 79
3.4.1.2 Density 80
3.4.2 Water Absorption Capacity and Sorption Analysis 80
3.4.3 Contact Angle/Wetting Tension 82
3.4.4 Mechanical Properties 82
3.4.4.1 Tensile 84
3.4.4.2 Puncture Tests 85
3.4.5 Permeability 88
3.4.5.1 Water Vapor Permeability 88
3.4.5.2 Gas Permeability 92
3.4.6 Optical Properties 93
3.4.7 Rheological Properties 93
3.4.7.1 Viscosity Tests 94
3.4.7.2 Melt Index Test 94
3.4.8 Thermal Properties 95
3.4.8.1 Differential Scanning Calorimetry 95
3.4.8.2 Thermogravimetric Analysis 95
3.4.8.3 Thermomechanical Analysis 96
3.4.8.4 Dynamic Mechanical Thermal Analysis 97
3.5 Applications 98
3.5.1 Composite Films or Multilayer Packaging 99
3.5.2 Nanostructured Film 99
3.5.2.1 Nanocomposite Films 99
3.5.2.2 Nanolaminated Films 101
References 101
4 Chitosan-Based Films and Coatings 110

Gitanjali Gautam, Ruchi Rani, Laxmikant S. Badwaik, and
Charu Lata Mahanta
4.1 Introduction 110
4.2 Sources, Structure, and Properties 111
4.2.1 Sources 111
4.2.2 Structure 112
4.2.3 Properties 114
4.3 Isolation, Characterization, and Modifications 115
4.3.1 Isolation 115
4.3.1.1 Extraction from Crustaceous Shells 115
4.3.1.2 Extraction from Fungal Cell Wall and Mushrooms 116
4.3.1.3 Extraction from Insect Cuticles 117
4.3.1.4 Extraction from Terrestrial Animal Exoskeletons 118
4.3.2 Characterization 119
4.3.3 Modifications 119
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viii Contents
4.4 Chitosan-Based Composite Films and Coatings 123

4.4.1 Gelatin-Based Edible Films and Coatings 123
4.4.2 Protein-Based Edible Films and Coatings 124
4.4.3 Starch-Based Edible Films and Coatings 125
4.4.4 Alginate-Based Edible Films and Coatings 125
4.5 Using Essential Oils as Antimicrobial Agent 126
4.5.1 Rosemary (Rosmarinus officinalis) 127
4.5.2 Cinnamon (Cinnamomum verum) 127
4.5.3 Oregano (Origanum vulgare) 127
4.5.4 Clove (Syzygium aromaticum L.) 128
4.5.5 Thyme (Thymus vulgaris) 128
4.6 Antimicrobial Activities 128
4.7 Effects on the Quality of Fruits and Vegetables 130
4.8 Effects on the Quality of Meat, Fish, and Seafood 130
References 138
5 Starch-Based Edible Films and Coatings 147

Priyadarshini, S.R., Srinivasan Krishnamoorthy, J.A. Moses,
and C. Anandharamakrishnan
5.2 Source, Structure, and Characteristics of Starch Granules 148
5.3 Physicochemical, Rheological, and Functional Properties 150
5.4 Chemical and Physical Modifications 152
5.4.1 Chemical Modifications 152
5.4.1.1 Crosslinking 152
5.4.1.2 Grafting 153
5.4.1.3 Esterification 153
5.4.1.4 Etherification 153
5.4.1.5 Oxidization 153
5.4.1.6 Cationic Modification 153
5.4.1.7 Dual Modification 154
5.4.2 Physical Modifications 154
5.4.2.1 Pregelatinized Starch 154
5.4.2.2 Annealing 154
5.4.2.3 Heat Moisture Treatment 154
5.4.2.4 Heat Drying 155
5.4.2.5 Osmotic Pressure Treatment 155
5.2.2.6 Freezing 155
5.2.2.7 Thermal Inhibition 155
5.4.2.8 Non-Thermal Modifications 155
5.5 Starch-Based Bionanocomposite Films and Coatings 156
5.6 Characterization 159
5.6.1 Film Thickness 159
5.6.2 Particle Size Determination 159
5.6.3 Scanning Electron Microscopy (SEM) 159
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Contents ix
5.6.4 Fourier Transform Infrared Spectroscopy (FTIR) 160

5.6.5 X-ray Diffraction (XRD) 162
5.7 Applications 164
5.8 Recent Developments and Future Directions 168
References 170
6 Protein-Based Films and Coatings 178

Manashi Das Purkayastha and Santosh Kumar
6.2 Types, Structures, and Properties 180
6.2.1 Casein 180
6.2.2 Whey 180
6.2.3 Gluten 181
6.2.4 Soy Protein 182
6.2.5 Collagen and Gelatin 182
6.2.6 Zein 183
6.3 Improvement in Physicochemical Properties of Proteins 183
6.3.1 Plasticizers 184
6.3.2 Physical and Chemical Crosslinking 185
6.4 Protein-Based Nanocomposites and Their Various Properties 187
6.5 Fabrication Techniques 192
6.5.1 Direct Casting 192
6.5.2 Coating 192
6.5.3 Spread Coating 193
6.5.4 Spin Coating 194
6.5.5 Spray Coating or Spraying 194
6.5.6 Dip Coating or Immersion Coating 194
6.5.7 Fluidized-Bed Coating 195
6.5.8 Pan Coating or Panning 195
6.5.9 Layer-by-Layer Assembly 195
6.5.10 Electrospinning 196
6.5.11 Extrusion 196
6.5.12 Compression Molding 198
6.5.13 Lamination 199
6.6.1 As Carrier of Antimicrobial Agents 201
6.6.2 As Carrier of Antioxidants 203
6.6.3 As Carrier of Flavoring Compounds 204
6.6.4 As Carrier of Live Microorganisms 206
References 209
7 Microbial Polysaccharides (MPs) in Food Packaging 225

C. Shashikumar, Sudip Mitra, and Siddhartha Singha
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x Contents
7.2 Production 227

7.3 Extraction and Purification 230
7.4 Characterization 230
7.4.1 Chemical Structure 234
7.4.2 Physicochemical Properties 239
7.4.2.1 Xanthan 239
7.4.2.2 Scleroglucan 239
7.4.2.3 Hyaluronic Acid or Hyaluronan 239
7.4.2.4 Xylinan or Acetan 239
7.4.2.5 Dextran 240
7.4.2.6 Gellan 241
7.4.2.7 Curdlan 242
7.4.2.8 Bacterial Cellulose 243
7.4.2.9 Pullulan 243
7.4.2.10Alginate 243
7.4.2.11Levan 244
7.4.2.12β-Glucan 244
7.4.2.13FucoPol 244
7.4.2.14Kefiran 245
7.4.2.15Polyhydroxyalkanoate 245
7.4.3 Film Formability and Properties Relevant for Packaging 245
7.5 Strategies for Tailoring MP Structures for Packaging Film or Coat
Applications 249
7.6 Applications and Their Commercialization Status 251
References 256
8 Polylactic Acid (PLA)-Based Composites in Food Packaging 264

M. Sukumar, K. Sudharsan, and Radha Krishnan K.
8.1.1 Production of Lactic Acid 266
8.1.2 Properties 267
8.1.3 PLA Composites as Food Packaging Materials 269
8.2 Isolation and Purification 272
8.3 PLA-Based Antimicrobial Nanocomposites 274
References 278
9 Antimicrobial Agents in Films and Coatings 282

Yashaswini Premjit, Gulshan Kumar Malik, and Jayeeta Mitra
9.2.1 Natural Antimicrobials 284
9.2.1.1 Plant-Based Antimicrobials 290
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Contents xi
9.2.1.2 Microbial-Based Antimicrobials 291

9.2.1.3 Animal-Based Antimicrobials 292
9.2.2 Chemical Antimicrobials 293
9.2.2.1 Nitrites 293
9.2.2.2 Chlorine Dioxide 293
9.2.3 Antimicrobial Nanostructures 294
9.2.3.1 Nanocarriers for Antimicrobials 294
9.2.3.2 Silver Nanoparticles 294
9.2.3.3 Chitosan Nanostructures 294
9.2.3.4 Nanoclays 294
9.2.3.5 Metal Oxide Nanoparticles 295
9.3 Choice of Materials 295
9.4 Methods of Addition 299
9.4.1 Antimicrobial Edible Coatings 299
9.4.2 Antimicrobial Films 303
9.4.3 Antimicrobial Pads 305
9.4.4 Antimicrobial Sachets 306
9.4.5 Modified Atmospheric Packaging 307
9.5 Effect on Packaging Film Properties 308
9.5.1 Effect on Mechanical Properties 308
9.5.2 Effect on Barrier Properties 310
9.5.3 Effect on Appearance, Color, and Transparency 310
9.5.4 Effect on Surface Hydrophilicity/Hydrophobicity of Films 313
9.6 Mechanisms of Action 313
9.6.1 Essential Oils 313
9.6.2 Organic Acids 314
9.6.3 Animal-Based Antimicrobials 314
9.6.4 Antimicrobial Peptides 315
9.6.5 Antimicrobial Nanoparticles 315
9.6.5.1 TiO2 315
9.6.5.2 ZnO 316
9.6.5.3 Ag NPs 316
9.7 Release Kinetics from Packaging Systems to Food 317
9.8 Food Regulations 319
9.9 Commercialization 320
References 322
10 Nanomaterials in Food Packaging 336

Santosh Kumar, Avik Mukherjee, Sweety Kalita, Namrata Singh, Vimal Katiyar
Atanu Mitra, and Dipankar Halder
10.2 Nanomaterials and Food Packaging Concepts 337
10.3.1 Supplementing Packaging Characteristics 339
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xii Contents
10.3.1.1 Nanoclay 342

10.3.1.2 Graphene 345
10.3.1.3 Organic Nanofillers 345
10.3.2 Antimicrobial Packaging 346
10.3.3 Extending Shelf-Life of Food 347
10.3.4 Inducing Smartness/Intelligence 351
10.4 Migration to Packaged Food Items 353
10.5 Environmental and Safety Aspects 354
10.5.1 Impact on Human Health and the Environment 354
10.5.2 Regulations on Use in the Food Sector 356
References 358
11 Silver and Zinc Oxide Nanoparticles in Films and Coatings 368

Abhishek Roy, K. Dharmalingam, and R. Anandalakshmi
11.2 Antimicrobial Properties 369
11.3 Biopolymer-Based Silver Nanocomposites 375
11.4 ZnO Nanostructures in Biopolymers 377
11.5 Applications of Silver Bionanocomposites 379
11.6 Applications of ZnO Bionanocomposites 383
References 385
12 Plant-Based Active Compounds in Food Packaging 394

N. Arul Manikandan, Kannan Pakshirajan, and G. Pugazhenthi
12.2 Plant-Based Active Compounds 396
12.2.1 Simple Phenolic Compounds 396
12.2.2 Flavones, Flavanols, and Flavonoids 396
12.2.3 Quinones 396
12.2.4 Tannins 397
12.2.5 Coumarins 398
12.2.6 Alkaloids 398
12.2.7 Terpenes 398
12.3 Active Components to Control Microbial Spoilage 398
12.3.1 Turmeric 405
12.3.2 Cinnamon 405
12.3.3 Lemongrass 405
12.3.4 Neem 406
12.3.5 Coriander 406
12.3.6 Garlic 406
12.3.7 Rosemary 406
12.3.8 Grapefruit Seed 407
12.3.9 Aloe Vera 407
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Contents xiii
12.3.10 Oregano 407

12.4 Active Materials to Control Food Oxidation (Food Antioxidants) 408
12.4.1 Quercetin 408
12.4.2 Carnosic Acid 409
12.4.3 Ellagic Acid 410
12.4.4 Ferulic Acid 410
12.4.5 α-Tocopherol 411
12.5 Polymer-Based Composites 411
References 415
13 Essential Oils in Active Films and Coatings 422

K. Dharmalingam, Abhishek Roy, and R. Anandalakshmi
13.2 Classifications and Components 423
13.3 Properties and Characteristics 424
13.4 Encapsulation 425
13.5 Biopolymer-Essential Oil Composites 428
References 439
14 Edible Films and Coatings 445

Indra Bhusan Basumatary, Sweety Kalita, Vimal Katiyar,
Avik Mukherjee, and Santosh Kumar
14.2 Biopolymers 447
14.2.1 Polysaccharides 447
14.2.2 Proteins 448
14.2.3 Lipids 450
14.3 Natural Active Components 450
14.3.1 Plant Extracts 450
14.3.2 Antimicrobial Peptides 452
14.3.3 Probiotics 453
14.4 Nanomaterials 453
14.4.1 Inorganic Nanomaterials 453
14.4.2 Organic Nanomaterials 455
14.5 Extending Shelf-Life of Food 456
14.5.1 Fruits and Vegetables 456
14.5.2 Meat, Poultry, and Fish 459
14.5.3 Milk and Dairy Products 460
References 465
Index 476
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xv
List of Contributors
R. Anandalakshmi K. Dharmalingam
Advance Energy & Materials Systems Advance Energy & Materials Systems
Laboratory (AEMSL), Department of Laboratory (AEMSL), Department of
Chemical Engineering, Indian Institute of Chemical Engineering,
Technology Guwahati, Guwahati, Indian Institute of Technology
Assam, India Guwahati, Guwahati,
Assam, India
C. Anandharamakrishnan
Computational Modeling and Nanoscale Joydeep Dutta
Processing Unit, Indian Institute of Food Functional Materials, Department
Processing Technology (IIFPT), Ministry of of Applied Physics, SCI School,
Food Processing Industries, Government KTH Royal Institute of Technology,
of India, Thanjavur, Tamil Nadu, India Stockholm, Sweden
Laxmikant S. Badwaik Gitanjali Gautam

Department of Food Engineering and Department of Food Engineering and
Technology, School of Engineering, Technology, School of Engineering,
Tezpur University, Napaam, Tezpur University, Napaam,
Assam, India Assam, India
Indra Bhusan Basumatary Dipankar Halder

Department of Food Engineering and Department of Food Technology and
Technology, Central Institute of Biochemical Engineering, Jadavpur
Technology Kokrajhar, Kokrajhar, University, Kolkata, India
Assam, India
Sweety Kalita
Arpita Das Department of Food Engineering and
School of Life Science and Biotechnology, Technology, Central Institute of
Adamas University, Barasat, West Bengal, Technology Kokrajhar, Kokrajhar,
India Assam, India
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xvi List of Contributors
Vimal Katiyar Atanu Mitra

Department of Chemical Engineering, Department of Chemistry, Sree Chaitanya
Indian Institute of Technology Guwahati, College, Habra, West Bengal, India
Guwahati, Assam, India
Jayeeta Mitra
Anjali Khuntia Agricultural & Food Engineering
Agricultural & Food Engineering Department, Indian Institute of
Department, Indian Institute of Technology Kharagpur, Kharagpur, India
Technology Kharagpur, Kharagpur, India
Sudip Mitra
Srinivasan Krishnamoorthy Centre for Rural Technology, Indian
Computational Modeling and Nanoscale Institute of Technology Guwahati,
Processing Unit, Indian Institute of Food Guwahati, Assam, India
Processing Technology (IIFPT), Ministry
of Food Processing Industries, J.A. Moses
Government of India, Thanjavur, Tamil Computational Modeling and Nanoscale
Nadu, India Processing Unit, Indian Institute of Food
Santosh Kumar of Food Processing Industries,
Department of Food Engineering and Government of India, Thanjavur, Tamil
Technology, Central Institute of Nadu, India
Technology Kokrajhar, Kokrajhar,
Assam, India Avik Mukherjee
Department of Food Engineering and
Charu Lata Mahanta Technology, Central Institute of
Department of Food Engineering and Technology Kokrajhar, Kokrajhar,
Technology, School of Engineering, Assam, India
Tezpur University, Napaam,
Assam, India Kannan Pakshirajan
Department of Biosciences and
Rajib Majumder Bioengineering, Indian Institute of
School of Life Science and Biotechnology, Technology Guwahati, Guwahati,
Adamas University, Barasat, West Bengal, Assam, India
India
N. Sai Prasanna
Gulshan Kumar Malik Agricultural & Food Engineering
Agricultural & Food Engineering Department, Indian Institute of
Department, Indian Institute of Technology Kharagpur,
Technology Kharagpur, Kharagpur, India Kharagpur, India
N. Arul Manikandan Yashaswini Premjit

Department of Chemical Engineering, Agricultural & Food Engineering
Indian Institute of Technology Guwahati, Department, Indian Institute of
Guwahati, Assam, India Technology Kharagpur, Kharagpur, India
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List of Contributors xvii
G. Pugazhenthi of Food Processing Industries,

Department of Chemical Engineering, Government of India, Thanjavur, Tamil
Indian Institute of Technology Guwahati, Nadu, India
Guwahati, Assam, India
C. Shashikumar
Manashi Das Purkayastha Centre for Rural Technology, Indian
Food Technology Programme, Department Institute of Technology Guwahati,
of Horticulture, Assam Agricultural Guwahati, Assam, India
University, Jorhat, Assam, India
Namrata Singh
K. Radha Krishnan Department of Food Engineering and
Department of Food Engineering and Technology, Central Institute of
Technology, Central Institute of Technology Kokrajhar, Kokrajhar,
Technology Kokrajhar, Kokrajhar, Assam, India
Assam, India
Siddhartha Singha
Ruchi Rani Centre for Rural Technology, Indian
Department of Food Engineering and Institute of Technology Guwahati,
Technology, School of Engineering, Guwahati, Assam, India
Tezpur University, Napaam,
Assam, India K. Sudharsan
Centre for Food Technology, Alagappa
Abhishek Roy College of Technology, Anna University,
Advance Energy & Materials Systems Chennai, India; Department of
Laboratory (AEMSL), Department of Microbiology, SRM Arts and Science
Chemical Engineering, Indian Institute of College, Kattankulathur, Chengalpattu
Technology Guwahati, District, Tamil Nadu, India
Assam, India
M. Sukumar
Priyadarshini S. R. Centre for Food Technology, Alagappa
Computational Modeling and Nanoscale College of Technology, Anna University,
Processing Unit, Indian Institute of Food Chennai, India
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xix
Preface
The idea of compiling a book on “Biopolymer-Based Food Packaging: Innovations and

Technology Applications” took seed in early 2019. It stemmed from the awareness and
growing interest among consumers and readers working at the interface of food, health,
and the environment. From the perspective of growing food needs of an ever-increasing
population, mostly in developing countries like India, the urge to develop such a book
project in this emerging area was perhaps more compelling for the food manufacturing
business. As the world is diligently focusing on developing sustainable alternatives to
petroleum-based products, including synthetic plastics-based food packaging, biopoly-
mers are gaining increasing attention as sustainable environmentally friendly alterna-
tives. This book is a complete, systematic, sequential account of the contemporary
development in the area of application of biopolymers as emerging alternatives in food
packaging applications. It aims to be a unique resource for academic researchers, profes-
sionals in food packaging and other related industries, research scholars, graduate stu-
dents, entrepreneurs, and people related to the area of food preservation and shelf-life,
environmental safety, and human health. Also, the book introduces the functionalities
and shortcomings of biopolymer-based food packaging materials, their characterization,
and benefits in preservation and/or packaging of food products.
This book comprises fourteen chapters, covering, in their purview, different polysac-
charide, protein, and microbial polymer-based food packaging films and coatings,
including biopolymer-based blends and nanocomposites. The first few chapters introduce
biopolymers, their blends and nanocomposites, and their chemistry, as well as providing
a general introduction to food packaging applications. Chapters 4–9 describe extensively
various biopolymers and their potential applications, including their importance as active
and intelligent food packaging systems. Chapters 10 and 11 focus on incorporation of
nanomaterials as fillers to improve the physicochemical, mechanical, thermal, barrier,
optical, and antimicrobial properties of food packaging nanocomposites. Chapters 12 and
13 detail the use of plant-based bioactive compounds, including essential oils and essential
oil-derived compounds in active biopolymer-based edible food packaging. The last chapter
of the book, Chapter 14, provides a comprehensive overview of biopolymer-based edible
food packagings and their effectiveness in shelf-life extension of perishable food items.
fpref.indd 19 21-03-2022 08:41:40

xx Preface
It has been a great pleasure and a privilege to collaborate with the contributing authors,
representing almost a dozen academic institutes/universities of international repute in
India and abroad. The success of this project depends on potential readers across the
entire spectra of food and associated areas in academia, industries, businesses, and
government bodies. The readers’ enthusiastic acceptance, appreciation, comments, and
critiques will inspire us to venture into more such collaborative efforts in future. We are
grateful for the support, cooperation, and understanding of our peers, friends, and fam-
ilies for rendering this daunting task possible. Hopefully through this small effort from
our part, and through the efforts of the contributing authors, we will be able to contribute
to accelerate further development in sustainable food packaging applications to meet the
growing demand for food worldwide.
Santosh Kumar
Avik Mukherjee
Joydeep Dutta
fpref.indd 20 21-03-2022 08:41:40

1
An Overview of Natural Biopolymers in Food Packaging

Santosh Kumar 1,*, Indra Bhusan Basumatary 1, Avik Mukherjee1,*, and
Joydeep Dutta2,*
1
Department of Food Engineering and Technology, Central Institute of Technology Kokrajhar, Kokrajhar 783370, Assam,
India
2
Functional Materials, Department of Applied Physics, SCI School, KTH Royal Institute of Technology, Hannes Alfvéns väg
12, 114 19, Stockholm, Sweden
*
Corresponding authors: Santosh Kumar, s.kumar@cit.ac.in; Avik Mukherjee, ak.mukherjee@cit.ac.in; Joydeep Dutta,
joydeep@kth.se
CHAPTER MENU
1.1 Introduction 1
1.3.3 Lipid-Based Biopolymers 13
1.3.4 Biopolymers Synthesized from Bio-derived Monomers 14
1.5 Properties and Applications 16
1.1 Introduction
The prefix “bio” in the term “biopolymer” signifies that these polymers are of biological
origin, i.e. inherently produced in living organisms. Biopolymers, bio-based polymers,
biodegradable polymers, and bioplastics are used synonymously in specific contexts, but
each term has a different meaning. Bio-based polymers are materials produced from
natural resources such as plants, animals, and microorganisms that can be biodegradable
(e.g. starch, polylactic acid [PLA]) or non-degradable (e.g. biopolyethylene) [1].
Biodegradable polymers are materials that completely degrade when exposed to soil, air,
water, and microorganisms over a specific time period. Biodegradable polymers may be
natural (e.g. starch, cellulose, proteins, lipids) or synthetically produced (e.g. polycapro-
lactone and polybutylene succinate). A bioplastic is a plastic polymer manufactured from
a natural or renewable source, and it is biodegradable [2]. Biopolymers are primarily com-
posed of repeating units of monomers made of carbon (C), hydrogen (H), oxygen (O), and
nitrogen (N) and are found in living organisms such as plants, animals, and microorgan-
isms. Based on this definition, biopolymers include bio-based polymers and natural poly-
mers, including biodegradable polymers such as polysaccharides, proteins, lipids, and
Biopolymer-Based Food Packaging: Innovations and Technology Applications, First Edition. Edited by
Santosh Kumar, Avik Mukherjee, and Joydeep Dutta.
© 2022 John Wiley & Sons Ltd. Published 2022 by John Wiley & Sons Ltd.
c01.indd 1 21-03-2022 08:47:57

2 1 An Overview of Natural Biopolymers in Food Packaging
polynucleotides (DNA and RNA). However, biopolymers such as DNA and RNA have
complex molecular structure, in which monosaccharide, protein/amino acids, and
functional groups such as phosphate groups are joined together by complex intramolec-
ular interactions like hydrogen bonding, disulfide bridges, and hydrophobic interactions
to create three-dimensional (3D) structure and termed as bio-based heteropolymers or
biomacromolecules [3].
The physicochemical properties of biopolymers such as stiffness, elasticity, conduc-
tivity of electricity and heat, resistance to corrosion, appearance such as transparency,
and color depend on the type(s) of monomer, degree of polymerization, and type(s) of
intramolecular bonds. Compared to synthetic polymers obtained from fossil fuels, bio-
polymers offer the obvious advantage of eco-friendly degradation, which leads to effective
waste management and a healthy environment. The biopolymers are excellent candidates
for various applications such as food, pharmaceuticals, and cosmetics and in several
industries including packaging, agriculture, textiles, and water treatment due to their bio-
compatibility, non-toxicity, and biodegradability [4–6]. However, impact strength, tensile
strength, permeability, and thermal stability of biopolymers are relatively inferior com-
pared to synthetic (i.e. petroleum-based) polymers. Reinforcement of fillers or additives in
biopolymers significantly improves the mechanical properties, such as tensile and impact
strengths of the resulting composites, and thermal and optical properties [7–9]. Cellulose,
chitosan, starch, polyvinyl alcohol (PVA), polylactic acid (PLA), polyglycolic acid (PGA),
polycaprolactone (PCL), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), etc.
have gained substantial attention as biopolymers in food packaging applications [5, 6, 8].
Synthetic polymers like polyethylene (PE), polypropylene (PP), nylon, polyester (PS),
polytetrafluoro-ethylene (PTFE), and epoxy are commonly known as plastic and are
derived from petroleum hydrocarbons [10]. These materials are still an integral part of
our human life, and they have found their way into our daily routine. The demand for
petroleum-based polymers in our commercial world is increasing because of their versa-
tility, high mechanical strength, flexibility, resistivity, transparency, chemical inertness,
low mass, and low cost [11]. Moreover, these plastic do not readily react with the product
with which they are in contact, and they have excellent resistance to water, gases, temper-
ature, and chemical degradation. Synthetic plastics are made from petroleum hydro-
carbon, which is a non-renewable resource, and they emit large quantities of greenhouse
gases during production [11]. In addition, burning of plastics can emit toxic chemicals
such as dioxins [12]. Plastics that are used for short time periods and single-use plastics
should not be made of synthetic plastics due to their low density and slow decomposition.
As reported by various environment protection agencies, plastics alone account for more
than 25% (by volume) of the total municipal solid waste generated. Synthetic plastics-
based food packages/containers and utensils take many years, sometimes even more than
a hundred years, to degrade in the environment (Figure 1.1a), whereas natural
biopolymer-based food packages/containers and utensils decompose within a few weeks
to a few months (Figure 1.1b). Thus, synthetic plastic-based food packages and containers
become a significant problem for the environment and living beings. They impact the
quality of air, water, and soil and indirectly plant, animal, and human lives. Accumulation
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1.1 Introduction 3
Figure 1.1 Lifecycle of (a) synthetic plastics-based food packages/containers and (b)
biopolymer-based food packages/containers and utensils.
of large amounts of plastic waste in the marine ecosystem causes choking and entangle-
ment of marine flora and fauna [13].
As an alternative to petroleum-based plastics, biopolymers have significant potential
to be used in food packaging applications [5, 6]. These would help to reduce the impact
of synthetic plastics waste because of rapid degradation of biopolymer-based plastics in
the environment. They are decomposed by the enzymatic activity of naturally occurring
microorganisms in the environment such as bacteria, fungi, and algae and by chemical
processes such as chemical hydrolysis. During biodegradation, biopolymer-based food
packages and containers are converted into simple organic molecules, carbon monoxide
(CO), methylene (CH), water, biomass, and other natural substances. Biopolymers such
as chitosan and PLA are naturally recycled by biological processes (Figure 1.2). Thus,
biopolymers are characterized by easy disposal, recycling, biodegradation, and com-
posting and by their eco-friendly nature. In addition, some of them have advantageous
features such as inherent antimicrobial and antioxidant activities, because of the
presence of different functional groups in their polymeric chains. Despite these advan-
tages, biopolymers lack adequate mechanical and barrier properties, which makes them
unsuitable for use as food packaging [14]. Many researchers have focused on this and
propose the use of crosslinkers such as nanofillers and blending of two or more biopoly-
mers to address these challenges. This chapter provides a comprehensive overview of
various biopolymers and their properties and applications in food packaging and
preservation.
c01.indd 3 21-03-2022 08:48:01

Figure 1.2 Lifecycle of chitosan (left) and PLA (right).
1.2 History and Background
“Biopolymers” can be defined as polymers that are naturally produced or are obtained
from living organisms. The repeating monomer units of biopolymers are saccharides,
nucleic acids, or amino acids, and sometimes various additional chemical side chains and
functional groups. Historically, biopolymers have been commonly used as food, for mak-
ing clothes and houses, and as fuel for cooking. They are biodegradable in nature and are
obtained from natural renewable resources, which has inspired a renaissance of research
interest. Biopolymer-based composite materials are sustainable and have the potential to
replace the fossil fuel-based synthetic plastics that have been used on a large scale since
the industrial revolution. Fossil fuels are limited resources, and due to non-biodegradability
they cause significant environmental problems. Therefore, biopolymers can be used as
sustainable and environmentally friendly alternatives to synthetic plastic for food pack-
aging applications.
Silk is an ancient protein polymer, with an amino acid composition that depends on the
producing species. Silks are produced by spiders, silkworms, and several lepidoptera
larvae. Bombyx mori, a silkworm, is the most popular species for silk production. This silk
is characterized by fibroin fibers held together by a glue-like protein called sericin, which
is absent in spider silk. Silk fibers have high toughness, good strength, and high elasticity.
These properties, including resistance to failure under compression, make silk an attrac-
tive material for food packaging applications. In a study, silk fibroin was used to develop
a coating formulation (Figure 1.3a) for postharvest shelf-life extension of fruits such as
strawberry (Figure 1.3b) and banana (Figure 1.3c) [15]. Researchers reported reduction in
oxygen diffusion through silk fibroin thin films/coatings due to increased beta-sheet
content. The fruits treated with water-based silk fibroin edible coatings had enhanced
postharvest shelf-life at ambient conditions by reducing the rate of cell respiration and
transpiration.
c01.indd 4 21-03-2022 08:48:05

- 23% beta-sheets
x1 D1
Dip coating Water 1 hour 36 beta-sheets
x2 D2 48% beta-sheets
x4 D4 annealing 6 hours
12 hours 58% beta-sheets
i ii iii iv v
a
No coating 23% beta-sheets 58% beta-sheets
i ii iii
As received Day 9
Silk fibroin Silk fibroin

No coating No coating
coating coating
Figure 1.3 (a) Dip-coating application of silk fibroin coating formulation on freshly picked
strawberries. (b) Images of coated strawberries: (i) no coating (freshly picked), (ii) coated with silk
fibroin edible coating (23% beta-sheet, i.e. no water annealing applied), and (iii) coated with silk
fibroin (58% beta-sheet, i.e. exposed to water annealing post-processing). (c) Time lapse
photography of silk fibroin coated banana stored at 22°C and 38% relative humidity (RH),
indicating that silk fibroin coating decreased the ripening rate [15]. (Source: (a) [15], Figure 01A, p
04, CC by 4.0 licence/with permission from Springer Nature. (b) [15], Figure 04, p 08 CC by 4.0 licence/
with permission from Springer Nature.)
In the nineteenth century, another natural polymer, cellulose, started impacting

everyday life. Cellulose was also known as Celluloid, Parkesine, Xylonite, and Ivoride,
and it was invented by Christian Schönbein (a Swiss professor), Alexander Parkes (an
English inventor), and John Wesley Hyatt (an American entrepreneur). In 1847, Parkes
started working on cellulose, and he developed the formulas and processes to manufac-
ture cellulose nitrate after spending the next 15 years in the laboratory.
Milk casein has been used as a dietary source of protein since the domestication of live-
stock. The technologies for making plastics from casein were first patented in 1885 and
1886, in Germany and the USA, respectively [16]. However, the patented material easily
biodegraded, and no useful products could be made due to lack of hardening agent in the
patented protocol. Clearly, easy biodegradation was a disadvantage or non-desirable a
century ago, but today biodegradability is one of the most desirable properties for sustain-
able packaging.
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1.3 Classification
Biopolymers can be grouped into two broad categories depending on the process of
obtaining them: polymers derived from biomass and polymers synthesized from mono-
mers (obtained from biomass) (Figure 1.4). Biomass-derived polymers include polysac-
charide, protein, lipid, peptide, polyhydroxyalkanoate (PHA), and gum that are directly
obtained from plants, animals, and microorganisms either by fermentation or by chemical
method. PHA, cellulose, xanthan, silk, etc. are obtained from carbohydrates – an example
of the fermentation approach – whereas chitosan obtained from shrimp and crab shells is
an example of a chemical extraction process [17]. The other group of polymers such as
PLA, PBS, polyisoprene, polyglycolide, polybutylene adipate-co-terephthalate (PBAT),
poly-γ-glutamic acid, poly-ε-L-lysine, and polyaspartic acid, are synthesized by chemical
polymerization or by condensation of monomer substrates that are obtained from renew-
able bio-based material or biomass [17].
1.3.1 Polysaccharide-Based Biopolymers

Polysaccharides are abundantly available and the most exploited family of macromole-
cules found in living organisms. Polysaccharides are high molecular weight polymers or
copolymers of repeating monosaccharide units joined together by glycosidic bonds. In
living systems, polysaccharides can be found as a structural material (e.g. cellulose),
energy storage material (starch in plants and glycogen in animals), and nutritionally
important components (glucose, fructose, etc.). Polysaccharides can be extracted or syn-
thesized from abundantly available natural resources such as plants (cellulose, starch,
pectin, and agar), microorganisms (bacterial cellulose, dextran, xanthan, gellan gum, pul-
lulan, and curdlan), animals (chitin/chitosan, chondroitin sulfate, glycosaminoglycans,
heparin, and hyaluronan), and algae (alginate, agarose, carrageenan, fucoidan, and ulvan)
[9, 18–20].
Among plant-based biopolymers, cellulose is the most abundant, and it is also obtained
from some microorganisms. Cellulose has been extensively studied for its application in
food packaging and preservation. It is a high-molecular-weight, semicrystalline homopol-
ymer of β-D-glucopyranose units linked by β-1,4 linkage, in which the repeating unit is
cellobiose, a dimer of glucose [21]. Cellulose is mainly obtained from plant resources such
as cotton, wood, cereal straw, and sugarcane bagasse. It is highly crystalline, which means
it is insoluble in most of the solvents. To make cellulose processable, it is modified to its
derivatives, such as cellophane, rayon, cellulose acetate, and cellulose ether. Sugarcane
bagasse fiber is biodegradable and degrades in landfill within 45 days. It is used to manu-
facture food packaging materials and disposable utensils such as films, plates, cups,
compartment boxes, and other containers (Figure 1.5) [21]. Food industry wastes such as
cocoa pod husk (waste from the chocolate industry) and sugarcane bagasse (waste from
the sugar industry) were used to develop cellulose-based food packaging films with differ-
ent ratios of fiber added: 100:0 (100% cellulose), 75:25 (cellulose:fiber), 50:50
(cellulose:fiber), 25:75 (cellulose:fiber), and 0:100 (100% fiber) [22]. These researchers
reported that the film having a combination of 75% cellulose and 25% fiber showed the
c01.indd 6 21-03-2022 08:48:06

Figure 1.4 Classification of biopolymers.
lowest water absorption percentage and water vapor permeability, and thus it was most
suitable for food packaging applications.
Chitin is the most abundantly available natural biopolymer after cellulose and pri-
marily extracted from the exoskeleton of crustaceans such as shrimps, lobsters, and crabs,
insects, and some fungi [23]. Chitin is a heteropolymer consisting of β-1,4-linked 2-acet-
amide-2-deoxy-D-glucopyranose (N-acetyl-D-glucosamine) and 2-amino-2-deoxy-D-
glucopyranose [5, 7]. Chitin and chitosan and their derivatives have the added advantage
c01.indd 7 21-03-2022 08:48:10

Figure 1.5 Sugarcane bagasse fiber-based food containers and utensils.
of being natural antioxidants with antimicrobial activities, making them functionally

attractive choices for fabrication of films and coatings for food packaging [8, 24]. Chitosan
is a soluble form of chitin that is obtained by partial deacetylation of chitin. Chitosan has
been used in various industrial applications including food preservation and packaging.
Chitosan has been recognized and approved as a generally recognized as safe (GRAS)
material by the US Food and Drug Administration (FDA), and the European Union (EU)
Commission [25]. Chemical and enzymatic modifications of chitosan are performed to
enhance its physicochemical and functional properties [25]. These functionalized chito-
sans with improved properties have wider applications in fabrication of films and coat-
ings for food packaging [5]. Costa et al. fabricated chitosan and cellulose nanocrystal
(CNC)-based film by solvent casting and used this as active packaging pads to prolong the
shelf-life of chicken meat. They reported that the incorporation of CNC improved thermal
stability, mechanical strength, and the gas barrier. In addition, these films showed bacte-
ricidal and fungicidal activities against Pseudomonas, Enterobacteriaceae, and Candida
albicans [26]. Chitosan-based nanocomposite films containing zinc oxide (ZnO) NPs and
gallic acid were evaluated for active food packaging application. The developed chitosan
composite films showed improved mechanical properties, oxygen and water vapor per-
meability (WVP), and ultraviolet-visible (UV-vis) light transmittance [23]. Similarly,
green synthesized ZnO NPs and silver (Ag) NPs were used to develop a chitosan-gelatin-
blended nanocomposite film for postharvest shelf-life extension of grapes, which showed
good antimicrobial activity against both Gram-negative (Escherichia coli) and Gram-
positive (Staphylococcus aureus) bacteria. Additionally, ZnO NP or Ag NP incorporation
led to improved thermal stability, elongation-at-break (EAB), and compactness of the
nanocomposite films [7, 8].
c01.indd 8 21-03-2022 08:48:12

Starch is made of amylose, a linear polymer and amylopectin having a highly branched
structure. Both amylose and amylopectin consist of large numbers of D-glucose units
linked by α-1,4 and α-1,6 glycosidic bonds, respectively. Starch is mainly obtained from
rice, wheat, maize, potato, and cassava, and it has various applications in the food industry
due to its abundant availability, biodegradability, and edible nature. Starch-based bio-
composites are widely used in the fabrication of food packaging films and edible coatings.
Starch does not have inherent antioxidant and antimicrobial properties, but it is often
used as a carrier for antimicrobial and antioxidant agents. Starch-based packaging films
lack mechanical strength, which makes them brittle. To overcome this shortcoming,
starch is blended with other biopolymers and nanomaterials, chemically modified, or
plasticized, or subjected to a combination of these treatments. Glycerol, polyethers, and
urea are commonly used plasticizers in starch-based films and coatings. Starch-based
films reinforced with cellulose fibers with added citric acid and phenolic extract of sun-
flower hull were developed to improve film integrity and antioxidant properties, respec-
tively. The incorporation of citric acid improved crosslinking and mechanical strength,
whereas addition of phenolic extract of sunflower hull enhanced antioxidant properties
[27]. Jha developed corn starch, chitosan, and nanoclay (sodium montmorillonite
[Na-MMT])-based bionanocomposite films containing antimicrobial agents (potassium
sorbate [KS]/grapefruit seed extract [GSE]) and reported that the composite films have
higher crystallinity, tensile strength, thermal stability, and water vapor barrier properties.
Compared to synthetic plastic film, bread samples wrapped in the developed composite
film showed high antifungal activity against Aspergillus niger and maintained the quality
of the bread for longer duration when stored at 25°C and 59% RH [28].
Algal polysaccharides, mainly alginate and carrageenan, are gaining popularity in food
packaging application due to their biodegradability, low cost, biocompatibility, non-
toxicity, and other inherent functional properties such as antimicrobial and antioxidant
activities. Alginate is mainly found as calcium, magnesium, and sodium salts of alginic
acid in brown algae (between 30 and 60%, on the basis of dry weight). Alginate is a binary
copolymer of β-D-mannuronic acid monomer and α-L-guluronic acid monomer which
are linked through 1,4-glycoside linkage [29]. Carrageenan is a linear heteropolysaccha-
ride composed of carrabioses and carrabiitols and is obtained from red seaweeds such as
Eucheuma spp., Kappaphycus spp., Chondrus crispus, and Gigartina stellate [30, 31]. It
exists in three forms: κ-, ι-, and λ-carrageenan, based on different structures of the disac-
charide (Figure 1.6). κ-carrageenan is the most commonly used in the food packaging
industry to fabricate edible films and coatings. Sedayu et al. fabricated semirefined carra-
geenan films plasticized with glycerol by the solution casting method [32]. The plasticizer
improved the tensile strength, thermal stability, optical properties, and water vapor
barrier properties of the carrageenan film [32]. Recently, two bioactive compounds, shiko-
nin (extracted from gromwell roots) and propolis (extracted from beeswax), were incorpo-
rated into gelatin- and carrageenan-based food packaging films [33]. Shikonin changes
color from violet to blue with changes in pH (within the pH range of 2–12), making it an
intelligent/smart primary packaging film indicating freshness of packaged fluid milk to
consumers. Propolis enhanced functionalities such as antibacterial, antioxidant, anti-
fungal, and antiviral activities of the composite biopolymer packaging film [33]. Another
study reported that κ-carrageenan bionanocomposite films added with carbon
c01.indd 9 21-03-2022 08:48:12

H2C
OSO–3
CH2OH O
O
n ∗
O
O
O
∗ OH
OH
K–carrageenan
H2C
OSO–3
CH2OH O
O
O n ∗
O
O
∗ OH
OSO–3
ι–carrageenan
O
n ∗
OH
CH2OH –
O CH2OSO3 OSO–
3
O
∗ OSO3– HO
λ–carrageenan
Figure 1.6 κ-, ι-, and λ-carrageenan.
nanocrystals had improved mechanical, barrier (against moisture and UV light), and
thermal stability compared to the pristine κ-carrageenan control film [34].
Microbial biopolymers primarily include exopolysaccharides (EPSs) such as gellan
gum, curdlan, pullulan, dextran, xanthan, and kefiran, and are used in the fabrication of
films and coatings for food packaging and preservation applications [35]. Gellan gum is
an anionic water-soluble EPS, which is industrially produced by the bacterium
Sphingomonas elodea. It is commonly used as a food additive as a gelling, thickening, and
stabilizing agent mainly for dairy products and confectioneries. In some studies, gellan
gum has also been used for fabrication of films and coatings due to its effective barrier
properties [35, 36]. Curdlan is a linear water-insoluble EPS produced by bacteria such as
Alcaligenes faecalis and Agrobacterium spp. In the food packaging industry, it has attracted
much attention as a biopolymer due to its excellent film-forming ability, non-toxicity, and
c01.indd 10 21-03-2022 08:48:12

biodegradability [37]. Due to its water insolubility and heat-gelling properties, curdlan
has the ability to enhance the thermal stability and water barrier properties of food pack-
aging films and coatings. Pullulan is a non-ionic EPS extracted from Aureobasidium pul-
lulans, a yeast-like fungus [38, 39]. It is a biodegradable, flexible, transparent, heat-sealable
polymer having good barrier properties as well as antifungal and antioxidant activities. It
has been blended with other biopolymers like chitosan, starch, alginate, and pectin to
improve the mechanical, thermal, and barrier properties of the blended films [38, 39]. It
is mainly used for the preparation of coating formulations for extending postharvest life
of fresh fruits and vegetables, as it results in lower oxygen (O2) and higher carbon dioxide
(CO2) concentrations in the surrounding atmosphere of the coated fruits and vegetables.
Xanthan gum is the first microbial polysaccharide produced by culture fermentation
using Xanthomonas campestris. Like pullulan, xanthan is used in blends in other biopoly-
mers for food packaging applications because of its ability to control viscosity [40].
However, the high production cost of xanthan is a major challenge for its large-scale
commercial application in the food industry.
1.3.2 Protein-Based Biopolymers

Protein is a heterogeneous polymer made of amino acids joined together by an amide
linkage. The number of amino acid residues in the polypeptide chain and their position
along the chain determine the protein’s physical and chemical properties. Proteins are
relatively abundant and have good film-forming ability, and many of them (with a
relatively short chain, e.g. 2–20 amino acids) are bioactive peptides having antioxidant
and antimicrobial properties [41]. Thus, many plant- and animal-derived proteins have
increasingly become popular choices for fabrication of films and coatings, including
edible films and coatings, for food packaging applications [41]. Among plant proteins,
gluten, zein, and soy protein, and among animal proteins, gelatin, casein, and whey pro-
tein are commonly used as biopolymers for food packaging applications [42–46].
Gluten is the primary storage protein in wheat, which can be classified into glutenin
(40–50% of gluten) and gliadin (50–60% of gluten) based on the difference in solubility in
aqueous alcohols, the former being soluble and the latter insoluble [41]. Wheat gluten is
one of the most abundant plant proteins, and the biopolymer is an attractive choice for
fabricating food packaging films and coatings due to its low cost, good tensile strength,
viscoelasticity, and excellent gas barrier properties [47, 48]. Disulfide bonds, hydrogen
bonds, and hydrophobic interactions primarily contribute to the mechanical strength of
gluten-based biopolymer film. Hydrophobic, non-polar fillers like mineral oil improve the
barrier properties of gluten films against moisture, whereas heat treatment of the casting
film leads to covalent crosslinking within gliadin polypeptide chains, resulting in
improved mechanical strength of the film [47]. Gluten-based edible films incorporated
with pomegranate peel and curry leaf extracts were fabricated and applied on cherry
tomatoes and mangoes for extension of their postharvest shelf-life [49]. The fabricated
films showed good structural stability and antimicrobial activity and also extended the
shelf-life of wrapped fruits. Sartori et al. developed blend films by blending pectin and
gluten and reported improved tensile strength and water vapor and UV-light barrier prop-
erties [48].
c01.indd 11 21-03-2022 08:48:12

Zein protein (ZP) is one of the major by-products of corn processing such as dry or wet
milling, and it constitutes about 45–50% of the total corn proteins. Due to an abundance
of hydrophobic amino acid residues in its structure, zein is insoluble in water and soluble
in organic solvents such as ethanol and acetone [21, 41]. Although zein forms biopolymer
films with good moisture barrier property, its films are brittle, and polyols or fatty acids
are common plasticizers used in the solvent (ethanol or ethanol solution)/wet process of
fabrication to improve the mechanical properties of the films. Due to its exceptional film-
forming property, zein, either neat or blended with other biopolymer(s), is one of the most
commonly used biopolymer proteins for fabrication of food packaging films and coatings
[43]. ZP films incorporated with core-shell NPs (TiO2 as core and silica as shell) were pre-
pared by the solution-casting method, and the film containing 1.5% w/w core-shell NPs
showed improved mechanical properties, increased hydrophobicity, and enhanced water
vapor barrier property [50]. Cui et al. prepared active bionanocomposite film from zein
impregnated with chitosan-encapsulated pomegranate peel extract for packaging/wrap-
ping of pork [51]. The bionanocomposite film had thermal stability and showed antimi-
crobial activity against Listeria monocytogenes inoculated in pork during refrigerated
storage. In addition, plasma-treated nanocomposite active film showed a slow release of
pomegranate peel extract into the pork sample due to encapsulation in chitosan and
ensured longer shelf-life of pork meat [51]. Similarly, a functional edible antioxidant film
was developed using curcumin-loaded sodium caseinate and zein, and the composite film
showed increased tensile strength (from 3.12 to 7.85 MPa) and water vapor barrier prop-
erty (from 0.87 to 3.56 × 10−10 g Pa–1 m–1 s–1) [43].
Other than casein, whey protein (WP) is also obtained from milk, and it is a by-product
of the milk processing industry. Many researchers have studied whey protein-based films
and coatings for food packaging and preservation applications. WP-based films showed
good oxygen barrier properties, but, like many other protein-based films, WP-based films
have relatively poor WVP [52]. To address these shortcomings, reinforcement of fillers
including nanofillers has been extensively used in WP-based films. Xylo-oligosaccharide
and galacto-oligosaccharide fillers were incorporated into WP films, resulting in lower
WVP (1.09–0.63 g mm h− 1 m−2 kPa−1, p < 0.05) and higher hydrophobicity (56.61–46.69°,
p < 0.05), as evidenced by contact angle measurement [53]. Alizadeh-Sani et al. reported
that cellulose nanofiber (CNF) incorporation in whey protein isolate bionanocomposite
film also reduced WVP [54]. In addition, CNFs (7.5%) and titanium dioxide (TiO2) (1%)
fillers significantly improved tensile strength and Young’s modulus (YM) of the whey
nanocomposite films. Whey protein concentrate (WPC) films added with a blend of three
essential oils (EOs) were developed, and the EOs improved the antioxidant property of the
composite films, which led to longer shelf-life of packaged salami [46].
Soybeans consist of about 38% protein that is composed of glycinin and conglycinin,
and they are obtained from soy flour, soy milk, or fractionated/concentrated forms such
as soy protein isolate (SPI)/soy protein concentrate (SPC). Soy protein not only has excel-
lent film-forming property but also has functionalities such as adhesiveness, cohesive-
ness, emulsifying ability, water and fat absorption, fiber formation, and texturizing
capacity [41]. Heating, extrusion, spinning, casting, and thermal compacting are common
processes used for fabrication of soy protein films. Addition of fillers such as sodium
dodecyl sulfate (SDS) and cysteine improves the moisture barrier properties and tensile
c01.indd 12 21-03-2022 08:48:12

strength of soy protein-based films, respectively. Besides chemical treatment, physical

treatment such as γ-irradiation and heat curing improves mechanical properties of the
films by enhancing crosslinks between amino acid side chains [55]. Yu et al. reported that
the addition of CNF improved tensile strength of soy protein-based nanocomposite pack-
aging films. Further, incorporation of pine needle extract in the composite film resulted
in enhanced light barrier property and antioxidant and antimicrobial activities [56]. SPI-
based films containing different concentrations of pinhão cooking water extract (0.5, 1,
and 2% w/w) were used as active packaging of linseed oil and showed enhanced oxidative
stability of the edible oils [57].
Gelatin is a natural water-soluble protein produced by the partial hydrolysis of collagen,
a fibrous protein mainly present in skins, bones, tendons, and connective tissues [7].
By-products of muscle food-processing industries such as fish, meat, and poultry indus-
tries are rich sources of gelatin. Gelatin can be categorized as type A, derived from acid
treatment of collagen, having an isoelectronic point at pH 8–9; and type B, obtained by an
alkali treatment, having an isoelectronic point at pH 4–5. Gelatin has a unique property of
being dissolved in aqueous solutions at ~ 40°C or at mouth temperature, and, upon
cooling, it forms a gel, which is a useful property for development of films and coatings.
Fish gelatin-based films containing different concentrations (0–60%) of palm wax had sig-
nificantly better tensile strength, lower WVP, and higher hydrophobicity [58]. Four
natural active components – green tea extract, grape seed extract, ginger extract, and
gingko leaf extract – were added to gelatin-based films as antioxidants, and the fabricated
active composite films showed improved antioxidant activity and barrier against UV light
and moisture [42]. Such composite gelatin films can be an ideal choice for active food
packaging and preservation. Ag NPs have been used as filler in gelatin-based nanocom-
posite films to improve their mechanical and antimicrobial properties [8, 20].
1.3.3 Lipid-Based Biopolymers

Lipids consist of a diverse array of functional groups, such as phospholipids, phospha-
tides, mono-, di-, and tri-glycerides, terpenes, cerebrosides, fatty alcohol, and fatty acids,
and are hydrophobic in nature. Unlike proteins and polysaccharides, the hydrophobicity
of lipids makes them attractive alternatives to fabricate coatings with better moisture
barrier properties for food packaging applications. Lipid(s) and/or lipid derivative(s) are
also incorporated in composite films and coatings to reduce their moisture permeability
[59]. Moisture barrier efficiency of a film or coating blended with or fabricated using
lipids/lipid derivatives depends on the nature of the lipid(s), chain length of the fatty
acids, structural arrangement, physical state (solid or liquid), and their interaction(s) with
other film components such as proteins and polysaccharides. Blending lipid(s) or lipid
derivative(s) in a food packaging film deteriorates the mechanical properties of the film
due to their lack of interaction(s) with protein and/or polysaccharide component(s) of the
film. It has been reported that more than 80% wax concentration in a composite bio-
polymer film led to discontinuity and cracks in the film matrices upon drying [59].
Carnauba wax, beeswax, shellac wax, and EOs are common lipid and lipid derivatives
used to fabricate food packaging films and coatings [60]. Among these, EOs possess func-
tionalities such as natural antioxidant and antimicrobial activities [61].
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Carnauba wax is a natural plant-based wax obtained from the leaf and leaf bud of the
Brazilian palm tree (Copernica cerifera). The plant secretes wax to protect the leaves from
damage due to hot, dry weather. Carnauba wax, also known as “Queen of Wax,” has a
higher melting point (78°C) than other waxes, and it is usually available in the form of
hard yellow-brown flakes. It is recognized as GRAS material for food application.
Carnauba wax mainly consists of aliphatic esters (40%), diesters of 4-hydroxycinnamic
acid (21%), ω-hydroxycarboxylic acids (13%), and fatty acid alcohols (12%) [62]. High
content of diesters and methoxycinnamic acid is the distinctive feature of carnauba wax.
Cinnamic acid is an antioxidant, which gives additional functionalities to carnauba wax-
based coatings. It is commercially available in several grades or labeled as T1, T2, and T4,
depending upon the purity level. It is commonly used for coating fruits and vegetables to
prevent postharvest weight loss due to moisture evaporation and to maintain a glossy
appearance. In combination with nisin it has been used as an antimicrobial and moisture
barrier coating that can extend the postharvest shelf-life of fruits and vegetables [63].
Recently, its effectiveness in reducing weight loss, respiration rate, ethylene production,
and flesh softening in jujube (plum) during postharvest storage at 20°C was reported [64].
Singh et al. used carnauba wax combined with shellac wax for postharvest coating of brin-
jal and reported significant improvement in postharvest shelf-life and quality retention
during storage at 20°C [65]. The Indian Council of Agricultural Research (ICAR) pub-
lished a report on the effectiveness of 10% carnauba wax coating on quality retention and
shelf-life extension of Nagpur mandarins during ambient and refrigerated (6°C) storage.
Beeswax is a natural, abundantly available wax produced by honey bees [6]. It is a tra-
ditional material for fabrication of food packaging films or coatings that have good mois-
ture vapor barrier, gas barrier, and grease-resistant properties [66]. Numerous researchers
have reported on fabrication of composite films of corn starch (2%) [66], cinnamon EO
[67], chitosan (2%) [68], gelatin [69], and carrageenan [70] with beeswax for application
in postharvest fruit coatings for their packaging and preservation. Oliveira et al. reported
that coatings based on corn starch (3%), cassava starch (2%), and gelatin (5%) with added
beeswax (10%) minimized weight loss and improved consumers’ acceptability of coated
guava [66]. Spray-coating of strawberries with the blend of 2% w/v modified tapioca starch
with 0.5 or 1.0% w/v beeswax microparticles resulted in reduced moisture loss and gas
transmission during refrigerated storage of the fruit [68].
1.3.4 Biopolymers Synthesized from Bio-derived Monomers

This category of biopolymers is synthesized from monomers, which are obtained from
renewable biomass [6, 71]. These biopolymers include PLA, PBS, polyisoprene, polygly-
colide, polybutylene adipate-co-terephthalate), poly-γ-glutamic acid, and poly-ε-L-lysine.
These biopolymers are biodegradable, belong to the polyester family, and are produced by
poly-condensation or ring-opening polymerization of bio-derived monomers. A low
molecular weight PLA was discovered in 1932 by Carothers by heating lactic acid under
vacuum [72]. However, a high molecular weight PLA was necessary for their commercial
application, and this was achieved through ring-opening polymerization of the lactide,
which was obtained from lactic acid. PLA is a linear aliphatic thermoplastic polyester
derived from 100% natural plant-based resources such as corn, potato, sugarcane, and
c01.indd 14 21-03-2022 08:48:12

beet, from which lactic acid is produced by fermentation. Among the family of biodegrad-
able polyesters, PLA has been receiving much attention for food packaging applications
due to its biodegradability, non-toxicity, and interesting physicochemical properties, such
as transparency and high mechanical strength, which mainly depend upon the stereo-
chemistry and molecular weight of PLA [73]. In the beginning, applications of PLA were
limited due to its production costs; however, production costs have fallen due to the high
volume of production and development of modern methodologies. PLA also has some
drawbacks, such as high brittleness, poor crystallinity, and low gas barrier properties.
High molecular weight, resistance to water/moisture, good processability to form films,
containers, coatings, etc., and biodegradability make PLA and its composites attractive
alternatives as food packaging materials. PLA-cyclodextrin-thymol and PLA-cyclodextrin-
carvacrol composite films showed reduced YM and improved EAB compared to the pris-
tine PLA control film [74]. In this study, encapsulated natural monoterpene antimicrobial
EO components into the PLA composite films resulted in complete inhibition of in-vitro
growth of Alternaria alternata, a major foodborne fungal pathogen. Like PLA-cyclodextrin,
PLA-limonene composite films showed plasticization effect due to addition of the natural
filler [75]. Rapa et al. also reported improved mechanical, thermal, and optical properties
of PLA-chitosan biocomposite films compared to pristine PLA films [76]. The added chi-
tosan also improved the antibacterial activities of the composite film against common
foodborne pathogens like S. aureus and E. coli. PLA-PHB composite film with added cat-
echin as natural antioxidant for packaging of fat-rich food products [77] and PLA-ZnO-Ag
NP bionanocomposite with improved mechanical, thermal, and barrier properties against
UV light, water vapor, gases and (O2, CO2) and with enhanced antibacterial activities for
active food packaging applications [78] were also reported.
1.4 Advantages and Disadvantages
Biopolymers have several advantages compared to synthetic plastics, some of which are
listed as follows:
1) Biopolymers are carbon neutral and sustainable. They are biodegradable, recyclable,
and obtained from living organisms; thus they can be used for sustainable food pack-
aging applications.
2) Biopolymers reduce greenhouse gas emissions. They naturally break down after disposal
in landfill/compost, emitting the same amount of gas back into the environment as
that used to create them in the first place. Switching to biopolymer-based packaging
will certainly reduce the greenhouse gas emissions caused by the industry, which will
compensate for the initial financial costs required to make the transition from synthetic
to biopolymer plastic packaging.
3) Biopolymers are biodegradable and compostable. Soil microorganisms easily break
down biopolymers by consuming/digesting their constituents, and the metabolic prod-
ucts again are utilized by plants completing their life-cycle.
4) Biopolymers have less environmental impact. They reduce dependency on non-
renewable fossil-fuel-based synthetic plastic that releases harmful gases and chemicals
c01.indd 15 21-03-2022 08:48:13

upon decomposition; thus biopolymer-based plastics greatly reduce the harmful effect
on the environment.
5) Biopolymers require less energy for manufacturing. Although cost of production of bio-
polymer-based packaging is slightly higher, energy consumption is less to produce bio-
polymers. This energy saving reduces the long-term cost of using biopolymers,
especially if the costs of clean-up of plastic pollution are considered in the
calculation.
6) Biopolymer-based plastics offer new business opportunities. In view of the above-
mentioned advantages, including biopolymers’ potential to replace conventional
synthetic plastics, and also restricted use of synthetic plastic products such as single-
use plastics by many developed countries, new business opportunities have been cre-
ated for developing biopolymer-based packages, not only for higher profit but also for
improved consumer goodwill.
However, biopolymer-based packaging suffers from a few disadvantages. The primary
disadvantage is their higher production cost. The current technology used to manufacture
bioplastics costs up to 50% more than that of their conventional counterpart. However, as
consumer demand increases, the scale of production will increase and eventually the
manufacturing cost will come down.
1.5 Properties and Applications
Biopolymers and their composites have emerged as alternatives to conventional synthetic

plastics for fabrication of films and coatings for food packaging applications. Biopolymer-
based films and coatings provide a semipermeable barrier to gases and water vapor, which
leads to reduced respiration and water loss, and they also act as a carrier for antimicro-
bials and antioxidants, which leads to retarded microbial spoilage and oxidative deterio-
ration, respectively [6]. They have also been reported to have a good barrier property
against UV light, which restricts its entry into packed and coated fruits and vegetables [71,
79–81]. Jafarzadeh and Jafari reviewed biopolymer-based nanocomposites and reported
significant improvements in mechanical, thermal, optical, antimicrobial, and barrier
properties due to uniform size and distribution of nanofillers throughout the biopolymer
matrix [82]. High intercalation of Na-MMT in xyloglucan biopolymer film showed
significant improvement in tensile strength and a remarkable improvement in oxygen
barrier property. Similarly, incorporation of ZnO NPs in agar-, carrageenan-, and carboxy-
methyl cellulose (CMC)-based films showed improved thermal stability and barrier prop-
erties against UV light and water vapor, and inhibition of foodborne pathogens such as L.
monocytogenes and E. coli [83].
Fruits and vegetables are living beings that can carry out most physiological processes
such as respiration, transpiration, transportation/translocation, growth, maturation, and
senescence, even after harvesting, as they do before harvesting. Respiration causes many
changes including weight loss, color change, ripening, tissue softening, loss of firmness,
and browning. Respiration influences several metabolic processes including chloro-
plastic, electron transport chains, leading to the production of reactive oxygen species
c01.indd 16 21-03-2022 08:48:13

(ROS) such as H2O2 and O2− [84]. Transpiration causes shriveling, wilting, browning,
textural changes, weight loss, and flavor loss, and thus it accelerates senescence. Ethylene
is a phytohormone that influences ripening of many fruits, leading to substantial quality
deterioration in fresh fruits and vegetables, and thus it reduces their postharvest shelf-life.
Therefore, by controlling respiration, transpiration, ethylene activity or production, and
other associated physiological processes, postharvest deterioration can be delayed sub-
stantially [85]. Environmental factors such as temperature, RH, atmospheric composi-
tion, and light also affect postharvest physiological changes in fruits and vegetables.
Besides physiological changes, fruits and vegetables are susceptible to postharvest con-
tamination by pathogenic and spoilage microorganisms such as E. coli, Erwinia carotov-
ora, Pseudomonas spp., Penicillium expansum, Botrytis cinerea, Alternaria alternata,
Rhizopus stolonifer, Phytophthora infestans, and Fusarium spp. Table 1.1 lists biopolymer-
based composite films and coatings, their active components, and their effects in main-
taining quality and extending postharvest shelf-life of fresh fruits and vegetables.
1.6 Conclusion and Perspectives
Biopolymers derived from plants, such as starch, cellulose, agar, and carnauba, those
derived from animals, such as gelatin, casein, whey protein, and beeswax, those derived
from microorganisms, such as dextran, xanthan, and pullulan, and those derived from
bio-based monomers, such as PLA, have been extensively studied and applied as biode-
gradable alternatives to synthetic plastics for food packaging applications. These sustain-
able food packaging films and coatings have been applied successfully on perishable foods
such as fruits, vegetables, meat, and milk products. Substantial research efforts have been
focused on the development of biopolymer-based composites and nanocomposites com-
monly incorporated with fillers such as NPs, EOs, antimicrobials, and antioxidants.
Contemporary and future researches have been and continue to be devoted to large-scale
manufacturing and commercialization of biopolymer-based food packaging systems in
order to reduce the burden of synthetic plastics on our environment.
c01.indd 17 21-03-2022 08:48:13

c01.indd 18
Table 1.1 Biopolymer films and coatings for postharvest shelf-life extension of fruits and vegetables.
Polymer Fruits and
class Biopolymer Active component vegetables Effect Reference
Polysaccharide Agar-based films ZnO NPs Green grape Composite film extended shelf-life up to 21 days [19]
Carrageenan-based ZnO NPs Mango Nanocomposite containing 1 wt% ZnO maintained shelf-life up to 19 days [86]
coatings
Chitosan-based TiO2 NPs Mango 0.03% TiO2 coating delayed decay rate (up to 19.73%) during first 15 days, [87]
coatings reduced weight loss (up to 6.2%) during 20 days of storage, and delayed
ripening up to 25 days
Aloe vera extract Tomato Coating delayed ripening and extended postharvest life up to 42 days at [88]
4 ± 1°C storage
Carbon dots Fresh-cut cucumber 4.5% w/w carbon dots containing coating inhibited microbial growth and [89]
maintained quality up to 15 days during storage at 4oC
Sodium alginate-based Monooxygenase Banana Coating increased shelf-life by 30% [90]
coatings
Cassava starch-based Starch nanocrystals Huangguan pear 6% SNC containing nanocomposite coating maintained shelf-life up to [91]
coatings (SNCs) 4 weeks at 20°C storage
CMC/guar gum Ag NPs Strawberry Film showed good preservation property and maintained shelf-life up to [92]
matrix films 6 days during ambient storage
Chitosan/cellulose ZnO NPs Black grape 5% w/w ZnO NP-loaded film extended shelf-life up to 9 days during ambient [93]
matrix films storage
Chitosan-guar gum – Mushroom 1:15 concentration of chitosan and guar gum maintained shelf-life up to [94]
composite coatings 16 days when stored at 4 ± 1°C
Pullulan-chitosan – Papaya Coatings maintained physiological and nutritional attributes during 14 days [95]
composite coatings of storage at 25oC
Chitosan-based Nanosilica Green tomato Coatings maintained weight loss, softness, senescence, titratable acids, and [96]
coatings total soluble solids during 15 days of storage at 23 ± 1oC
Gellan gum-based Aloe vera gel and Fresh-cut papaya 5% CaCl2-containing coating effectively maintained sensory quality and [97]
coatings calcium chloride acceptability up to 12 days when stored at 5°C
(CaCl2)
Guar gum-based Nanoclay, beeswax, Pomegranate Active films improved shelf-life up to 12 days during storage at 10 ± 0.5oC [98]
active coatings grape pomace extract
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c01.indd 19
Furcellaran/ Se-Ag NPs Kiwifruit Film showed high antimicrobial activity against E. coli, S. aureus, [80]
gelatin-based films methicillin-resistant S. aureus (MRSA), and extended shelf-life longer than
low-density polyethylene (LDPE) commercial film
Protein Soybean protein Cinnamaldehyde, Banana Composite films maintained nutrient content and delayed water loss, [99]
isolate-based coatings ZnO carbohydrate hydrolysis, pectin conversion, and fruit respiration, effectively
inhibiting fruit fungus spoilage during storage
Zein TiO2 Cherry tomato Improved shelf-life [100]
Pectin-based Magnesium hydroxide Cherry tomato Passive modified atmosphere packaging (PMAP) coupled with low- [101]
bionanocomposite NPs temperature (10°C) storage prolonged shelf-life till 24 days of storage
films
Olive flounder bone ZnO NPs Spinach Film showed antimicrobial property against Listeria monocytogenes and [102]
gelatin-based films inhibited microbial growth on packaged spinach during 7 days of storage at
cold (4°C) temperature and maintained fruit quality throughout storage
period
Zein/polyethylene Hexanal Peach 1:2:5 w/w hexanal/zein/PEO-coated peach extended shelf-life up to 4 days [103]
oxide (PEO) mix
coatings
Tilapia protein Clove EO Fresh-cut melon Coating maintained quality up to 12 days when stored at 4 ± 1°C [104]
isolate-based coatings
Soy protein Lemon extract Fresh-cut melon Coating maintained sensory attribute and edibility property up to 12 days [105]
isolate-based coatings when stored at 4°C
Pectin-based edible Potassium sorbate, Fresh-cut Coated persimmon slices were marketable up to 7 days [106]
coatings sodium benzoate, persimmon
nisin, citric acid
Soy protein Ferulic acid Fresh-cut apple 4 g L–1 ferulic acid-containing coating extended shelf-life up to 7 days [107]
isolate-based coatings during storage at 10°C
Lipid Carnauba wax-based Glycerol monolaurate Indian jujube Coated fruit showed delayed flesh softening and change of skin color, [64]
coatings (Zizyphus weight loss, respiration rate, and ethylene production
mauritiana Lamk.)
Beeswax Coconut oil Lemon Coating especially with MAP maintained color and firmness, and delayed [108]
shriveling, weight loss, and ethylene production throughout 18 days of
storage at ambient condition
(Continued)
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c01.indd 20
Table 1.1 (Continued)
Polymer Fruits and

class Biopolymer Active component vegetables Effect Reference
Beeswax-chitosan – Mango 2% beeswax maintained firmness and prolonged shelf-life up to 3 weeks [109]
composite coatings
Beeswax- – Red guava Coating containing 20% beeswax maintained freshness and shelf-life [110]
hydroxymethyl throughout 8 days of storage at 21oC
cellulose edible
coatings
Lacquer wax – Kiwifruit 2% lacquer wax extended postharvest life and maintained the sensory and [111]
quality attributes o
Wax – Pineapple Wax treatment maintained color, firmness, and respiration, and delayed [112]
ethylene production and internal browning up to 15 days
Carnauba wax-based – Eggplant Treated eggplant remained acceptable up to 12 days compared to 3 days in [65]
coatings untreated sample at ambient condition
Carnauba wax-based Nanoclay Valencia orange Nanoclay incorporation in carnauba wax formulation greatly enhanced [113]
coatings fruit sensory acceptability and nutritional quality and effectively prevented
fruit weight loss during 8 weeks of storage at 4oC
Polylactic acid PLA-poly(3- Angelica EO Peach Developed film effectively delayed oxidation and extended shelf-life to more [114]
(PLA) hydroxybutyrate-co-4- than 15 days
hydroxybutyrate) EO
extrusion films
PLA-PBAT films – Passionfruit PLA-PBAT films effectively maintained edible quality during 21 days of [115]
storage at 20oC
PLA-based films Halloysite nanotubes Tomato 3 wt% halloysite nanotubes containing PLA-based film extended shelf-life [116]
Polylactide-cellulose- – Fresh-cut tomato Tomato slices packed under polylactide-cellulose composite film showed [117]
based films longer shelf-life compared to conventional PP Coex film (Corapack srl,
Como, Italy) during 12 days of storage at 4oC
PLA Bergamot EO, TiO2-Ag Mango PLA nanocomposite films maintained quality and extended postharvest life [118]
NPs up to 15 days at room temperature storage
PLA-chitosan fiber Carbon nanotube Strawberry Film with chitosan content at 7 wt% enhanced strawberries for a maximum [119]
films period of 8 days at room temperature
21-03-2022 08:48:13
References 21
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c01.indd 27 21-03-2022 08:48:13

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Bruce, David, author of political volume, 196
Brunot, Dr. Felix, 48, 51
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Burr, Aaron, 57;
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Business centre of the town, 164
Butler, General Richard, 95, 122–123
Butler, Colonel William, 95
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Calhoun, Samuel, 117
Campbell, Colonel John, 4, 5
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Card industry, 104
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Chapman, Thomas, 30–31
Cheetham, James, 201
Christy, William, Merchant, 107, 131–132, 154, 184
Church records, 174
Churches, German, 10, 93, 186;
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City Hall, 50
“Clapboard Row,” 127;
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“Clapboardonian Democracy,” 127
Clark, General George Rodgers, 141
Clark, Josiah, 188
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Cochran, Dr. J. B., 206
Cochran, John Spear, 206
Cochran, Mary, 206
Cochran, Susan Cramer, 206
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Common Almanac, 174
Commonwealth, The, newspaper, 138, 140
Concerts, 69
Constitutionalists, 140
Coppinger, 78
Cotton mills, 92, 93
County jail, 24, 157
Court House, present, 50;
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Cramer, Mrs. Zadok, 206
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Cuming, F., Tour of the Western Country, 192–193
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Davis, Joseph, 131, 154
Declary, Peter, 69
“Democratic” party, 54
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Denny, Major Ebenezer, 131, 150–151
Denny & Beelen, 150, 151
Dent, Julia, 153
Dobbins & McElhinney, 110
Dress, Freemasons’, 12;
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Drinking, 80–82
Duane, William, 51
Dubac, Gabriel, Chevalier, 48, 111
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Echo, The, 197–198

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Gallatin, Albert, 57, 162;

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Gazzam, William, 121;
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social intercourse, 45;
establish newspaper, 45;
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starts library, 168
Glass factories, 32, 92
Grant’s Hill, pleasure ground, 49, 70–71, 77
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Gregg’s (Isaac) Ferry, 30
Hall, Joseph, 14
Hamilton, report on manufactures, 91
Hamsher, John, 40, 41, 155
Hancock, Richard, 122, 125
Hannastown, 2;
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Harmar, General Josiah, 151
Harris, Joseph, 157
Harris, Rev. Thaddeus Mason, 181
“Hartford Wits,” 197
Haymaker, Jacob, 40, 42, 126
Henderson, Rev. Matthew, 57
Henderson, Robert, 30, 80
Herald of Liberty, newspaper,62
Herd, William, 121
Herron, Rev. Francis, 83–84
Hilliard, Elizabeth Bausman, 125–126
Hilliard, James, 125, 126
Horse racing, 72–73;
condemned, 203–204
Houses, construction, 31 ff., 101;
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comforts in, 63
Hufnagle, Michael, 43, 96
Hughes, Rev. James, 190
Hutchins, Capt. Thomas, 175–176;
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Imlay, Gilbert, North America, 176

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Indians, the Penns’ dealings with, 6;
treaty with, 8;
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Insurgents, 71, 81, 119–120;
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McLane, D., 34
McLaughlin, Alexander, 132, 153
McMillan, Rev. Dr. John, 57, 81
McNickle, A., 130
Madison, James, 57
Magazine Almanac, 174
Magee, Samuel, 121
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Mail robbed, 119
Map of Pittsburgh published, 192
Marie, John, 49, 50
Marie, Mrs. John (Jane), divorce case, 50–51
Marie’s tavern, 56, 75
Market House, 155
Market Street, 96–98, 99, 104
Mechanical Society of Pittsburgh, 17–19, 78, 187
Mellish, John, 181
Methodists, 94–95, 201
Michaux, Dr. F. A., 48, 50
Mifflin, Thomas, 54, 56
Military plan of the town, 30–31
Military spirit, 74
Militia of Pennsylvania, 74–77
Modern Chivalry, by H. H. Brackenridge, 26
Money, circulation of, 15, 28–29
Montpensier, Duke of, 111
Moore, Hamilton, Practical Navigator, 182
Moreau, Jean Victor, 199
Morgan, General Daniel, 69, 115–116
Morrow, William, 12, 79
Morse, Jedidiah, American Gazetteer, 176
Mowry, Dr. Peter, 114, 132
Murphy, Mrs. Mary (Molly), 122, 152
Nail factories, 92, 93

National currency established, 99
National Gazette, 51
Nationalities in Pittsburgh, 38
Navigator, 174, 187;
sources of its material, 175, 176, 178;
various editions, 176–182;
advertised, 177;
local information in, 180–182
Negley, Alexander, 41
Negley, Jacob, 41
Negroes, 38–39
Neville, Emily Morgan, 144
Neville, General John, Freemason, 95;
residence, 105;
offices held, 106;
Federalist, 131
Neville, Morgan, 48
Neville, Colonel Presley, public offices, 105, 106;
residence, 115;
saves Brackenridge, 116;
Federalist, 131;
opinion of Democrats, 144
New Era in 1800, 90
New Orleans, steamboat, 189
Newspapers, first, 14;
German, 45;
see also Pittsburgh Gazette and Tree of Liberty
Nicholson, James W., 32
“Office of Discount and Deposit,” 116

O’Hara, Colonel James, 95, 120, 131;
glass manufacturer, 32;
brewer, 78;
candidate for burgess, 105
Ohio and Mississippi Navigator, 176–177
Ohio River, navigation of, 7, 176–178
Orleans, Duke of, 111
Ormsby, John, 78, 95
Ormsby, Oliver, 184
Patterson, Rev. Joseph, 81

Penn, John, 4–5, 6
Penn, John, Jr., 4–5, 6
Penn, William, 4
Penns, the, 42, 98
Pentland, Ephraim, editor, 138;
attacks on Bates and Baldwin, 145–147, 149
Peters, Judge Richard, 106
Philadelphia, post route from Pittsburgh, 17
Pipe manufactory, 92
Pittsburgh Academy, 17
“Pittsburgh Bookstore,” 116, 163, 184, 186 ff.
Pittsburgh Circulating Library, 167–171
Pittsburgh Fire Company, 24, 130
Pittsburgh Gazette, established, 14;
and politics, 56, 62, 133;
contributors, 75;
in religious revival, 85;
owner, 114;
Cramer’s advertisement in, 162–163;
advertises Navigator, 177
Pittsburgh Library Company, 171
“Pittsburgh” manor, 5
Pitt Township, 23, 28
Plan of town, 4, 5, 30–31
Population, in 1786, 9;
nationalities, 38;
in 1800 and 1810, 90;
Protestant, 93
Porter, William, 122
Post office, 17, 114, 128
Post route, 17
Practical Navigator, 182
Presbyterian Church, 9, 10, 83, 93, 94
Printing offices, 187
Protestants, 10, 93–94
Public improvements, 98
Publishing business, 164, 184–185
Race horses, 73
Reed, John, 79, 157
Reel, Casper, 41
Religion, 9–11, 82–83, 93;
revival, 84–85;
books on, 191
Republican General Assembly, radical, 138–139
Republican party, headquarters, 50;
“Democratic Republican,” 54;
rapid growth in Pennsylvania, 55;
leader in Pittsburgh, 55;
French influences, 55, 56;
influence on dress, 65;
spoils doctrine, 58;
emblem, 75–76;
dominant throughout country, 132;
in national election, 165–167
Richards, Charles, 39
Richardson, Dr. Andrew, Freemason, 96, 108;
conducts drug store, 107;
political leader, 108;
speech on Freemasonry, 108–109;
left Republican party, 109–110;
death, 110
Riddle, James, 96, 121, 128
Robinson, James, 30, 80
Robinson and Ensell, 92
Roman Catholics, 94
Ross, James, trouble with Mrs. Marie, 50–51;
candidate for governor, 50, 57;
Freemason, 96;
Commissioner to meet Insurgents, 123;
political leader, 131, 132
Roup, Jonas, 41
St. Clair, General Arthur, 151

St. John the Baptist’s Day, observance of, 12–13
St. John the Evangelist’s day, observance of, 12, 13, 108
St. Patrick’s Church, 94
Schoepf, Dr. Johann David, 7
Schools, 4, 14, 50, 186
Schultz, Christian, on Navigator, 181–182
Scotch, 38
Scott, Dr. Hugh, 96, 121, 128
Scott, John, 117
Scott & Trotter, 120
Scull, John, establishes Pittsburgh Gazette, 14–15;
postmaster, 17;
printer, 26, 187;
residence, 114;
attacks on Brackenridge, 133–134
Semple, Samuel, 78
Semple, Steele, 116
Semple, William, 27, 115
Shippinsburg, 2
“Sign of the Black Bear,” 13, 158
“Sign of the Cross Keys,” 57, 79
“Sign of the Franklin Head,” 116, 164
“Sign of General Butler,” 125;
and social affairs, 68;
name, 122;
during Whisky Insurrection, 123, 124;
political headquarters, 127
“Sign of General Washington,” 34
“Sign of the Green Tree,” 13, 34, 68;
meeting place of masonic lodge, 12, 96
“Sign of the Indian Queen,” 79–80
“Sign of the Negro,” 122
“Sign of the Sheaf of Wheat,” 153
“Sign of the Waggon,” 68, 79, 157
Six Nations, treaty with, 8
Slavery, 38, 39, 41
Smith, Thomas, 130
Smith, Rev. Dr. William, 44
Smith & Shiras, 78
Smur, John, 126
Snyder, Simon, 50, 51, 140
Social life, 71–72, 77
South School, 50
Spanish milled dollar, 99
Spear, John, 171, 188, 206
Spoils doctrine, 58
Steele, Rev. Robert, 13, 96, 129;
dress, 66;
appointment, 85
Stevenson, Dr. George, 120–121, 131
Stewart, Thomas, 147, 149
Stores, 102, 103, 116–117, 120 ff., 150, 154 ff., 184
Streets, 35, 98
Sturgeon, Jeremiah, 57, 79
Supreme Court, 118, 130, 139
Swiss-Germans, 10, 38
Tannehill, Adamson, 130

Tanneries, 92
Tavern-keeping, 78, 79
Tavern signs, 33–35
Taverns, 33, 68, 77, 78
Temperance movement, 96
Theatrical performances, 69, 70
Thorn, William, 82–83
Tinware manufactory, 92
Town meetings, 102
Town officials, 101
Townships, 23, 28
Trade, 7, 102
Trade centre, 7, 29
Transportation, 25, 93
Tree of Liberty, established, 62;
contributors, 75;
office, 115;
charge against editor, 127;
in politics, 132, 140;
in mourning, 149;
advertises Navigator, 177
Tree of Sedition, Blasphemy, and Slander, 56
Trees, 33, 97
Trinity Church, 93
Turnbull, William, 115
United States Mint authorized, 99

University of Pittsburgh, 17
Veech, Judge James, on whisky, 80–81
Wallace, Judge George, 117

Washington, George, President, 78, 123
Washington County, 22
Water Street residences, 105–107
Watson, Andrew, tavern, 18, 117, 118
Weber, Rev. Johann Wilhelm, 10–11
Welsh, 38
Western Gleaner, The, magazine, 193–195
Westmoreland County, 2, 22
“Whale and the Monkey,” Sign of, 34
“Whisky Boys,” 81
Whisky Insurrection, 29, 59, 106;
cause, 25, 77;
expedition against, 29, 59;
at its height, 119–120;
Government conference with Insurgents, 123–125
Wilkins, John, 117
Willock, Andrew, Jr., 153
Wills, Alexander, 158
Wills, James, 153
Wills, John, 158
Wilson and Wallace, sale of books, 14
Winebiddle, Conrad, 41
Wood, John, History of John Adams, 200
Woods, George, 5
Woods, General John, 125, 131, 132, 198
Woods (Wm.) & Company, 155
Wrenshall, John, local preacher, 84, 201;
Farewell to Pittsburgh and the Mountains, 153;
bookstore, 184
Wusthoff, William, 41, 96
Yeaman, James, 78, 158

Yeates, Jasper, 123, 130
“Young Messenger,” race horse, 73, 79
Transcriber’s Notes
Punctuation, hyphenation, and spelling were made
consistent when a predominant preference was found in the
original book; otherwise they were not changed.
Simple typographical errors were corrected; unbalanced
quotation marks were remedied when the change was
obvious, and otherwise left unbalanced.
The index was not checked for proper alphabetization or
correct page references.
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Biopolymer-Based Food Packaging:

Innovations and Technology Santosh

ffirs.indd 1 21-03-2022 08:41:47

ffirs.indd 3 21-03-2022 08:41:47

ffirs.indd 4 21-03-2022 08:41:47

1 An Overview of Natural Biopolymers in Food Packaging 1

2 Biopolymers: The Chemistry of Food and Packaging 29

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2.2.3.4 Whey Protein 36

3 Technologies for Biopolymer-Based Films and Coatings 66

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4 Chitosan-Based Films and Coatings 110

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4.4 Chitosan-Based Composite Films and Coatings 123

5 Starch-Based Edible Films and Coatings 147

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5.6.4 Fourier Transform Infrared Spectroscopy (FTIR) 160

6 Protein-Based Films and Coatings 178

7 Microbial Polysaccharides (MPs) in Food Packaging 225

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7.2 Production 227

8 Polylactic Acid (PLA)-Based Composites in Food Packaging 264

9 Antimicrobial Agents in Films and Coatings 282

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9.2.1.2 Microbial-Based Antimicrobials 291

10 Nanomaterials in Food Packaging 336

ftoc.indd 11 21-03-2022 08:41:52

10.3.1.1 Nanoclay 342

11 Silver and Zinc Oxide Nanoparticles in Films and Coatings 368

12 Plant-Based Active Compounds in Food Packaging 394

ftoc.indd 12 21-03-2022 08:41:52

12.3.10 Oregano 407

13 Essential Oils in Active Films and Coatings 422

14 Edible Films and Coatings 445

ftoc.indd 13 21-03-2022 08:41:52

Laxmikant S. Badwaik Gitanjali Gautam

Indra Bhusan Basumatary Dipankar Halder

flast.indd 15 21-03-2022 08:42:04

Vimal Katiyar Atanu Mitra

N. Arul Manikandan Yashaswini Premjit

flast.indd 16 21-03-2022 08:42:04

G. Pugazhenthi of Food Processing Industries,

flast.indd 17 21-03-2022 08:42:04

The idea of compiling a book on “Biopolymer-Based Food Packaging: Innovations and

fpref.indd 19 21-03-2022 08:41:40

fpref.indd 20 21-03-2022 08:41:40

An Overview of Natural Biopolymers in Food Packaging

c01.indd 1 21-03-2022 08:47:57

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c01.indd 3 21-03-2022 08:48:01

Figure 1.2 Lifecycle of chitosan (left) and PLA (right).

1.2 History and Background

c01.indd 4 21-03-2022 08:48:05

Silk fibroin Silk fibroin

In the nineteenth century, another natural polymer, cellulose, started impacting

c01.indd 5 21-03-2022 08:48:06

1.3.1 Polysaccharide-Based Biopolymers

c01.indd 6 21-03-2022 08:48:06