Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications [2] 0323899706, 9780323899703

Table of contents :
Front-Matt_2021_Biopolymer-Based-Metal-Nanoparticle-Chemistry-for-Sustainabl
Front Matter
Copyrigh_2021_Biopolymer-Based-Metal-Nanoparticle-Chemistry-for-Sustainable-
Copyright
Contributo_2021_Biopolymer-Based-Metal-Nanoparticle-Chemistry-for-Sustainabl
Contributors
Chapter-1---Application-of-bio_2021_Biopolymer-Based-Metal-Nanoparticle-Chem
Application of biopolymers in bioplastics
Introduction
Degradation of bioplastics
Bioplastic biodegradation under different environmental conditions
Soil
Compost
Aquatic environments
Bioplastic-degrading microorganisms
Biopolymeric sources of bioplastics
Polyethylene
Polylactic acid
Polyhydroxyalkanoates
Polybutylene succinate
Thermoplastic starch
Zein
Cellulose
Lignin
Albumin
Natural rubber
Chitosan
Other examples of biopolymers in bioplastic preparation
Current applications of bioplastics
Conclusion and future perspective
References
Chapter-2---Polysaccharides_2021_Biopolymer-Based-Metal-Nanoparticle-Chemist
Polysaccharides in food industry
Introduction
Structural organization of polysaccharides
Major functions of polysaccharides in a food system
Water-binding capacity
Gelation
Emulsions and emulsifiers
Major food applications of polysaccharides
Texture improvement
Oil emulsification
Flavor release
Polysaccharides as dietary fibers
Control of syneresis
Gluten-free bakery products
Stability of polysaccharides to processing
Important factors for the use of polysaccharides in the food industry
Microbial polysaccharides in food industry
Xanthan
Gellan
Pullulan
Alginate
β-Glucan in food industry
Plant polysaccharides in food industry
Guar gum
Starch
Pectin
Chitin and chitosan in food industry
Conclusion and future prospects
References
Chapter-3---Proteins-in-_2021_Biopolymer-Based-Metal-Nanoparticle-Chemistry-
Proteins in food industry
Introduction
Structure and chemistry of food proteins
Functional properties of proteins
Gelation
Emulsifying and foaming
Factors affecting properties of proteins in food products
Interactions of proteins with food components
Water
Carbohydrates
Salts
Food processes
Other processes
Proteins used in food industry
Casein
Collagen and gelatin
Whey
Egg proteins
Soybean protein
Gluten
Conclusion and future prospects
References
Chapter-4---Food-packaging-applicati_2021_Biopolymer-Based-Metal-Nanoparticl
Food packaging applications of biopolymer-based (nano)materials
Introduction
Properties of bionanocomposites for food packaging
Mechanical properties
Barrier properties
Biodegradation properties
Antimicrobial properties
Polysaccharide-based (nano)materials for food packaging
Cellulose-based packaging materials
Starch-based packaging materials
Chitin and chitosan-based packaging materials
Other polysaccharide-based packaging materials
Lignin-based (nano)materials for food packaging
Protein-based (nano)materials for food packaging
Gelatin-based packaging materials
Zein-based packaging materials
Whey-based packaging materials
Casein-based packaging materials
Conclusion and future perspective
References
Chapter-5---Biomedical-applications_2021_Biopolymer-Based-Metal-Nanoparticle
Biomedical applications of biopolymer-based (nano)materials
Introduction
Biopolymer-based (nano)materials for biomedical applications
Drug delivery
Chitin and chitosan-based (nano)materials in drug delivery
Cellulose-based (nano)materials in drug delivery
Alginate-based (nano)materials in drug delivery
Pectin-based (nano)materials in drug delivery
Gelatin-based (nano)materials in drug delivery
Lignin-based (nano)materials in drug delivery
Tissue engineering
Chitin and chitosan-based (nano)materials in tissue engineering
Cellulose-based (nano)materials in tissue engineering
Alginate-based (nano)materials in tissue engineering
Pectin-based (nano)materials in tissue engineering
Gelatin-based (nano)materials in tissue engineering
Lignin-based (nano)materials in tissue engineering
Wound dressing/healing
Chitin and chitosan-based (nano)materials in wound dressing/healing
Cellulose-based (nano)materials in wound dressing/healing
Alginate-based (nano)materials in wound dressing/healing
Pectin-based (nano)materials in wound dressing/healing
Gelatin-based (nano)materials in wound dressing/healing
Lignin-based (nano)materials in wound dressing/healing
Other biomedical applications (e.g., bioimaging, sensors, etc.)
Application of chitosan-based (nano)materials
Application of cellulose-based (nano)materials
Application of alginate-based (nano)materials
Application of pectin-based (nano)materials
Application of gelatin-based (nano)materials
Conclusion
References
Chapter-6---Biological-applications_2021_Biopolymer-Based-Metal-Nanoparticle
Biological applications of biopolymer-based (nano)materials
Introduction
Biopolymer-based (nano)materials for biological applications
Antioxidant applications
Chitin and chitosan-based (nano)materials
Cellulose-based (nano)materials
Pectin-based (nano)materials
Alginate-based (nano)materials
Gelatin-based (nano)materials
Lignin-based (nano)materials
Antibiofilm applications
Chitosan-based (nano)materials
Pectin-based (nano)materials
Gelatin-based (nano)materials
Lignin-based (nano)materials
Antibacterial applications
Chitin and chitosan-based (nano)materials
Cellulose-based (nano)materials
Pectin-based (nano)materials
Alginate-based (nano)materials
Gelatin-based (nano)materials
Lignin-based (nano)materials
Antifungal applications
Chitin and chitosan-based (nano)materials
Cellulose-based (nano)materials
Pectin-based (nano)materials
Alginate-based (nano)materials
Gelatin-based (nano)materials
Lignin-based (nano)materials
Antiviral applications
Chitin and chitosan-based (nano)materials
Pectin-based (nano)materials
Gelatin-based (nano)materials
Lignin-based (nano)materials
Conclusion
References
Chapter-7---Catalytic-applications-_2021_Biopolymer-Based-Metal-Nanoparticle
Catalytic applications of biopolymer-based metal nanoparticles
Introduction
Catalytic applications of polysaccharide-based metal nanoparticles
Cellulose
Starch
Alginate
Chitin & Chitosan
Gum
Catalytic applications of lignin-based metal nanoparticles
Catalytic applications of proteins-based metal nanoparticles
Collagen
Gelatin
Conclusion and future perspective
References
Chapter-8---Environmental-applicati_2021_Biopolymer-Based-Metal-Nanoparticle
Environmental applications of biopolymer-based (nano)materials
Introduction
Types, chemistry, and properties of biopolymer-based (nano)composites
Polysaccharides
Lignocellulosic complex
Proteins
Applications of biopolymer-based (nano)composites in water treatment
Chitosan-based (nano)composites
Cellulose-based (nano)composites
Gum-based (nano)composites
Alginate-based (nano)composites
Starch-based (nano)composites
Pectin-based (nano)composites
Lignin-based bio(nano)sorbents
Protein-based (nano)composites
Other environmental applications
Biohydrogen production
Electrochemical applications
Conclusion and future perspective
References
Chapter-9---Biopolymer-based-meta_2021_Biopolymer-Based-Metal-Nanoparticle-C
Biopolymer-based metal nanoparticles for biosensing
Introduction
Types of biosensors
Electrochemical biosensors
Optical biosensors
Thermal biosensors
Piezoelectric biosensors
Properties of biopolymers for biosensing
Biocompatibility
Immobilization matrix
Bioresponsiveness
Biopolymer-based metal nanoparticles for biosensing
Chitosan-based biosensors
Cellulose-based biosensors
Alginate-based biosensors
Other biopolymer-based biosensors
Conclusions and future perspectives
References
Chapter-10---Biopolymer-based--nano-_2021_Biopolymer-Based-Metal-Nanoparticl
Biopolymer-based (nano)materials for supercapacitor applications
Introduction
Principles of supercapacitors
Different types of supercapacitors
Electrode materials
Electrolytes
Aqueous and organic electrolytes
Ionic liquids
Biopolymeric composites for supercapacitor applications
Polysaccharide-based (nano)materials for supercapacitor applications
Cellulose-based supercapacitors
Chitin and chitosan-based supercapacitors
Starch-based supercapacitors
Lignin-based (nano)materials for supercapacitor applications
Protein-based (nano)materials for supercapacitor applications
Gelatin-based supercapacitors
Silk-based supercapacitors
Conclusion and future perspective
References
Chapter-11---Biopolymer-based--na_2021_Biopolymer-Based-Metal-Nanoparticle-C
Biopolymer-based (nano)materials for hydrogen storage
Introduction
Methods of hydrogen storage
High pressure
Liquefaction
Solid state
Mechanism of hydrogen storage
Chemical storage
Physisorption
Biopolymer-based (nano)materials for hydrogen storage
Lignin
Cellulose
Chitosan
Starch
Conclusion and future perspective
References
Index_2021_Biopolymer-Based-Metal-Nanoparticle-Chemistry-for-Sustainable-App
Index
A
B
C
D
E
F
G
H
I
K
L
M
N
O
P
Q
R
S
T
U
V
W
X
Z

Citation preview

Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications

Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications Volume 2: Applications

Mahmoud Nasrollahzadeh

Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

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 © 2021 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-323-89970-3 For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Susan Dennis Acquisitions Editor: Anneka Hess Editorial Project Manager: John Leonard Production Project Manager: Joy Christel Neumarin Honest Thangiah Cover Designer: Mark Rogers Typeset by SPi Global, India

Contributors Numbers in parenthesis indicate the pages on which the authors’ contributions begin.

Mahmoud Nasrollahzadeh (1, 47, 97, 137, 189, 333, 423, 517, 573, 609, 673), Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran Zahra Nezafat (1, 47, 97, 137, 189, 333, 423, 517, 573, 673), Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran Nasrin Shafiei (1, 47, 97, 137, 189, 333, 423, 573, 609), Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran Fahimeh Soleimani (47, 189, 333, 673), Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran Nayyereh Sadat Soheili Bidgoli (137, 189, 333, 423), Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran Talat Baran (189, 333, 573), Department of Chemistry, Faculty of Science and Letters, Aksaray University, Aksaray, Turkey Mohaddeseh Sajjadi (517), Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran Gurumurthy Hegde (609), Centre for Nano-materials and Displays, B.M.S. College of Engineering, Basavanagudi, Bengaluru, India

xi

Chapter 1

Application of biopolymers in bioplastics Mahmoud Nasrollahzadeh, Nasrin Shafiei, and Zahra Nezafat Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

1.1

Introduction

Plastics are widely utilized materials. They are daily used almost everywhere: in cell phones, packaging, toys, printers, pharmaceutical industry, electronics, automobiles, textiles, etc. Since 1940s, synthetic plastics have attracted a lot of attention due to their remarkable properties such as mechanical strength, lightness, flexibility, and durability. These properties are assigned to a material of low cost, which is capable of replacing products made from other materials including paper, glass, and metal [1, 2]. However, there is an all-known concern about the damages made by petrochemical-derived plastics to the environment after disposal. For instance, mostly around 7.8–8.2 million tons of the plastics enter the oceans every year. The negative effect of this long-lasting contribution to environmental contamination is depicted in Fig. 1.1 [3–5]. Therefore, researchers have been trying to find eco-friendly alternatives to manage the waste of plastics, which resulted in the study, production, and utilization of “bioplastics.” Bioplastics are plastics, which are biodegradable, biobased, or both. Examples of well-known, nonbiodegradable and biobased plastics include polyethylene (PE), poly(ethylene terephthalate) (PET), and polyamide (PA), poly(trimethylene terephthalate) (PTT). Petroleum-based biodegradable plastics include polybutylene adipate terephthalate (PBAT) and polycaprolactone (PCL). Some plastics such as polylactic acid (PLA), polyhydroxyalkanoates (PHAs), polybutylene succinate (PBS), and starch blends are both biobased and biodegradable (Fig. 1.2). Biodegradability of a compound means that it can be broken into smaller parts by enzymatic actions of microorganisms to form carbon dioxide, methane, water, biomass and various other natural substances, which can be easily eliminated. The biodegradation mechanism depends on the thickness and composition of the material. The term biobased plastic refers to plastics derived from natural sources or biomass. They may be biodegradable or not, but they are recyclable [6, 7]. Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00001-9 Copyright © 2021 Elsevier Inc. All rights reserved.

1

2 Biopolymer-based metal nanoparticle chemistry for sustainable applications

FIG. 1.1 Negative impact of plastic waste disposal [3].

FIG. 1.2 Three different classes of bioplastics [6].

Biopolymers are great candidates for the preparation of bioplastics as they are nontoxic, recyclable, and widely produced by nature. Biopolymers are generally considered eco-friendly alternatives for petrochemical polymers due to the renewable feedstock used to produce them and their biodegradability. This

Application of biopolymers in bioplastics Chapter

1

3

substitution also helps reduce greenhouse gas emissions. Biopolymers can play an important role in CO2 cycle as, with greater agricultural production, more CO2 (resulting from biopolymer degradation) is absorbed and, hence, CO2 release to the atmosphere is reduced, thereby leading to reduction in global warming. Natural polymers can be obtained from different resources such as microorganisms, plants, animals, biowastes, etc. Polysaccharides (cellulose, chitin, gum, etc.), lipids (oils, fats, etc.), proteins (casein, gelatin, etc.), PLA, and some bacterial compounds (such as PHA, xanthan, curdlan, and pullulan) are some examples of biopolymers. At present, the most commonly used commercial bioplastics are PLA and starch-based plastics. PHAs, biopolymer blends, and some bio-sourced thermoset materials such as furan resin also exist. PHAs are among the most desired biodegradable biopolymers, which can be produced by bacteria and plants and used to prepare bioplastics [4, 6, 8–15]. The production of bioplastics is estimated to grow from 200,000 tons in 2006 to 1 million tons in 2011. Bioplastics produced thus far have had lots of applications in different industrial sectors such as transportation, packaging, furniture, agriculture, construction, and consumer products. The products, which have used bioplastics, can be labeled to help distinguish between conventional and biobased plastics. In addition, there are some logos showing the capability of products to be recycled, biologically degraded, and compostable (Fig. 1.3). Novel bio-sourced biopolymers have been developed to meet the requirements of novel applications. Common requirements for distinct materials in mass production are low-price, processability, appropriate performance,

Bioplastic symbol

vs.

Recyclable

vs.

Biodegradable

Compostable

FIG. 1.3 Various types of notations of biodegradable symbols. (Reproduced with permission from Gnanasekaran D. Green biopolymers and its nanocomposites in various applications: state of the art. In: Green biopolymers and their Nanocomposites. Singapore: Springer, 2019. p. 1–27.)

4 Biopolymer-based metal nanoparticle chemistry for sustainable applications

and light weight. Weight reduction in products can be achieved by design, material choices, and eventually foaming. The variety of biomaterials, number of material combinations, processing technologies, and applications offer tremendous opportunities. However, there are many challenges, which must be met during the development of bioplastics to meet the demands of different industrial sectors [10, 14, 16].

1.2 Degradation of bioplastics A plastic can be considered biodegradable if a significant change in the chemical structure, i.e., degradation, occurs in the exposed material resulting in the formation of carbon dioxide, water, inorganic compounds, and biomass (new microbial cell constituents) but no visible or toxic residues under composting conditions. During the degradation process, long polymeric chains are broken down due to the effects of water, temperature, and sunlight (i.e., photodegradation) to shorter oligomers, dimmers, or monomers. These shorter units are small enough to pass through the cell walls of microorganisms and be used as substrates for their biochemical processes and can thus be degraded by microbial enzymes (Fig. 1.4) [17, 18].

FIG. 1.4 Biodegradation of biopolymers: aerobic vs anaerobic degradation. Dark pink (dark gray in print version) symbols represent the microorganisms involved in the processes [17].

Application of biopolymers in bioplastics Chapter

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5

Two main kinds of enzymes are involved in microbial depolymerization procedures: extracellular and intracellular depolymerases. The extracellular enzymes act outside the cells to break the longer units down into shorter molecules, preparing them for further degradation by intracellular enzymes. As biodegradation can occur in two ways, aerobically and anaerobically, it offers two types of biological waste treatment [17].

1.2.1 Bioplastic biodegradation under different environmental conditions 1.2.1.1 Soil The degradation rate of bioplastics in soil is closely related to the main components present in the bioplastics, the physical and mechanical properties of the bioplastic, and the bacterial biomass in soil. Several microorganisms such as Bacillus sp. and Aspergillus sp. have been isolated and identified as bioplastic degraders from the soil environment. Soil environments involve a vast variety of microorganisms, which enable plastic biodegradation to be more feasible in comparison with other environments such as water or air. An important objective is that the degradation of bioplastic does not affect the nitrogen circulation in the soil [17, 18]. 1.2.1.2 Compost Other than soil, compost is another ecological condition, which can be taken into account for the biodegradation of bioplastics as it contains high microbial diversity. A compostable plastic is a plastic, which undergoes degradation by biological processes during composting to yield water, carbon dioxide, inorganic compounds, and biomass at a rate consistent with other known compostable materials and leaves no toxic or visually distinguishable residues. Thus, a compostable plastic is biodegradable while a biodegradable plastic is not always compostable [19, 20]. 1.2.1.3 Aquatic environments Plastic wastes are also widely found in marine environments. Different habitats of the sea may show different rates of biodegradability. Sediments may have a favorable effect on biodegradation. It has been found that highest biodegradation could be achieved at the interface of water-sediment since the environmental conditions at the interface support the activity of plastic-degrading microorganisms. The temperature of water can also affect biodegradation of bioplastics. It was reported that the rate of biodegradation of PHA films had been different in the years 1999 and 2000 due to changes in temperature. Another parameter affecting the biodegradation role of aquatic systems is the existing bioplastic-degrading microorganisms, which may not be identical in different seawater environments. The shape of the biopolymer is also effective on the degree of biodegradation in marine water. Polymers with a larger surface

6 Biopolymer-based metal nanoparticle chemistry for sustainable applications

Temperature

Habitats

Bioplastic biodegradation in aquatic systems Micro organisms

Polymer shape

FIG. 1.5 Different parameters affecting biodegradation of bioplastics in aquatic systems.

area are degraded faster as they present higher polymer-water interface and facilitate the attachment of microorganisms to the surface of the biopolymer (Fig. 1.5) [19, 21–25].

1.2.2 Bioplastic-degrading microorganisms More than 90 types of microorganisms including aerobes, anaerobes, photosynthetic bacteria, archaebacterial, and lower eukaryotic present in different environmental conditions are responsible for biodegradation and catabolism of bioplastics. The degradation of bioplastics by microorganisms is distinguished through the appearance of a clear zone surrounding the growth in a plate containing the bioplastic as the only carbon source, followed by the consideration of the diameter for the biodegradation extension. Intracellular or extracellular depolymerase enzymes afforded by microorganisms are responsible for enzymatic degradation of bioplastics [19, 26, 27]. Depolymerase enzymes from Rhodospirillum rubrum and Bacillus megaterium are responsible for degrading polyhydroxybutyrate (PHB) [27, 28]. Degradation of PHB results in the transition of PHB granules in the intracellular compartment from an amorphous to a denatured semicrystalline state. Lemoigne first discovered that Bacillus megaterium releases PHB in an aqueous environment. It is now known that such secretion is due to the activity of PHB depolymerase. The commercial production of recombinant PHB depolymerase from Streptomyces exfoliates is now carried out by immobilizing the enzyme on an inert additive such as bovine serum albumin [28]. Furthermore, PLA can be degraded by different kinds of bacteria such as Amycolatopsis sp., Saccharothrix sp., Lentzea sp., Kibdelosporangium sp., Streptoalloteichus sp., and Burkholderia cepacia [29].

Application of biopolymers in bioplastics Chapter

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There are different kinds of fungi capable of degrading PLA. Fennellomyces linderi and Fusarium solani present in soil, Verticillium sp. and Lecanicillium saksenae present in compost, and Thermomyces lanuginosus, Aspergillus fumigatus, Mortierella sp., Doratomyces microspores present in both soil and compost degrade PLA residue [30]. PLA coupons (96% L-isomer) were buried in soil or compost at 25°C and unburied PLA coupons remained transparent after 8 weeks. However, when PLA was buried in compost or soil at 50°C, films became opaque and white after 1 week and physical disruption of the surface was visible with holes disrupting the integrity of the coupons. While no microorganisms were observed on the surface of unburied PLA (200
magnification; Fig. 1.6A), or PLA coupons buried in compost or soil at 25°C after 6 weeks (data not shown), extensive networks of branched hyphae were observed by ESEM when PLA was buried in soil and compost at 50°C for 6 weeks at 200
and 150
magnifications (Fig. 1.6B and C). More fungal hyphae were observed on PLA coupons buried in compost compared with PLA coupons buried in soil. At a higher magnification (1000
), septa were visible within the hyphae (Fig. 1.6D). Fungal spores (ca. 8 μm diameter) were also observed adjacent to the holes in the PLA surface recovered from compost at 500
and 2000
magnifications (Fig. 1.6E and F) [30]. Furthermore, the depolymerize enzyme responsible for PCL degradation was isolated from Streptomyces thermoviolaceus subsp. Thermoviolaceus 76T-2 [31]. Other enzymes such as lipase from Alcaligenes faecalis, esterase from Comamonas acidovorans, and serine from Pestalotiopsis microspora are also prominent for bioplastic biodegradation [32]. Table 1.1 presents some examples of microorganisms responsible for the biodegradation of bioplastics. Biodegradability of bioplastics affords the chance for them to be recycled. Proper disposal enters bioplastics in the recycling process (Fig. 1.7) [4].

1.3

Biopolymeric sources of bioplastics

Biopolymers are attractive feedstocks to produce bioplastics. They may be found in the nature in the shape of polymers prepared by animals, plants, or microorganisms, or its monomers may have natural sources, which are then polymerized to afford biobased polymers [64].

1.3.1

Polyethylene

Polyethylene (PE) is one of the most widely used thermoplastics known as HDPE, LLDPE, and LDPE (high density PE, linear low-density PE, and low-density PE, respectively). It is an aliphatic polyolefin produced by polymerization of ethylene (Fig. 1.8) and represents more than 30% of the global plastic market. Bio-ethylene, made from ethanol based on biomass, represents a chemically identical alternative to ethylene from petrochemical feedstock. However, the overall production process of ethylene from sugar-based ethanol

8 Biopolymer-based metal nanoparticle chemistry for sustainable applications

(A)

(B)

(C)

(D)

(E)

(F)

FIG. 1.6 Environmental electron scanning microscopy (ESEM) of the surface of PLA coupons showing fungal colonization and degradation. (A) Unburied control; (B) buried at 50°C for 6 weeks in soil; (C–F) buried at 50°C for 6 weeks in compost. Hyphae (Hp), septa (St), spores (S), and holes (H) were clearly visible and are indicated by arrows. (Reproduced with permission from Karamanlioglu M, Houlden A, Robson GD. Isolation and characterization of fungal communities associated with degradation and growth on the surface of poly(lactic) acid (PLA) in soil and compost. Int Biodeterior Biodegradation 2014;95:301–310.)

TABLE 1.1 Isolated bioplastic-degrading microorganisms from different environments. Environmental conditions

Type of microorganism

Name of bioplastic

Ref.

Soil

Bacteria

Amycolatopsis sp., Amycolatopsis thailandensis, Thermoactinomyces sp., Laceyella sp., Nonomuraea sp., Bacillus licheniformis, Actinomadura keratinilytica, Micromonospora sp., Streptomyces sp., Bortetella petrii, Paenibacillus amylolyticus, Paenibacillus sp.

PLA

[33–37]

Bacteria

Bacillus stearthermophilus

PDLAa

[38]

Bacteria

Streptomyces bangladeshensis

PHB

[39]

Bacteria

Pseudomonas aerogusina, Bacillus subtilis

PHA

[40]

Bacteria

Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas aeruginosa, Pseudomonas sp.

PHA

[41, 42]

Bacteria

Pseudomonas lemoignei

PHB

Microorganism

[43] b

Bacteria

Actinomadura sp.

PHBV

[44]

Bacteria

Clostridium acetobutylicum

Starch-based

[45]

c

Bacteria

Laceyella sacchari

PLLA + Starchbased

[46]

Bacteria

Stenotrophomonas

Nylon 4 (PA)

[47]

Bacteria

Amycolatopsis sp., Streptomyces sp., Streptomyces thermovioaceus, Paenibacillus sp.

PCL

[31, 37]

Bacteria

Paenibacillus amylolyticus

PCL

[33] Continued

TABLE 1.1 Isolated bioplastic-degrading microorganisms from different environments—cont’d Environmental conditions

Compost/soil

Type of microorganism

Microorganism

Name of bioplastic

Ref.

Bacteria

Amycolatopsis sp., Streptomyces sp., Paenibacillus sp., Paenibacillus amylolyticus

PBS

[33, 37]

Bacteria

Paenibacillus amylolyticus, Pseudomonas aeruginosa, Burkholderia cepacia, Bacillus pumilus

PBSAd

[26, 33, 48–51]

Bacteria

Paenibacillus amylolyticus

PESe

[26, 33]

Fungi

Candida albicans, Fusarium oxysporum

PHA

[40]

Fungi

Aspergillus niger

PHB

[43]

Fungi

Penicillium sp., Trichoderma pseudokoningii, Paecilomyces lilacinus, Cogronella sp., Acremonium recifei

PHB

[52]

Fungi

Fusarium sp., Fusarium solani, Fusarium oxysporum, Clonostachys rosea

Nylon 4 (PA)

[47, 53]

Fungi

Purpureocillium sp., Cladosporium sp.

PCL

[37]

Fungi

Purpureocillium sp., Cladosporium sp., Aspergillus fumigatus, Aspergillus niger, Fusarium solani

PBS

[37, 54–56]

Fungi

Aspergillus clavatus

PESe

[57]

Fungi

Penicillium sp., Aspergillus sp.

PHB

[58]

Fungi

Aspergillus sp.

Starch-based

[59]

Compost

Bacteria

Streptomyces thermonitrificans

PCL

[60]

Aquatic systems

Bacteria

Streptomyces sp., Burkholderia cepacia, Bacillus sp., Cupriavidus sp. Mycobacterium sp., Nocardiopsis sp.

PHB

[52, 61]

Bacteria

Streptomyces sp.

PCL

[61]

Bacteria

Pseudomonas putida, Leptothrix sp., Variovorax sp.

PHA

[23]

Bacteria

Enterobacter sp., Bacillus sp., Gracilibacillus sp.

PHB

Bacteria

Micrococcus sp., Bacillus sp.

PHBV

[62]

Bacteria

Bacillus pumilus

PCL

[26]

Bacteria

Pseudomonas sp., Tenacibaculum sp., Alcanivorax sp.

PCL

[24]

Bacteria

Psychrobacter sp., Pseudomonas sp., Moritella sp., Shewanella sp.

PCL

[63]

Bacteria Bacteria a

[25] b

Streptomyces sp. Bacillus pumilus

PES

e

[61]

e

[26]

PES

Poly-D-lactide. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate). c Poly-L-lactide. d Poly(butylene succinate-co-adipate). e Poly(ethylene succinate). Reproduced with permission from Emadian SM, Onay TT, Demirel B. Biodegradation of bioplastics in natural environments. Waste manage 2017;59:526–536. b

12 Biopolymer-based metal nanoparticle chemistry for sustainable applications

FIG. 1.7 Proposed presentation for reuse of bioplastics [4].

FIG. 1.8 Production route to PE bioplastics [64].

has to be further optimized. The most well-developed production routes for bio-ethanol are the fermentation of sucrose (e.g., sugarcane feedstock) and hydrolysis followed by fermentation of starchy biomass (e.g., corn feedstock) [64].

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Polylactic acid

Polylactic acid (PLA) is an aliphatic polyester produced by the polymerization of lactic acid obtained from agricultural resources such as corn, cotton waste, coffee waste, and food waste (Fig. 1.9). Polylactic acid is the second most produced bioplastic at present times after starch-based materials. It has high strength and high modulus with low percent elongation [64, 65]. Its abundant renewable source, high transparency, and excellent mechanical properties have made it a good alternative for traditional petrochemical plastics. In a study by Tengrang and co-workers, the transparency of PLA has been compared with that of PBS and Mater-Bi, as two other bioplastics and PLA have shown to have the highest transparency [66]. PLA can be used in a wide range of applications including geotextile, agricultural film, packaging, as binder fiber for cellulosic nonwovens and recently as one major thermoplastic for 3D printing, using the fused deposition modeling method (Fig. 1.10) [64].

FIG. 1.9 Production route to PLA bioplastics [64].

FIG. 1.10 PLA-based filaments containing wood fibers for 3D printing by fused deposition modeling (left). PLA-based 3D printed finger orthosis (right). (Reproduced with permission from Brodin M, Vallejos M, Opedal MT, Area MC, Chinga-Carrasco G. Lignocellulosics as sustainable resources for production of bioplastics—a review. J Clean Prod 2017;162:646–664.)

14 Biopolymer-based metal nanoparticle chemistry for sustainable applications

However, given its intrinsic chemical structure and composition, PLA suffers from high flammability with a very low limiting oxygen index (LOI) of 19– 21 vol%. Moreover, upon ignition, it easily gives rise to melt dripping during burning, which extremely restricts its practical applications in many fields such as packaging, textile, electric and electronic, and agriculture [67–70]. PLA shows just a slight decrease in mechanical properties after recycling. Recycled PLA can be easily used as an additive in the processing of PLA [71]. In a study, bioplastic composites were successfully prepared by extrusion and compression molding of starch-based bioplastics and PLA on a small scale to determine its properties. It was proved that raising PLA concentration can decrease the density of bioplastic composite to become light bioplastic, which would be an advantage for bioplastics. PLA can also increase the stability of hydrophobic characteristics and insoluble properties. It was observed that adding PLA can resist water molecules up to 20% compared with bioplastic without PLA. Thus, bioplastic composites have a good resistance against dissolution in water. Furthermore, adding PLA can improve the mechanical properties of bioplastic composites up to 5 MPa (10 wt% of PLA) [72]. In another study, different composites were prepared based on poly(L-lactic acid) (PLLA) in combination with DNA, whey protein (WP), and collagen (COL). Through the condensation of amino and carboxyl groups, whether from DNA, WP, or COL, chains could be grafted onto the PLLA molecules. COL/PLLA composites exhibited a higher heat resistance compared with DNA/PLLA and WP/PLLA composites. Moreover, COL exhibited the maximum improvement of tensile strength and elongation at break compared with DNA and WP, and the increases in the rate of tensile strength and the elongation at break were 88.6% and 154.9%, respectively [73].

1.3.3 Polyhydroxyalkanoates PHAs are a large class of biobased polyesters with homopolymer and copolymer structures, produced from renewable feedstocks (e.g., glucose, sucrose, and fatty acids) via biotechnological routes using different microorganisms (Fig. 1.11). When a complete range of nutrients is not available for cell growth, microbes synthesize and store the polyesters from a generous supply of carbon source. The biosynthesis of PHA is promoted by a lack in one or multiple nutrients, including sulfate, magnesium, nitrogen, phosphate, and oxygen. Depending on carbon source, the choice of microorganism, process conditions, and additives, polymers with different monomeric compositions and characteristics (such as crystallinity, chain length, brittleness, and elasticity) will be obtained [64, 74–76]. In general, PHAs are considered for material, which are used up in the environment, such as flowerpots used in planting, foils, bags, fishing lines, and nets (which should decompose if lost), materials used in biomedical applications, and other disposable items such as bottles, cups, plates, and cutlery, which can be composted but not recycled [13].

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FIG. 1.11 Production route to PHA bioplastics [64].

The utilization of activated sludge to convert carbon sources into PHAs can not only produce bioplastics but it may also solve part of the problem of the disposal of municipal activated sludge. The selection of industrial food wastes as a carbon source can also further decrease the cost of production of PHAs [77]. Polyhydroxybutyrate (PHB) is a biocompatible and biodegradable thermoplastic produced by various microorganisms as stored food. The organism needs anaerobic conditions with CO2 and N sources to form PHB. This bioplastic can be converted into films, sheets, fibers, or molded to the shape of a bag and bottle. However, considering the small share of PHB in total bioplastics and its unique characteristics, it is worthwhile to develop PHB for biomedical devices for tissue and organ engineering, cosmetics and health products, food packaging materials, and delivery systems for the controlled release of drugs, fertilizers, and pesticides [28, 78–81]. PHB monomer is a chiral molecule, which is insoluble in water and exhibits a high degree of polymerization. Being chiral, the monomers can be used for the synthesis of complex chiral pharmaceutical compounds. PHB is suggested as a source for chiral biopolymers. For instance, R-hydroxy carboxylic acid prepared by the acidic alcoholysis of PHB is widely used in the synthesis of chiral molecules [82, 83]. PHB can be implanted in the body with no inflammatory response due to its biocompatibility. Degradation of PHB takes place slowly inside the human body. Hence, PHB can be used as a carrier for the slow release of pharmaceuticals. The biocompatibility of PHB can also make it suitable for application in the field of tissue engineering. This property can be improved by treating PHB with lipase and NaOH.

16 Biopolymer-based metal nanoparticle chemistry for sustainable applications

The mechanical and biocompatibility properties of PHAs can be enhanced further by blending them with other polymers, modifying the surface or combining PHA with other inorganic materials to make them appropriate for a wider range of applications. The biocompatibility of PHB in vitro has been demonstrated on different cell lines: fibroblasts, mesenchymal stem cells, osteoblasts, bone marrow cells, articular cartilage chondrocytes, endothelial cells, smooth muscle cells, etc. [28, 84, 85]. Poly-3-hydroxybutyrate (P(3HB)) is the most common type of PHAs produced by microorganisms. P(3HB) homopolymer is a highly crystalline, stiff, yet relatively brittle material depending on the molecular weight [86]. Compared to polylactic acid (PLA), which is a popular, commercially available, renewable and biodegradable polymer, diverse combinations of PHA monomeric subunits offer a wide range of properties [87, 88]. Poly-3-hydroxyvalerate (P(3HV)) homopolymer exhibits a tensile strength of 31 MPa and an elongation to break of 14%, which demonstrates that P(3 HV) shows less stiffness and higher flexibility than P(3HB). P(3HB-co-3HV) copolymer is unique among the PHA family of copolymers in that the size and structure of 3HB and 3HV monomers are similar. This similarity allows 3HB and 3HV to participate in a co-crystallization process, in which 3HV could be incorporated into the 3HB crystal lattice and vice versa. As a result, the melting temperatures of the P(3HB-co-3HV) copolymers decrease to a minimum point as the ratio of 3HV to 3HB repeating units increases, and, after this minimum melting temperature is reached, it increases as the 3HV mole fraction further increases. PHA copolymers with lower melting temperatures are importantly advantageous in industrial applications, which require melt processing at lower temperatures [88, 89]. PHBV is another copolymer form of PHAs obtained from bacterial resources, specifically from the bacteria Alcaligenes eutrophus [90]. Different feeding, glucose, and propionic acid ratios produce different copolymer compositions, with the valerate content varying from 0% to 24%. The valerate content in the PHA family of polymers helps increase their processability and elasticity [91]. As shown by different tests, PHBV bioplastic is recyclable and can be processed multiple times with no significant loss in the properties [91].

1.3.4 Polybutylene succinate Poly(butylene succinate), an aliphatic polyester, is a biodegradable and economical biopolymer synthesized from biobased resources, providing further incentive to study this material [92–94]. The synthesis of PBS normally involves polycondensation reaction between 1,4-butanediol and succinic acid [95]. Compared with other aliphatic polyesters, PBS shows better biodegradability, thermal properties, melt processability, and chemical resistance, which make it appealing as the core material in the plastic industry. PBS has already been used in making injection-molded products, fibers, and films [95–97]. To enhance the properties of the materials made of PBS, various studies have been

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conducted and several methods have been introduced. The best approach for enhancing PBS properties is mixing it with fillers. Not only is this approach easy and economical but it is also efficient. Instead of using artificial fibers such as glass, carbon, or aramid, scientists are increasingly considering the application of natural and biodegradable fibers as the reinforcing fillers in composite materials [98]. Recently, great efforts have been made to tailor the properties of PBS and many works have been published on PBS-based copolymers and composites for different kinds of applications. In some studies, PBS has been added to the PLA matrix. The presence of PBS inside PLA strongly increases the nucleation of PLA, thus leading to high crystallinity of the material by cold crystallization [99, 100].

1.3.5

Thermoplastic starch

Starch is one of the major resources in the development of bioplastics obtained from a great variety of crops. For example, in a study by Johari and Sultan, it was reported that banana peel and corn starch may have a good future in the development of bioplastics [101]. Due to its large availability, low cost, renewability, interesting physicochemical characteristics, and biodegradability, starch is commonly used in the production of bioplastics. Currently, about 50,000 tons/year of starch are converted to plastic materials. It has been investigated widely for the potential manufacture of products such as water-soluble pouches for detergents and insecticides, flushable liners and bags, and medical delivery systems and devices [102]. Native starch commonly exists in a granular structure with about 15%–45% crystallinity [103]. It can behave like a thermoplastic when plasticizers, elevated temperatures, and shear are present. During the thermoplastic process, water and other plasticizers play an indispensable role because plasticizers can form hydrogen bonds with starch. This is because starch is a multihydroxyl polymer with three hydroxyl groups per monomer. There are vast intermolecular and intramolecular hydrogen bonds in starch. When the plasticizers form hydrogen bonds with starch, the original hydrogen bonds between the hydroxyl groups of starch molecules are broken, thus enabling starch to display plasticization [103, 104]. Thermoplastic starch (TPS) can be prepared by kneading, extrusion, compression molding, and injection molding of several native starches with the addition of glycerol as a plasticizer. The choice of plasticizer affects TPS even when these have similar plasticization principles. Native starch-based films are limited due to high water affinity and brittleness. Therefore, other natural biopolymers are often added as fillers to modify and improve the properties of films [105–109]. Unfortunately, the properties of TPS are not appropriate for applications such as packaging. TPS has two main disadvantages in comparison to most plastics currently in use, i.e., it is mostly water soluble and has poor mechanical properties. The water resistance of TPS may be improved by mixing it with biodegradable polymers, adding cross-linking agents such as trisodium trimetaphosphate,

18 Biopolymer-based metal nanoparticle chemistry for sustainable applications

Na3P3O9, or adopting the multilayer technique. Multilayer films based on plasticized wheat starch (PWS) and various biodegradable aliphatic polyesters have been prepared through flat film co-extrusion and compression molding. Biodegradable aliphatic polyesters are chosen as the outer layers of the stratified “polyester/PWS/polyester” film structure [110–112]. Furthermore, another approach is the use of fibers as the reinforcement for TPS. The fibers reported in the literature for this purpose are natural fibers, cellulose microfibers, and commercial regenerated cellulose fibers [113–115]. The SEM micrograph of the fragile fractured surface of TPS filled with different fiber contents shown in Fig. 1.12 reveals the dispersion of the fiber in the TPS matrix. The surface of the fiber appeared to be covered by TPS and fiber breakage was clear. This was attributed to the strong interaction between the fiber and TPS. However, a spot of starch granular figures, pointed out by the arrows in Fig. 1.12c and d, existed in TPS containing 15% or 20% fiber contents while there were no obvious starch granular figures in TPS with low fiber content (as shown in Fig. 1.12a and b). This indicates that by increasing the fiber content, the starch granular fusion was affected by the fiber during the thermoplastic processing of TPS. The fiber content was limited by high viscosity or insufficient dispersion during

FIG. 1.12 SEM micrograph at 500
magnification of fragile fractured surface of TPS filled with different fiber contents. (a) 5% Fiber contents, (b) 10% fiber contents, (c) 15% fiber contents, and (d) 20% fiber contents. (Reproduced with permission from Ma X, Yu J, Kennedy JF. Studies on the properties of natural fibers-reinforced thermoplastic starch composites. Carbohydr Polym 2005;62(1):19–24.)

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processing. TPS with less than 15% fiber content could be processed quite well without the additional plasticizer when the weight ratio of the gross plasticizer and cornstarch (0.3:1) was kept constant [103]. In a study by Corradini and co-workers, blends of TPS and zein were obtained by melt processing of cornstarch and zein, both plasticized with glycerol. Zein reduces the water absorption of the blends and decreases their water diffusion coefficient even at the lowest contents. Moreover, the processing of the blends is greatly facilitated by zein due to a strong reduction in their viscosity. These two favorable factors make zein a suitable and promising fully biodegradable compound for blending with starch (Fig. 1.13) [116].

20 µm

20 µm

20 µm

FIG. 1.13 SEM of fragile fracture surfaces obtained in liquid nitrogen of starch/zein blends plasticized with 20% glycerol: (a) 80/20; (b) 50/50; and (c) 20/80. (Reproduced with permission from Corradini E, de Carvalho AJF, da Silva Curvelo AA, Agnelli JAM, Mattoso LHC. Preparation and characterization of thermoplastic starch/zein blends. Mater Res 2007;10(3):227–231.)

20 Biopolymer-based metal nanoparticle chemistry for sustainable applications

1.3.6 Zein For more than 100 years, there has been ongoing interest in using cereal prolamin proteins such as maize zein to make plastics because of its various advantageous such as good film-forming properties, good tensile and moisture properties, antimicrobial and antifungal activity, good mechanical properties, and low oxygen and CO2 permeability. Zein is found in corn endosperm and has been the object of research, as well as industrial interest, for its film-forming ability and unique hydrophobicity, which is due to its high content of nonpolar amino acids. Like any other protein, upon isolation from the native state, zein shows high density and brittle behavior. Its brittleness can be overcome by using plasticizers such as water, glycerol, and ethylene glycol [117–120]. In a study by Di Maio and his research group, it was shown that the supramolecular design of the protein can be achieved by modifying the hierarchical structure of zein using a highly interactive additive such as lignin to obtain bionanocomposites characterized by enhanced mechanical performances and specific functional properties (from hydrophilic to hydrophobic behavior) suitable for specific applications (from biomedical uses to food packaging) [119].

1.3.7 Cellulose Cellulose in its unmodified form is the dominant component of many major agricultural and forestry products. Purified cellulose is produced mainly from the bleached wood pulp resulting from the sulfite or Kraft process, which removes most of the associated hemicellulose, lignin, pectin, and other compounds. Isolated cellulose cannot be used for plastics because it is crystalline, has a stiff rod-like conformation, and the individual chains are too tightly connected by hydrogen bonds. Unmodified cellulose fibers are used as reinforcing agents in biocomposites, improving tensile and flexural modus [121]. Cellulose can be involved in various chemical modifications or treatments to afford different applicability. Nitrocellulose combined with camphor and other components yielded the first thermoplastic, known as Parkesine and Celluloid, which was used as an ivory replacement. Given its flammability and easy decomposition, only minor applications such as those in guitar picks and table tennis balls survived [13]. Cellophane is made of restructured cellulose produced by dissolving it in a base and carbon disulfide (the solution is known as viscose), extruding through a slit into dilute sulfuric acid and sodium sulfate, washing, and adding glycerol. The resulting film is still widely used for food packaging [13]. Cellulose acetate, prepared by the treatment of purified cellulose with glacial acetic acid, is used in frames for eyeglasses, adhesives, photography films, paint, textile fibers, packaging materials, artificial kidney, reverse osmosis membranes, and many other applications. Other derivatives are carboxymethyl cellulose (CMC), methyl cellulose (MC), hydroxypropyl cellulose (HPC), and

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hydroxyethyl cellulose [13, 122]. Plastic materials made of cellulose derivatives are produced by the route shown in Fig. 1.14 [64]. The mechanical properties of CA can get better when combined with starch acetate (SA). The resulting films combine the advantages of CA and SA while reducing their disadvantages. For example, SA film is fragile and easily torn, and CA film degrades slowly when buried in the soil. However, by changing the proportion of SA, the mechanical properties of the film improve and the degradation properties can be controlled [122]. A study by Mohanty et al. was focused on the fabrication of low-cost, valueadded biodegradable composite materials from a recycled biobased product such as recycled cellulose fibers (RCF) and PHBV. The incorporation of RCF considerably improved the properties of PHBV such as tensile, storage moduli, and heat deflection temperature. The biodegradable nature and competent properties of RCF-reinforced PHBV composites make it a sustainable alternative to conventional thermoplastic-based materials [123]. In another study, Cai et al. fabricated bioplastics of a new class from cellulose hydrogels prepared in an alkali hydroxide/urea aqueous solution by changing the aggregated structure via hot pressing process (Fig. 1.15) [124]. The bioplastics had a uniformly orientated structure in the parallel direction and displayed good optical transmittance. Moreover, the cellulose bioplastic exhibited much higher tensile strength, flexural strength, and thermal stability, as well as a lower coefficient of thermal expansion than common plastics and the regenerated cellulose films.

FIG. 1.14 Production route to bioplastics made of cellulose derivatives [64].

22 Biopolymer-based metal nanoparticle chemistry for sustainable applications

FIG. 1.15 Schematic representation of the preparation approach for the cellulose bioplastic: (i) generation of homogeneous cellulose/NaOH/urea aqueous solution; (ii) formation of physical hydrogel via a nonsolvent and then washing; (iii) preparation of cellulose bioplastic by simple hot pressing of the hydrogel [124].

Shi and co-workers also prepared functional cellulose bioplastics with isotropic thermal properties, which were enhanced by three-dimensional interconnected graphene aerogels (Fig. 1.16) [125]. Hence, the three-dimensional interconnected GA endows the cellulose bioplastic with high thermal conductivity and, in turn, the cellulose bioplastic strengthens the fragile GA, resulting in the better mechanical performance of the composites, which will replace fossil fuel plastics in the field of thermal management and broaden the applications of the cellulose bioplastic. Fig. 1.17 shows the photographs of cellulose, cellulose/GA, and GA.

1.3.8 Lignin Of 70 million tons of lignin obtained from the paper-making industry, only 2% is processed and utilized as lignin and the rest is added into fuels. In bioplastics, lignin can be used as reinforcement. Blending this biopolymer with other

FIG. 1.16 Fabrication process of cellulose/GA composites [125].

Application of biopolymers in bioplastics Chapter

(1)

(2)

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23

(3)

2cm (1) Cellulose (2) Cellulose/GA

(3) GA

FIG. 1.17 Photographs of cellulose, cellulose/GA, and GA. (Reproduced with permission from Chen L, Hou X, Song N, Shi L, Ding P. Cellulose/graphene bioplastic for thermal management: enhanced isotropic thermally conductive property by three-dimensional interconnected graphene aerogel. Compos Part A Appl Sci Manuf 2018;107:189–196.)

biopolymeric materials is attractive because of its wide availability, biodegradability, and good mechanical properties, along with the diversity of potential modifications due to its chemical structure. The utilization of lignin as reinforcement reduces cost and water uptake and improves strength and can afford antioxidant properties as a stabilizer [126–128]. In a study by Darie and co-workers, novel bioplastics were prepared by melt compounding of two types of lignin obtained from softwood (LB), hardwood (LO), and PLA [127]. The addition of lignin improved the thermal stability of PLA and its mechanical properties. The SEM micrographs suggest that both types of lignin can be well dispersed in PLA matrix during melt processing and there is good adhesion between lignins and PLA. The accelerated weathering had no significant effect on the elastic properties of PLA lignin composites. However, the tensile and impact strength of these composites slowly decreased. All composites showed an increase in water sorption capacity, with PLA/LB material having the highest water sorption capacity. The free surface energy increased after weathering for all materials, especially for PLA and PLA/LB composite while the thermal properties were less affected after UV exposure in the composite containing Lignoboost lignin. Their results showed that a suitable combination of PLA and lignin, as polymers derived from natural resources, allowed the development of novel, environmentally friendly materials with higher values than the corresponding starting materials. In another study, Zollfrank and co-workers investigated the effects of high lignin loading on the properties of lignin/polyethylene-co vinyl acetate (EVA) rubber composites [129]. The SEM photographs of the organized composites are shown in Fig. 1.18. The results of this study can enhance the attractiveness of lignin obtained from various feedstocks for wide industrial applications.

1.3.9

Albumin

To determine the potential uses of protein-based bioplastics, thermal and mechanical properties must be examined. Since protein-based bioplastics require a lower processing temperature and possess tensile properties similar

FIG. 1.18 SEM images of fracture surfaces of composites with lignin contents of 25 wt% (LIG25), 50 wt% (LIG50), 62.5 wt% (LIG62.5), and 75 wt% (LIG75) at low magnification (a–d) and high magnification (e–h). (Reproduced with permission from Dorrstein € J, Scholz R, Schwarz D, Schieder D, Sieber V, Walther F, Zollfrank C. Effects of high-lignin-loading on thermal, mechanical, and morphological properties of bioplastic composites. Compos Struct 2018;189:349–356.)

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to plastics such as high-density polyethylene (HDPE), it is possible to manufacture a bioplastic at a lower production cost. However, one potential drawback of using the protein in plastics is its hygroscopic properties as it was determined that the water absorption of various bioplastics ranged from 40% to 320%. This tendency for bioplastics to absorb water may result in plastics with lower elasticity as the moisture content may alter the elastic modulus of the resulting plastic [130, 131]. Albumin protein provides one possible source of raw material with inherent antimicrobial properties, which may make it suitable for medical applications [132]. In a study by Sharma, bioplastics with albumin and different plasticizers, viz. water, glycerol, and natural rubber, were prepared [132]. It was found that the blending ratios yielding the best combination of initial modulus and elasticity were the 75:25 albumin-water, 75:25 albumin-glycerol, and 80:20 albuminnatural rubber ratios. Of these blends, it was found that the 80:20 albuminnatural rubber bioplastic provided the best thermal, viscoelastic, and tensile properties. However, the properties of the 75:25 albumin-water and 75:25 albumin-glycerol plastics were not comparable due to moisture loss in the water-based bioplastics over time while glycerol leaching occurred in the glycerol-based bioplastics as time passed. In addition, Jones and Sharma have compared the thermal properties of the protein-thermoplastic blends [133]. They stated that adding more LDPE into the thermoplastic blend causes the resulting plastics to have thermal properties more similar to those of LDPE plastics than pure protein plastics. In terms of mechanical properties, they found that there was a synergistic effect between albumin and LDPE, which produced a plastic with higher modulus and elongation compared to pure LDPE and albumin plastics. In another study, albumin and zein thermoplastic blends were plasticized with glycerol and mixed with varying amounts of LDPE [134]. When subjected to soil burial, albumin completely biodegrades as a bioplastic within 2 months while a zein-based bioplastic is more resilient to attacks from microbes within the soil. If albumin and zein proteins are used in the production of thermoplastics in tandem with LDPE, it could be possible to produce a plastic, which will naturally biodegrade over time, decreasing the environmental impact of the use of thermoplastics in medical and food packaging applications. Ferna´ndez-Espada et al. selected two well-known proteins to produce bioplastics through injection molding [135]. A soy protein isolate (SPI) and an egg white albumen concentrate (EW) were separately mixed with glycerol (GL) and the characteristics of the obtained bioplastics were compared. The results showed that EW/GL bioplastics were more transparent than SPI/GL. Specifically, when measuring the transmittance (T) through the sample and considering air as the reference (T ¼ 100%), albumen bioplastic presented a T value 26% higher than that of soybean bioplastic. In general, the clarity of the films may be improved with increasing the processing temperature. On the other hand, SPI possesses a more thermoplastic characteristic than EW protein. In

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addition, the higher hydrophilic characteristic of SPI bioplastics is responsible for their remarkable enhancement in water uptake capacity (either in the air or water media) compared with EW bioplastics. This would make soybean an excellent candidate to produce protein-based bioplastics for different potential applications in which the absorption of water is critical (e.g., superabsorbent materials).

1.3.10 Natural rubber Natural rubber is a remarkable polymer consisting of isoprene units linked in a 1,4-cis configuration. It is produced in over 2500 plant species and used about 1.5 times more than synthetic rubber. This is due to the superior properties of natural rubber such as efficient heat dispersion, superior resilience, elasticity, resealing after a puncture, abrasion and impact resistance, and malleability at cold temperatures, which are a function of its enantiopure structure, high molecular weight, and additional components present in the latex such as proteins, lipids, carbohydrates, and minerals [136–138]. Natural rubber is almost irreplaceable in many applications such as heavy duty tires for trucks, buses, and airplanes, as well as latex products for medical applications [137].

1.3.11 Chitosan Typically, chitosan is produced from wastes generated from crustacean processing (shrimp and crabs), even though it is also possible to obtain it from the chitin component of fungal cell walls. Chitosan shows physical, chemical, and biological properties, which make it appropriate for several industrial (biomedical and biotechnological) applications [139, 140]. Fig. 1.19 shows the fabrication of 3D objects with chitosan [141]. Chitosan can also be a natural filler for bioplastics. For example, Lubis and co-workers reported that the analysis of jackfruit seed starch showed moisture, ash, starch, amylose, amylopectin, protein, and fat contents of 6.04%, 1.08%, 70.22%, 16.39%, 53.83%, 4.68%, and 0.54%, respectively [142]. They used starch of jackfruit seed (Artocarpus heterophyllus) as the raw material for manufacturing bioplastics using sorbitol and chitosan as plasticizer and filler, respectively. The best bioplastic was obtained from jackfruit seed at a starchto-chitosan ratio of (w/w) ¼ 8:2 with a sorbitol concentration of 25% and a tensile strength of 13.524 MPa. In another study, El Kadib and co-workers reported the preparation of the aldehyde-functionalized, transparent, and flexible chitosan-montmorillonite hybrid films, which act as a new generation of eco-friendly, controlled chemical release bioplastics [143]. Fig. 1.20 shows the general scheme for the preparation of the aldehyde-functionalized bioplastics. Another study focused on the bioplastic synthesis of chitosan and yellow pumpkin starch (Cucurbita moschata) with castor oil as plasticizer [144].

FIG. 1.19 (a) Diagram of the fabrication process. An initial solution of 3% chitosan is concentrated until it reaches the viscosity necessary to be molded. To cast the solution, it is warmed up to decrease the viscosity and then poured over the mold. The viscosity increase at room temperature helps keep the polymer on the walls of the mold. The final crystallized form of chitosan is separated from the mold after the remaining solvent is evaporated. In the case of injection molding, the polymer or its mixture with a filler is concentrated to a plastic state and warmed up at 80°C before being injected into the mold. Just after the injection, the mold is opened and the fabricated objects are removed. (b) Examples of geometric 3D shapes fabricated from chitosan by the casting method. (c) Examples of cast chitosan objects colored with water-soluble dyes (i.e., tartrazine, allura red, brilliant blue FCF, and fast green FCF). (d) Detailed photograph of a casted object. Letters are 50 μm tall (bar is 10 mm). (e) Color intensity, measured by spectrophotometry, of the solvent in which a piece of red-colored (dark gray in print version) chitosan is submerged. The release of the dye is high at low pH values and negligible at high pH values (>6.0). Insets show graphic representations of retaining or removal of color dye molecules (red spheres; dark gray in print version) depending on the pH of the environment. (f) Mechanical properties (strength and toughness) of the material measured before (dry) and after 12 h underwater (hydrated) when treated with different organic waterproof coatings of beeswax or parylene-C (parylene). (g) The detailed picture of a wood/chitosan king chess piece made by injection molding. The Maltese cross is 5.8 mm wide and 2 mm thick (bar is 10 mm). (h) Example of chess pieces (dyed black and colorless) made by injection molding using wood flour as filler. Queen is 41.08 mm tall. (Reproduced with permission from Fernandez JG, Ingber DE. Manufacturing of large-scale functional objects using biodegradable chitosan bioplastic. Macromol Mater Eng 2014;299(8):932–938.)

28 Biopolymer-based metal nanoparticle chemistry for sustainable applications (A)

O

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OH

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OH Ar4CHO

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y

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FIG. 1.20 General scheme for the preparation of the aldehyde-functionalized bioplastics. (A) Description of the three players in these variants. From left to right: chitosan, referred to as CS, a pyranosic copolymer featuring both acetyl glucosamine and glucosamine units. Layered sodium-exchanged montmorillonite, referred to as Mnt, in which d shows the basal distance between the galleries without functionalization. The chemical structure of the four used aromatic aldehydes. (B) Illustration of the preparation procedure for the bioplastics, involving only water and acetic acid as chemical reagents and CS and Mnt as raw materials. (C) Imine bond formation by reacting chitosan with aldehyde [143].

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The absorption capacity of the solvent, tensile strength, and biodegradability were tested. The optimum absorption capacity of the solvent was obtained on the pumpkin/chitosan composition of 50/50 in H2O and C2H5OH solvent. Meanwhile, the optimum absorbency in HCl and NaOH solvents was shown by 60/40 composition. The optimum tensile strength of 6.787  0.274 MPa was obtained using the 40/60 composition, and the fastest biodegradation test process within 5–10 days occurred using the 50/50 composition. The more the chitosan content, the higher the value of tensile strength test obtained while the fastest biodegradation rate occurred in the yellow pumpkin/chitosan composition of 50:50.

1.3.12 Other examples of biopolymers in bioplastic preparation A study by Hindi and co-workers used gum Arabic (GA) collected from Acacia senegal trees with polyvinyl alcohol (PVA) to prepare biodegradable membranes (Fig. 1.21). Great success was achieved for the production of transparent bioplastic membranes by applying a novel casting method termed as free horizontal flow [145].

FIG. 1.21 Biodegradable membranes from GA and PVA. (Reproduced with permission from Hindi S, Albureikan MO, Al-Ghamdi AA, Alhummiany H, Ansari MS. Synthesis, characterization and biodegradation of gum arabic-based bioplastic membranes. Nanosci Nanotechnol 2017;4(2):32–42.)

30 Biopolymer-based metal nanoparticle chemistry for sustainable applications

Blood meal (BM) can be used as the source of different proteins to form thermoplastic materials. Blood meal can be converted into a thermoplastic called Novatein thermoplastic (NTP) using water, urea, sodium dodecyl sulfate (SDS), sodium sulfite, and triethylene glycol (TEG). To increase the range of applications of NTPs and consumer satisfaction, its color and odor must be removed without compromising its ability to be processed into a bioplastic using common thermoplastic-processing techniques [146–148]. As another example, whey protein bioplastics were obtained via blending the protein with two abundant biopolymers, namely natural latex and egg white albumin, by compression molding in which water was added as a plasticizer. It was demonstrated that the addition of about 10% of latex and albumin to wheybased bioplastics improved the toughness of whey-based materials without compromising their strength and stiffness [149]. Table 1.2 summarizes some other examples of utilization of biopolymers in the preparation of bioplastics.

1.4 Current applications of bioplastics Growth rates of the demand for biobased plastics might seem impressive. The largest application of plastics today is packaging, and within the packaging niche, food packaging amounts as the largest plastic-demanding application. The biodegradability of bioplastics may be attractive for specific applications such as food service items and compostable bags, particularly where composting or anaerobic digestion facilities are available. The most suitable packaging applications for biodegradable and compostable plastics are those in which the biodegradability or compostability provide significant benefits, the collection is easy (e.g., from large restaurants, stores, and institutions, etc.), or there are tax incentives or legal constraints (as in Italy) [178, 179]. These applications include the following: l

l

l l

l

Single-use compostable refuse bags for organic wastes (e.g., kitchen and yard waste) Single-use compostable thermoformed and injection-molded foodservice products, food trays, and food and beverage cartons or marinebiodegradable versions for marine use Grocery carrier bags Agricultural and horticultural uses, such as fertilizer bags, potato bags, plant pots, seed trays, and mulch films Loose-fill packaging [178]

Biomedical applications of bioplastics are also notable, for example, the application of collost bioplastic collagen material for the treatment of burns [180] or chitin-based bioplastics for bone repair [153]. In academic literature, there are many applications for bioplastic materials in numerous biomedical and

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TABLE 1.2 Bioplastics prepared using biopolymers and their properties. Bioplastic feedstock

Bioplastic properties

Ref.

Gelatin/ferulic acid

Very good gas barrier properties

[150]

Keratin from chicken feathers with 2 wt% of glycerol

Good mechanical and thermal properties, compatible morphologies without edge, cavity, and holes

[151]

Wheat gluten-based bioplastics with fish scale

Higher tensile strength than the neat wheat gluten-based bioplastic

[152]

Chitin/hydroxyapatite

Viability, biocompatibility, hemocompatibility and in vivo histocompatibility

[153]

Agarose bioplastic cross-linked by citric acid

Tensile strength over twice the tensile strength of noncross-linked control films, less water absorption, and slower degradation rate

[154]

Glycerol/gluten

Good rheological properties and thermosetting potentials

[155]

Glycerol/albumen

Good rheological properties and thermosetting potentials

[155]

Methyl cellulose/gluten

Methyl cellulose enhances material elongation properties and affects material hydrophilic characteristics

[156]

Carboxymethyl cellulose/gluten

Carboxymethyl cellulose enhances material elongation properties and affects material hydrophilic characteristics

[156]

Starch/PHBV

PHBV degradation was metabolically repressed by glucose derived from starch

[157]

Glycerol, water, and wheat gluten

High ability for thermosetting modification, due to protein denaturation, which may favor the development of a wide variety of biomaterials; high water absorption and slow KCl release

[158]

Wheat gluten and glycerol

Strong protein network; barrier properties

[159]

Starch (corn and potato)/ albumen/glycerol

Transparent; strength at low deformation

[160]

Glycerol/gluten

Bioplastic obtained by mechanical processing showed higher thermal susceptibility, which was related to the denaturation degree and thermosetting and cross-linking potentials of proteins

[161]

Continued

32 Biopolymer-based metal nanoparticle chemistry for sustainable applications

TABLE 1.2 Bioplastics prepared using biopolymers and their properties— cont’d Bioplastic feedstock

Bioplastic properties

Ref.

Starch from cassava (Manihot esculenta Crantz)/different amounts of glycerin, glutaraldehyde, polyethyleneglycol and lithium perchlorate

Biofilms with higher amounts of lithium perchlorate portray higher values of conductivity

[162]

Albumen/tragacanth gum/ glycerol

Tragacanth gum in egg white albumenbased bioplastics enhances their water uptake; higher glycerol content in albumen-based bioplastics increases their water uptake; higher glycerol content results in lower flexural moduli of albumen-based bioplastics; tensile properties of albumen bioplastics decrease when glycerol content is higher; control of relative humidity promotes water migration in the bioplastic formulation

[163]

Amylose

Cytotoxicity, chemical durability, in vitro biocompatibility

[164]

Gum Arabic

Hydrophilic behavior, low oxygen barrier properties, potent antioxidant activity, and promising biodegradability

[165]

Cellulose/chitosan/sorbitol plasticizer

The optimal result of tensile strength test was 0.089 kgf/cm2 with elongation percent 15.90%

[166]

Carboxymethyl cellulose from pineapple peel

Suitable properties for packaging of dehydrated food

[167]

Tragacanth gum/egg white (EW)

The presence of tragacanth gum in EW bioplastics enhances their water uptake; a higher content of tragacanth gum results in higher water uptake values; tragacanth gum influences the mechanical properties of EW bioplastics

[168]

Cellulose acetate/triethyl citrate

The tensile strength, modulus and thermal stability of cellulosic plastic reinforced with organoclay showed a decreasing trend with an increase in plasticizer content from 20 to 40 wt%. Nano-reinforcement at lower volume

[169]

Application of biopolymers in bioplastics Chapter

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TABLE 1.2 Bioplastics prepared using biopolymers and their properties— cont’d Bioplastic feedstock

Bioplastic properties

Ref.

fractions (ϕ  0.02) reduced the water vapor permeability of cellulosic plastic by 2 times and the relative permeability better fits with larger platelet aspect ratios (α ¼ 150) Starch citrate

Barrier against water vapor and moisture

[170]

Gluten

Antimicrobial activity and suitable biocide release

[171]

Albumen protein/starch (potato and corn)

High transparency and a suitable mechanical behavior

[172]

Gelatin/potato starch/glycerol

Mechanical properties (such as strength and elasticity), transparency, and film thickness strongly depend on the starch content

[173]

Waste chicken feather keratin

The thickness of bioplastic film was 1.12
104 mm with tensile strength of 3.62  0.6 MPa. Young’s modulus and break elongation for synthesized bioplastic film were 1.52  0.34 MPa and 15.8  2.2%, respectively

[174]

Switchgrass/lignin/PBS

Impact strength of the material enhances by isocyanate-terminated polybutadiene prepolymer. The composites exhibited about 252%– 333% higher storage modulus than the virgin plastic

[175]

PBS/carbon black

The mechanical performance of the material improved in impact strength, 131%, max flexural stress, 17%, tensile stress at yield, 5%, and storage modulus, 19%. The thermal and electrical conductivity of the bionanocomposite increased 50% and 102%, respectively

[176]

Pea protein/nisin

Antimicrobial and mechanical properties of the bioplastics are modified by adding nisin

[177]

33

34 Biopolymer-based metal nanoparticle chemistry for sustainable applications

nanotechnological areas such as tissue engineering, “smart nanodevices,” drug delivery, and protein purification [181]. Furthermore, bioplastics have the potential for application in architecture. Recent advances in the mechanistic development of bioplastic materials and the computer-aided design approach and robotics have improved the ability to construct more sustainable architectural systems. They can derive the future of architecture as green composites [182, 183]. There has also been an increasing demand for durable biobased products for electronic, optical, household, consumer, automotive applications, etc. [178, 184–188].

1.5 Conclusion and future perspective According to the report, the utilization of petroleum-based polymers makes numerous adverse damages to the environment. Most of the plastic wastes that end up in the landfill cause pollution with the accumulation of chemicals. On the other hand, biopolymers can be converted into biomass with the help of living organisms, which will be later used as manure in agriculture. Disposal of biowastes in landfill creates environmental problems due to the huge production of CO2 and NH3. Since the wastes contain a large number of sugars, carbohydrates, and cellulose, their industrial application in an eco-friendly way is a good approach. The future market for biopolymers is significantly increasing due to their sustainability. There is a possibility to control marine pollution with the increasing use of biopolymers for the green economy. The carbon footprint of biopolymers can be much lower than that of petroleum-based equivalents. Bioplastics can provide excellent biodegradability, helping the world deal with the increasing problems of litter, particularly in rivers and seas. Durable plantbased bioplastics can also be recycled as well as their conventional equivalents. Besides the sustainability and advantages provided by the preparation and utilization of bioplastics, there are also some concerns: Ø The use of bioplastics over conventional plastics is now limited due to their high cost, which is a concern for their development. Ø There should be programs to enhance consumer awareness to increase the demand of bioplastics, as well as new laws facilitating companies to produce them. Ø Improved interactions between academia, industry, and government institutions are needed. Ø As with conventional plastics, future material developments should concentrate not only on novel monomers or polymers but also on further development of existing polymers through the creation of copolymers and terpolymers’ blending and addition. Ø Further studies need to focus on the design and preparation of new bioplastics with high degradation rates in soil and on the safety of environmental microorganisms.

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Ø Fast biodegradation of plastics is not desired in most cases, since plastic is a valuable material (as a finished good), a raw material (for conversion to chemicals for reuse in the value chain), and energy source (via anaerobic digestion or incineration).

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Chapter 2

Polysaccharides in food industry Mahmoud Nasrollahzadeh, Zahra Nezafat, Nasrin Shafiei, and Fahimeh Soleimani Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

2.1

Introduction

Polysaccharides are polymeric carbohydrates, which include monosaccharide units connected by glycosidic bonds. Polysaccharides broadly exist in the nature and can be synthesized by plants, animals, and microorganisms. Polysaccharides, originated from plants such as starch and guar gum, microbes such as xanthan and algae, and animals such as glycogen and chitin, are often applied in the food industry [1]. The most widely used polysaccharides in the food industry are shown in Fig. 2.1 [2]. In the nature, polysaccharides exist as linear or branched polymers, which help as a main energy resource. Polysaccharides also exist as hydrated complexes in exo and endo central matrices of plants and marine organisms [2]. Polysaccharides have various biological functions such as storage of energy (starch), cell wall architecture (cellulose), and cellular communication (glycosaminoglycans) [3, 4]. Polysaccharides are such big macromolecules, which may have molecular weights of up to millions of Daltons [5, 6]. Polysaccharides might be homopolymers or heteropolymers comprising of neutral (pentoses and hexoses) or anionic sugars (uronic acid), and may or may not contain linked, nonsugar compounds [7]. Polysaccharides are broadly applied in food processing and preparation [8–11]. Occasionally, they are present for technological aims, for example, as process aids to stabilize emulsions and suspensions and offer the physical structure necessary for packaging or delivery. More frequently, the thickening and gelling properties of these biopolymers are used to improve or standardize the eating quality of a product [11]. Polysaccharides frequently change the food matrix with respect to the changes in their rheological properties, which increases water retention and gel formation, leading to the thickening of the food matrix. Their gelling capability has allowed the improvement of various processed food products such as jams, jellies, salad dressings, and sauces. In the food industry, polysaccharides are generally applied at levels as low as 1–3 wt.% [12]. Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00002-0 Copyright © 2021 Elsevier Inc. All rights reserved.

47

L-Guluronic acid

D-Mannuronic acid

polysaccharides

FIG. 2.1 Some polysaccharides and their structural illustration [2].

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Other applications include the stabilization of foams, emulsions, and suspended particulate materials, better adhesion, preventing or reducing the formation of ice crystals in frozen foods and connecting to other biomolecules [13]. Polysaccharides control ice crystal formation in frozen food products and stabilize products going through successive freeze-thaw cycles. They have also exhibited excellent properties as substitutions for fats in diverse products [14]. Though the mainstream of the polysaccharides currently being applied in the food industry are of plants and seaweed origins, polysaccharides from microorganisms with new and unique physical properties have recently emerged as significant biopolymers. Today, polysaccharides such as gums from microbial origin have been shown to be novel polymeric materials economically competing with other natural gums such as Arabic gum and carrageenan formed by plant and marine algae [15, 16]. The use of microbial polysaccharides has some advantages such as easy recoverability and genetic modification to produce new products [17]. Some of the microbial polysaccharides commercially applied in the food industry are bacterial cellulose, pullulan, xanthan gum, gellan gum, bacterial alginates, levan, and hyaluronic acid [18, 19]. While several food polysaccharides are not digested in the upper gastrointestinal tract of humans, they frequently aid functions other than having nutritional value. For instance, plant cell wall polysaccharides such as arabinoxylans and β-glucan present in cereal-based foods and “plant gums” are applied as thickeners, emulsifiers, emulsion stabilizers, gelling agents, and encapsulating agents [20]. These nondigestible polysaccharides are significant for health since they are considered dietary fibers, which promote colon health, regulate postprandial blood glucose levels, and reduce serum cholesterol levels [21]. In spite of the fact that nature offers different sources of polysaccharides and that scientific research on their utilization as food materials is increasingly active, a moderately low number of polysaccharides are allowed to be applied as food ingredients. For instance, in the European Union (EU) and Switzerland, among the 334 allowable food additives (identified by an E number), less than 40 are polysaccharide-based (native or structurally modified). The differences among food ingredients and additives are mainly due to the quantity applied in any given product. Food components can be consumed alone as food such as starch while food additives such as carboxymethyl cellulose are applied in minor quantities (commonly less than 2%) relative to the total food composition. However, they play a major role in the food products. A huge number of polysaccharides applied as food ingredients are plant-based. For instance, guar gum (galactomannan) is extracted from the seeds of the leguminous plant Cyamopsis tetragonolobus and gum Arabic is an exudate obtained from the sap of Acacia trees (Acacia seyal or Acacia senegal) [1]. O-Acetylgalactoglucomannan (GGM) from spruce (Picea abies) is an example of a very interesting wood-based polysaccharide, which can be applied in food. However, GGM is not currently in the list of the accepted food ingredients including food

50 PART

I Biopolymer-based structures and the food industry

FIG. 2.2 Polysaccharide structure of spruce galactoglucomannan (GGM) [1].

additives [22]. The polysaccharide structure of GGM involves (1 ! 4)-linked β-D-mannopyranosyl and β-D-glucopyranosyl units with (1 ! 6)-linked galactose side units attached to mannose units (Fig. 2.2) [1]. Nevertheless, GGM refers to the complete extract mixture obtained from wood, in which polysaccharides are the main constituents [1]. Various polysaccharides have been reported to have applications in the food industry since they are safe, biodegradable, environmentally friendly, biocompatible, and edible molecules. Polysaccharide-based biopolymers are diverse and complex since the bonds linking the sugars can be designed at different positions. Many polysaccharides are comprised of branched structures chemically modified by the addition of other molecules. Herein, we explain some of the polysaccharides applied as biopolymers, which play a critical role in the food industry [2].

2.2 Structural organization of polysaccharides The basic structure of polysaccharides has the following characteristics [6]: l l l l l l l

Presence of various sugars (monomers) Substitute groups such as sulfate or phosphate and substitution points Sequence of sugars Glycosidic linkages: (1 !4), (1 ! 3), and (1 ! 2) Anomeric configuration (α or β configuration) Ring size (pyranose or furanose rings) Unconditional configuration (D or L)

Table 2.1 shows the kinds of glycosidic linkages of polysaccharides [12]. Polysaccharides in the solid state have diverse kinds of secondary structures, each displaying a unique set of helix parameters. The type-A helix is a ribbonlike structure consisting of structural polysaccharides such as cellulose, hemicellulose, or pectin. Alginate and carrageenan also have a type-A secondary structure containing polysaccharides with β-(1,4) linkages. These polysaccharides show relatively robust interchain hydrogen bonding and elimination of

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TABLE 2.1 Kinds of glycosidic linkages in several polysaccharides and their occurrence. Polysaccharide

Glycosidic linkage

Occurrence

Alginic acid

(1!4) (linear)

Seaweed

Amylose

(1!4) (linear)

Plant

Amylopectin

(1!4), (1!6) (branched)

Plant

Carrageenan

(1!3), (1!4)

Seaweed

Cellulose

(1!4) (linear)

Plant cell wall

Dextran

(1!6), with branching at (1!3) and occasionally at (1!4) or (1!2)

Microorganism (Streptococcus and Leuconostoc spp.)

Glycogen

(1!4), (1!6) (branched)

Mammals

Laminarin

(1!3) (linear)

Seaweed

Unnamed

(1!3), (1!6) (branched)

Fungi, mushroom

Xanthan

(1!4), with branching at C3

Microorganism (Xanthomonas spp.)

water. Storage polysaccharides such as amylose, amylopectin, and glycogen form type-B helix. These polysaccharides are relatively less compact with a large number of residues (n ¼ 8) per turn. The hollow helix is rather water soluble and unstable in solutions except in a double helix form. The type-C helix, or flexible coil, is formed by a range of monomers joined by β-(1,2) linkages. This structure is anticipated to display substantial steric hindrance and hence a low probability of occurrence [6, 12]. The shape of a biopolymer in a solution, gel, or solid state is called its tertiary structure. Dry polymers have monocrystalline and amorphous tertiary structures. Heating results in a glassy state of the polymer. In the case of glassy polymers, no rotation around the bonds connecting adjacent monomers is observed in the polymer backbone. The backbone remains rigid and the viscosity of the system is very high. The glass transition temperature (Tg), when the backbone mobility begins to occur, can be measured by various techniques such as rheology and differential scanning calorimetry. Tg is limited to certain polysaccharides such as amylopectin, pullulan, and guar gum. Water is an efficient plasticizer for biopolymers and by adding water, Tg decreases. Tg has a considerable effect on processes such as caking and crystallization, and operations such as drying, extrusion, and flaking [6, 23–25]. In the dissolved state, polymer-polymer contacts are switched by polymer-solvent interactions, leading to a random conformation [26, 27].

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2.3 Major functions of polysaccharides in a food system Table 2.2 displays different factors determining the functions of polysaccharides in food systems [12, 28–30]. Some of the most important ones are described in the next section.

2.3.1 Water-binding capacity Polysaccharides are capable of binding to water and dispersing it in the food. Differences in the water-binding ability exhibited by polysaccharides from different sources as seaweeds, crustacean shellfish, and microorganisms are due to the various functional groups in their structures, which powerfully interact with water. For example, alginate contains many carboxylic groups, carrageenans, depending on their type, contain variable amounts of sulfonic groups, and chitosan has amino groups in its structure. These groups simplify the binding of water as much as 98–100 times of their weight [6]. Xanthan, guar gum, and

TABLE 2.2 Different functions of polysaccharides in food. Function

Application

Adhesive

Icings and glazes

Binding, texture modification

Pet foods

Coating

Confectionery

Emulsification

Salad dressings

Encapsulation

Powdered flavors

Film formation

Protective coatings, sausage casings

Fining (colloid precipitation)

Wine and beer

Gelling agent

Confectionery, milk-based desserts, jellies, pie and pastry fillings

Inhibition of ice-crystal formation

Frozen foods, pastilles, sugar syrups

Stabilization

Ice cream, salad dressings

Stabilization of foam

Beer

Swelling agent

Processed meat products

Syneresis inhibition

Cheeses, frozen foods

Synergistic gel formation

Synthetic meat gels

Thickening agent

Jams, sauces, syrups, pie fillings

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alginate are able to bind 230, 40, and 25 mL of water per gram, respectively. Propylene glycol alginate (PGA) and locust bean gum (LBG) are the commonest water binders. Nuclear (1H) magnetic methods have been applied to measure the degree of water binding in polysaccharide gels [31]. The water-binding properties of polysaccharides, and therefore their performance in different foods are interrelated to their rheological properties [30, 32, 33]. The capability of polysaccharides to undergo gelation under mild conditions of temperature and pH and the presence of Na or K ions provide different benefits concerning the modification of food texture, matrix stabilization, and many other functions beneficial for adding value to different food commodities [6].

2.3.2

Gelation

The capability to undergo gelation is perhaps the most significant functional property of polysaccharides. A gel is an intermediate state between a solution and a solid. The term “gel” is derived from gelatin and the words “gel” and “jelly” both originate from the Latin gelu for “frost” and gelare, meaning, “freeze” or “congeal.” Gels are solid-like materials, which are elastic and have some fluid characteristics. A gel is a solid made up of at least two components, one of which (polymer) forms a three-dimensional network in the medium of the other component (liquid). Gels can be classified as covalently cross-linked gels, entangled networks, and physical gels [34]. Basically, food gels are physical gels. Physical gels are commonly prepared by cooling heated solutions of polymers. Gels melt upon heating, showing their thermoreversible characteristics. Such gels are formed by noncovalent interactions such as hydrogen bonding and hydrophobic and ionic interactions, which oscillate with time and temperature [12]. Through these interactions, junction zones are created between the polymer molecules. These junction zones are the entanglements happening at network junctions due to hydrogen bonding and ionic interactions. An elastic gel is formed when the junction zones between polysaccharides and solvents are formed in solutions. A very amount of solvent is necessary to maintain the flexibility and elasticity of the gel. Polysaccharides such as cellulose, which have a branched structure, cannot form these junction zones. Therefore, they cannot form strong elastic gels [12]. Chemical gels are thermally irreversible [34, 35]. In a food system, gel networks are made because of the interactions of polysaccharides with water under suitable conditions of temperature, pH, and pressure. Polysaccharides are capable of holding a large amount of water in the network, which stabilizes the system [12]. The first studies in this field were carried out by Ferry in 1948 [36]. In the field of gel formation, polysaccharides have been of special attention due to their important roles in determining the texture of food. Polysaccharide gel formation occurs through a disorder-to-order transition made by cooling. By reheating the gel, the process is reversed. The technique by which cross-links between individual chains is made depends on the individual polysaccharide. The concentration and kinds

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of junction zones in the gel network control the features of polysaccharide gels. Depending on the degree of interaction of the polymers, the gel can have different types including rigid, flowing, brittle, firm, soft, spreadable, sliceable, rubbery, or grainy. If the junction zones are short and the chains are not kept together powerfully, the polysaccharide molecules will be divided under physical pressure or with a small enhancement of temperature [12]. The gels become more brittle as the concentration increases [35, 37]. A polysaccharide gel usually contains the highest amount of water (98%–99%) and the lowest amount of polysaccharide (1%–2%) [38, 39]. Polysaccharide gels are reversible compared to other gels. The word weak gel is applied to distinguish a gel-like polymer dispersion from a real gel. A weak gel displays robust shear or thinning behavior, which simplifies the handling of these gel materials at a moderately high shear rate. An aqueous solution of xanthan is the most widely used weak gel in the food industry. Weak gels of polysaccharides such as curdlan and carrageenan have been described [12, 35].

2.3.3 Emulsions and emulsifiers Emulsions and foams are significant physical forms, which affect the improvement of colloidal systems in various products including food items. A colloid is defined as a dispersion of distinct particles in a continuous medium. Emulsions and foams are good distributions of oil, water, or air (droplets and air bubbles) in an immiscible liquid. Usually, an emulsion contains a minimum of two immiscible liquids (frequently oil and water), one of the liquids being dispersed as minor spherical droplets in the other. Gravitational separation is one of the most usual reasons for instability in food emulsions and might take the form of either creaming or sedimentation, depending on the comparative densities of the dispersed and continuous phases. Food emulsions can be generally of three kinds including (1) oil-in-water (O/W) or water-in-oil (W/O) emulsions, which refer to the dispersion of oil and water droplets in the aqueous and oil phase, respectively; (2) foam, in which air (gas) bubbles are dispersed in an aqueous phase; and (3) sol, which is small solid particles dispersed in a liquid medium. In addition, the multilayer emulsions of oil and water such as W/O/W and O/W/W are possible. Figs. 2.3 and 2.4 show various types of emulsions [40] and formation of conventional and multilayer emulsions, respectively [12, 41]. Best food emulsions are oil-in-water emulsions comprising of milk, cream, mayonnaise, sauces, salad dressings, custard, made-up meat products, and cake batter. Examples of water-in-oil emulsions are butter, margarine, and spreads. Emulsions of O/W, W/O/W, or O/W/W kind are usually applied as delivery systems for bioactive lipids in the food and other industries. Emulsifiers are applied to simplify the formation, stabilization, and controlled destabilization of emulsions. The most broadly applied polysaccharide emulsifiers in food applications are gum Arabic (Acacia senegal), modified starches, modified celluloses, some kinds of pectin, and some galactomannans [12, 42–44].

Polysaccharides in food industry Chapter

FIG. 2.3 Types of emulsions [40].

FIG. 2.4 Illustration of the formation of conventional and multilayer emulsions [12].

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2.4 Major food applications of polysaccharides Polysaccharides can be used as excellent additives for food formulations owing to their different functional properties, which permit them to act as gelling and thickening agents, stabilizers, water retention compounds, emulsifiers, ingredient binders, viscosity modifiers, and foam stabilizers (Fig. 2.5) [12]. They postpone crystal growth in ice cream and confections, and products comprising fluid and mixed gels improve satiety. Weak gels of biopolymers are often applied in food applications. Given their natural origin, they are quite nontoxic, unlike many synthetic food additives. Owing to their exciting functional properties, polysaccharides, together with sugars, corn syrup, and dextrose, represent 90% of additives applied. The food-related functions of polysaccharides are briefly discussed in the next section [12, 45–47].

2.4.1 Texture improvement In the food industry, polysaccharides are widely used as thickeners and stabilizers in various foods such as sauces and dressings because of their appropriate properties at concentrations as low as 0.5%–1%. The viscosity and thickening properties are dependent on various factors such as polymer concentration, molar mass, stiffness of the polymer, temperature, shear rate, and solvent characteristics (e.g., ion concentrations, nature of the ions, pH). These factors can give rise to the necessary food texture [12]. Polysaccharides are applied to enhance the stability of foods, control syneresis, improve flavor, replace fat, and enhance fiber contents in foods. Foods, the texture of which is affected by using polysaccharides and their interactions with water, include frozen desserts, confectioneries, salad dressings, puddings, gravies, cheese, pie fillings, and a diversity of diet foods. Entrapment of plentiful water or air in gel matrices decreases the caloric density and as a result improves saturation [48]. Polysaccharide foams and gels have encouraged modern chefs to improve light and attractive textures [12]. Polysaccharides have found many usages in bakery Factors determining the functions of polysaccharides in a food system

FIG. 2.5 Schematic representation of factors determining the functions of polysaccharides [12].

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products. Hydrocolloids comprising polysaccharides are applied in commercial baking to simplify processing, compensate for differences in raw materials, guarantee constant quality, and maintain freshness and food properties. These additives improve dough handling properties and stability, viscoelastic properties, and other quality-related criteria such as water absorption and particular loaf volume. In addition, they can replace the wheat protein gluten [23]. The improvement of fruit analogs is a prosperous area in the food industry. The benefits of these fruit analogs are uniformity in size and shape, reduced sugar content, enhanced flavor, and color stability during storage. The products should have the crispy texture of fresh fruits, but the improper texture has been an important problem. Polysaccharides affect the current properties of fluid fruit fillings. The addition of gums to fruit fillings affects their seeming viscosity, changing with the kind of gum, amount added, and shear rate. The addition of guar gum, locust bean gum, and carboxymethylcellulose enhances the consistency and flow indices, whereas xanthan gum and κ-carrageenan reduce these properties [12, 37, 49].

2.4.2

Oil emulsification

Polysaccharides play a significant role in the development of emulsions and food foams. Gels of polysaccharides function as texture modifiers by thickening or gelling the continuous phase in the presence of a dispersed fat phase (emulsion gels). Polysaccharide emulsifiers have certain common functional features resembling those of other food emulsifying agents such as proteins, surfactants, and solid particles. Polysaccharides, either alone or in combination with other hydrocolloids, are useful in stabilizing foams and dispersions. If these stabilizers are not present, the dispersion of the oil solution is inherently unstable due to aggregations. The most widely applied polysaccharide emulsifiers in food applications are gum Arabic (Acacia senegal), modified starches and celluloses, pectin, and galactomannans. Some semisolid foods are mixtures of high moisture gel matrices and dispersed microstructural elements such as fiber, globules, or air bubbles (e.g., frankfurters, cheeses, mousses). Polysaccharides enhance texture by protecting the solids dispersed in a medium such as chocolate in milk, air in whipping creams, fat in salad dressings, canned meats or fish, marshmallows, and jelled candies. Other applications of polysaccharides include carbonated soft drinks, beverage emulsions, ice cream, sauces, and dressings [12, 44, 50].

2.4.3

Flavor release

Polysaccharides can be added to change the flavor and aroma (in addition to the texture) of foods. The distribution of aroma compounds is affected by the viscosity of the food which, in turn, is controlled by the presence of hydrocolloids [51]. Polysaccharides preserve volatile flavor compounds in various food systems, ranging from salad dressings to dessert gels. Since flavors are frequently

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present in foods at small levels, a rather small amount of binding can have a noteworthy result on the apparent flavor. However, in food products comprising of high levels of water, the addition of flavors to most of the polysaccharides is minimal [37].

2.4.4 Polysaccharides as dietary fibers Dietary fiber is a material, which includes plant cell walls, structurally complex and chemically diverse nonstarch polysaccharides, and other related substances. Unlike other nutrients, fiber is not attacked by the enzymes of the stomach and small intestine and reaches the colon undegraded. In 2001, the American Association of Cereal Chemists defined dietary fiber as “that fraction of the edible part of plants or their extracts or synthetic analogs, which are resistant to digestion and absorption in the human small intestine, generally with complete or partial fermentation in the large intestine.” Recently, this definition has been expanded to include not only plants but also fibers of animal origin such as chitosan. The main advantages of dietary fiber are a reduction in the intestinal absorption of nutrients, a reduction in colonic luminal toxicity and systemic results, adaptation of colonic microflora, and direct action on colonic mucosa. Foods comprising soluble fiber include whole-grain foods such as breakfast cereals, multigrain bread, vegetables such as carrot and celery, oatmeal, nuts, legumes, whole-grain barley, and fruits such as pears, ripe strawberries, and bananas. Various polysaccharides such as chitosan, alginate, and carrageenan can act as dietary fibers [12, 52]. Fig. 2.6 shows the benefits of using fiber in food. Table 2.3 lists the technological functional properties of dietary fibers [12].

2.4.5 Control of syneresis Syneresis is the unfavorable separation of water observed in many foods. Freeze-thaw stability is a significant property of starch-based products, which allows them to resist physical changes happening through freezing and thawing. However, when starch pastes or gels are frozen, phase separation always happens due to the formation of ice crystals. Thawing leads to syneresis since water can simply penetrate through the dense network of starch pastes and gels. Separation of water is due to the amylopectin retrogradation in the starch-rich phase. The amount of syneresis water can be applied as an indicator of the trend of starch to retrograde. This property can be estimated by gravimetric measurement of the water of syneresis, which separates from starch pastes or gels. Due to the excellent capability of polysaccharides to bind water, they can control syneresis. For instance, tapioca starch forms a clear paste through processing with a bland taste and high viscosity, which are beneficial in various food applications. However, the tapioca starch is apt to retrogradation through freezing and thawing [12, 33, 38].

f

FIG. 2.6 Various advantages of fiber in foods [12].

TABLE 2.3 Technological functionality of dietary fibers. Functional property

Advantage

Chelating capacity

Several types of fibers possess the capability of binding minerals, favoring reduced metal-induced functions such as lipid oxidation

Fat-binding capacity

The porosity of the fiber rather than molecular affinity affects the fat-binding capability. Water-soaked fibers have more fat-binding capacity

Gel-forming capacity

Fibers such as carrageenans, chitosan, and pectin form gel networks, which absorb water and solutes in the network. Network formation is dependent on factors such as temperature, concentration, ions, and pH

Viscosity

Soluble fibers from algae form highly viscous solutions, a property which also makes them beneficial as thickeners in foods

Water-holding/binding capacity (WHC)

Soluble fibers such as algal fibers, pectin, gums, and glucans have a higher WHC than cellulosic fibers. Algae fibers, depending on their type, can bind water 20 times their own weight

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2.4.6 Gluten-free bakery products Gluten is the main ingredient in wheat, which improves the quality of bread and is a necessary structure-binding protein. In pasta products, gluten forms a viscoelastic network, which surrounds the starch granules, thus limiting swelling and leaching during boiling and making this product group a relatively rich source of resistant starch. In bread making, interactions among the gluten protein and duff polysaccharides (starch, pentosans) are significant in the formation of the resulting fixed or flowing dough, thus determining the product texture. About 1% of the world’s population suffers from celiac (gluten-sensitive enteropathy) such that there should be no gluten in their diet. For this purpose, the request has grown for gluten-free products. However, the discovery of alternatives to gluten with similar properties has established an important challenge for food scientists. Several water-soluble polysaccharides such as xanthan mimic the viscoelastic properties of gluten and can be applied for the improvement of gluten-free products [12, 23]. Today, many gluten-free products are produced such as cookies, muffins, and cakes, which have the same appeal as gluten-free products. About 25% of β-glucan is used in these products instead of gluten. Products comprising the ingredient are qualified for the FDA heart health [12, 53, 54].

2.4.7 Stability of polysaccharides to processing The stability of polysaccharides used to improve food products is very important because some of them change at temperatures of 100°C or higher. For example, when starch is heated in the absence of water, it experiences thermal degradation, resulting in lower paste viscosity upon cooking [55]. Polysaccharides might also undergo hydrolysis owing to interactions with acids in foods such as acetic acid (vinegar), citric acid (fruit juices), and potassium acid tartrate (cream of tartar). In general, such hydrolysis is unfavorable as it can lead to the loss of the capability of polysaccharides to gel or thicken the food. Carrageenan is highly susceptible to acid interactions unlike alginate. In addition, polysaccharides might interact with ionic species in foods, particularly cations. The result can sometimes reduce the dispersion viscosity [56].

2.5 Important factors for the use of polysaccharides in the food industry For the effective use of polysaccharides in food products, it is significant to understand various factors such as their molecular properties, interactions among the food materials, and the effect of processing conditions (Table 2.4) [12]. Addition and replacing of different materials can lead to variations in the food structure. Addition of even a single polysaccharide needs a full understanding of the hydrocolloidal structure and function in real food systems.

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TABLE 2.4 Factors affecting the utilization of a specific polysaccharide in food product improvement. Factors

Influence

Rheological properties

The result of a polysaccharide on texture is significantly dependent on its hydrodynamic properties viz., the volume it sweeps out in solution and its effects on shear thinning at a high shear rate

Molecular properties

The molecular variety of a simple hydrocolloid affects textural properties in different ways by its impact on gelation, oil emulsification, and foam stability

Sugar effects

The texture of such products as ice cream and desserts is considerably influenced by the presence of sugar. In addition, gelation is influenced by the sugar reactivity of some hydrocolloids

Salt effects

Incorporation of salt to consumer taste affects the behavior of hydrocolloids; for instance, cations such as Na+, K+, and Ca2+ affect the gelation of alginate and κ-carrageenan

Process conditions

Temperature and shear rate importantly affect the rheological properties and hence the texture of food products

Mixed hydrocolloid systems

The effects can be added (formation of mixed gels), antagonistic (phase separation), or synergistic, depending on the kind of hydrocolloid. For instance, the gel strength of xanthan is synergistically improved by locust bean gum (LBG)

Factors to be considered when incorporating polysaccharides in food products include their gelation kinetics, viscosity, and gel properties, the effects of the industrial process such as cooling, shearing, and dehydration, effects of other systems on the polymers, how amenable they are to processing, and other complex composite properties, in addition to their result on texture improvement, phase separation, flavor release, and the overall stability and quality of the final product. The appropriate use of additives under suitable processing conditions can lead to a food microstructure, which produces a perfect texture and stability [37, 57]. In addition, the incorporation of polysaccharides requires the understanding of the relationship between food structure and its sensory properties. Commercial food products, which comprise polysaccharide-based thickeners, can be less than favorable with regards to their sensory perception [48].

2.6

Microbial polysaccharides in food industry

Microbial polysaccharides improve the quality, texture, and flavor of the food as thickeners, stabilizers, texturizers, and gelling agents [58–60]. Microbial

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FIG. 2.7 Properties of polysaccharides and their applications in the food industry [61].

polysaccharides have properties, which can meet the expectations of the food industry (Fig. 2.7) [61–65]. In addition, microbial polysaccharides play an important role in the appearance, color, and flavor of prepared foodstuffs [62, 66, 67]. Various microbial polysaccharides secreted by different organisms and their applications are shown in Table 2.5 [6, 63, 68, 69]. Some of the most important ones are listed in the next section.

2.6.1 Xanthan Xanthan gum was first discovered in the 1960s and commercialized in the 1970s [69, 70]. Xanthan is a microbial polysaccharide secreted by Xanthomonas campestris and produced in tons in the aerobic fermentation process for marketable application in food and pharmaceutical industries. An important feature of xanthan is its high viscosity at low concentrations, which makes it an exceptional food additive for syruping, stabilizer, and thickening agent. Another property, which makes xanthan appropriate in the food industry, is the great shear thinning, viz. good pourability [19, 63]. Xanthan is replaced in various low-calorie drinks to enhance the thinning consistency where the total or partial sugars are replaced by synthetic sweeteners. Furthermore, xanthan can act as a stabilizer in most liquid and semiliquid foods and provide a physical form in most dairy products. Since xanthan is stable at low temperatures and freezing,

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TABLE 2.5 Microbial polysaccharides with the name of producer microorganism and their role in the food industry. Microbial polysaccharide

Organism(s)

Application in food industry

Xanthan

Xanthomonas campestris

Gelling agents for cheese spreads, ice creams, puddings, and other deserts

Pullulan

Aureobasidium pullulans

Food additive, providing bulk and texture. It can be used as a food additive in low calorie foods and drinks, as an alternative for starch or other fillers

Glucan

Saccharomyces cerevisiae

Glucans resist breakdown when attacked by digestive enzymes, and thus can be used as noncaloric food thickeners

Gellan

Pseudomonas elodea

Gellan can be used as a gelling agent in frostings, glazes, icings, jams, and jellies

Levan

Alcaligenes viscosus

Levan can be used as a food additive with prebiotic and hypocholesterolemic effects

Alginates

Azotobacter chroococcum and Azotobacter vinelandii

Used as thickeners, stabilizers, and gelling agents in jams, sauces, soups, and dairy products

Dextran

Leuconostoc mesenteroides and Leuconostoc dextranicum

Used as a viscosifier. A film of dextran is used in frozen foods; especially ice cream

Curdlan

Alcaligenes faecalis

Curdlan is used in texture modification and improves viscosity. It is also used as a gelling agent in processed foods, sauces, and freezedried foods

Acetan

Acetobacter xylinum

Acetan is used as a viscosifier and gelling agent in the production of sweet confectionery and vinegar

Emulsan

Acinetobacter calcoaceticus

Emulsan acts as an emulsifying agent, stabilizing hydrocarbon/water emulsions at very low concentrations (0.1%–1.0%)

Kefiran

Lactobacillus hilgardii

Kefiran improves viscoelastic properties of acid milk gels Continued

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TABLE 2.5 Microbial polysaccharides with the name of producer microorganism and their role in the food industry—cont’d Microbial polysaccharide

Organism(s)

Application in food industry

Welan

Alcaligenes spp.

Production of jellies, beverages, dairy products, and salad dressings

Scleroglucan

Sclerotium

Improvement of frozen or heattreated edibles, such as Japanese cakes, steamed foods, rice crackers, and bakery products

Reproduced with permission from Jindal N, Khattar JS. Microbial polysaccharides in food industry. In: Grumezescu AM, Holban AM, editors. Biopolymers for food design. Handbook of food bioengineering. Academic Press, Elsevier; 2018. p. 95–123.

it is the main additive in the frozen food industry. Xanthan is widely applied in bakery products to help retain water in baking food and thus increase the shelf life of the food. It is applied in low-fat foods to enhance the viscosity of the aqueous phase and stabilize food systems such as mayonnaise, cheese, ready to eat meals, etc. [71]. For decades, xanthan has been accepted by the FDA as an allowable additive and has been widely used in the food industry [63]. Fig. 2.8 shows several foods in which xanthan is applied.

2.6.2 Gellan Gellan gum is an extracellular polysaccharide synthesized using fermentation by Sphingomonas elodea [72, 73]. Gellan is a linear, anionic heteropolysaccharide with a straight chain consisting of D-glucose, L-rhamnose, and D-glucuronate building blocks in a molecular ratio of 1.5:1:1. The chain consists of tetrasaccharide repeated units in which β-(1 ! 4)-linked glucose, glucuronate, glucose, and rhamnose in α-(1 !3) linkage are bonded [6, 74]. Fig. 2.9 shows the structure of gellan [75]. The presence or absence of acyl groups on the gellan gum alters its physical and functional properties. Gellan gum is simply dispersible in cold and hot water. When the concentration of gellan in solution is high, it forms a network-like structure referred to as demoldable gel. However, if the concentration of gellan is low, it forms a so-called fluid gel. To improve the rheology, stability, and heat performance of solutions, gellan is mixed with other gelling and nongelling hydrocolloids [76–78]. To form soft gels, gellan is combined with xanthan or carboxymethyl cellulose [79]. Gellan was accepted by the

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FIG. 2.8 Applications of xanthan in food industry.

D-Glucose

D-Glucuronate

D-Glucose

L-Rhamnose

FIG. 2.9 Structure of gellan [75].

FDA as a food additive in 1992. It is applied as a stabilizer, gelling agent, and thickening agent in various food sources [73]. Gellan mainly stabilizes waterbased gels such as desserts and drinking jellies. Gellan can replace gelatin in several dairy products such as yogurt and sour cream in vegan items. Moreover, it is also applied in low calorie (sugar-free) jams in which pectin is not

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functional, fruit preparations, yogurt, sauces, nonfat salad dressings, and films. Furthermore, gellan can be used in the confectionery industry to reduce the setting time and inhibit sticking with candies when exposed to a warm environment [80, 81]. Although Galen has many advantages, it is the most expensive food gum. The low productivity and requirement for difficult and costly downstream processing steps of gellan impair its economic viability of microbial production [23, 82, 83].

2.6.3 Pullulan Pullulan is a linear, homopolysaccharide consisting of maltotriose as the building block. Three glucose units of maltotriose are linked by α-(1 !4) glycosidic bonds while maltotriose units are linked by α-(1 ! 6) bonds (Fig. 2.10) [6, 84, 85]. Pullulan is an extracellular glucan prepared by fermentation by the fungal strain Aureobasidium pullulans generally referred to as “black yeast” [72, 86]. Pullulan is a stable compound, which forms a viscous solution when dissolved in cold or hot water, but the gel does not form. It does not dissolve in any organic solvent except for dimethylformamide and dimethyl sulfoxide [87, 88]. A characteristic feature of pullulan is that it is a tasteless, odorless white powder. The solution of pullulan is stable over a wide range of pH values and it is heat resistant [89, 90]. Pullulan is used as a binder, thickener (0.2%–3%), and coating agent in food. Generally, pullulan is applied in instant beverages, creams, icings, soy sauces, other sauces, desserts, confectionery, and so forth. Pullulan is used as a low-calorie food additive and replaces gelatin in coatings [15, 91]. Pullulan has mainly been applied to make snack foods in Japan based on cod roe and powdered cheese, but it has to be applied at low doses as it is slowly digested in the human body [19, 92]. In the United States, FDA accepted pullulan as a safe compound in 2002. In the European Union, it was lately accepted as a food additive (E 1204) for capsules, tablets, and films under

FIG. 2.10 Structure of pullulan [6].

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directive 2006/52/EC. Application of pullulan in the food industry is also allowed in some Asian countries, Russia, and some South American countries [93].

2.6.4

Alginate

Alginate is mostly derived from the liquid bacterial cultures such as Pseudomonas aeruginosa, Azotobacter chroococcum, and Azotobacter vinelandii [94]. Alginate has various properties such as thickening, gelling, and film forming, which cause it to be widely applied in the food and drink industries as one of the most important food additives. As a functional food ingredient, alginate is categorized with many other substances as a food additive used to improve food preservation and enhance flavor, taste, and appearance. Thickening is beneficial in sauces, syrups, toppings for ice cream, and so on. Gelling is essential in instant milk desserts and jellies, bakery filling cream, fruit pies, animal foods, and reformed fruit. Alginates are generally applied as thickening agents in jams, marmalades, and fruit sauces, as alginate pectin interactions are heat reversible and provide a higher viscosity than does either individual component [95]. In addition, alginates are applied to thicken desserts and savory sauces containing mayonnaise [96–98]. The common colloidal properties are significant when sodium alginate is added to ice cream or propylene glycol alginate (PGA) (Fig. 2.11) is applied to stabilize beer foam or suspend solids in fruit drinks. Furthermore, alginate is beneficial for water-in-oil emulsions such as mayonnaise and salad dressings [99]. PGAs are generally applied to retain foam stability including applications in mousse and other desserts [100, 101]. Salts of alginate (Na, K, and Ca) and alginic acid are applied in food as per GRAS (Generally Regarded as Safe) [63]. Alginates are accessible in a various range of viscosities, affording stability to foodstuffs under both high and low temperatures. Therefore, they have an extensive range of usages as gelling agents. Alginate in the form of gel at low temperatures is very beneficial in the restructuring of foodstuffs such as meat products, fruits, and vegetables, which may become damaged or oxidized under high temperatures. The most usual restructured foods produced by means of alginates are reconstituted onion rings and pimento sections for application in

FIG. 2.11 Conversion of alginic acid into propylene glycol alginate [99].

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olives. In both cases, the presence of alginate generates products of uniform size and consistency [95, 102]. In addition, alginates have a number of similar applications in meat [103–106], seafood [107], fruit [108–111], vegetables [112], and some extruded food products such as pastas and noodles [95]. Tedious use of alginates in bakery creams gives a cream with freeze/thaw stability and decreases the separation of the solid and liquid components (syneresis) [95]. Alginate can be applied to enhance the physicochemical and rheological properties of wheat flour noodles. The hydration properties (water absorption index, water solubility, and swelling power) of wheat flour are enhanced by increasing the ranks of alginate due to its high affinity to water. This is demonstrated in enhanced water absorption and dough improvement time of the flour and reduced tolerance of the dough to mixing. Furthermore, alginate has a significant use as a dietary fiber since it is not digestible [113]. Alginates are applied in combination with other hydrocolloids to thicken and stabilize ice cream. Although this allows the control of the product viscosity, it also increases heat shock resistance, decreases shrinkage and ice crystal formation, and gives the ice cream the desired melting characteristics [114]. The common applications of alginate in different food products are displayed in Table 2.6 [95, 99].

2.7 β-Glucan in food industry β-Glucans belong to a group of polysaccharides characterized by their location in the cell wall. Some microorganisms and cereals such as barley and oats are rich in β-glucans [115–119]. These polysaccharides are of excellent economic importance. In microorganisms, these compounds generally contain a linear central backbone of D-glucose linked in the β(1 ! 3) location with glucose side branch linkages β(1 !6) of different sizes (Fig. 2.12A) at diverse intervals along the central backbone [120, 121]. Other β-glucans, derived from cereals, are polysaccharides of glucose residues with β(1 !3) and β(1 ! 4) linkages (Fig. 2.12B) [120, 122]. General cereal sources of β-glucan are barley, oats, rye, and rice. Barley and oat are considered richer in terms of β-glucan with the content of 4%–7%. The US FDA (1997) and UK Joint Health Claims Initiative (JHCI) accepted the claim that oat β-glucan is effective in decreasing the cholesterol level of plasma and lowering the risk of heart disease [123]. Several health advantages of β-glucan have been reported in the literature, which show its appropriateness for incorporation into different food products. Some of the health effects include activity against colon cancer, depression of hunger, better gut health, improved stool bulk and elimination of toxic substances, anticonstipation, reduction of glycemic index, reduction of serum cholesterol, leveling of postprandial glucose level, and prevention of coronary heart disease [124–130]. Health effects may not be sufficient to use β-glucan in the large food industries. Of course, this is due to its favorable features, making it applicable as stabilizing, thickening, gelating, and emulsification agents. β-Glucan is the main factor for controlling the quality of the product [131]. Dietary fiber is the portion of the

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TABLE 2.6 Common usages of alginates in food products. Application

Remark

Foam stabilizer in beer

PGA offers better foam retention and avoids foam negative contaminants

Texturized foods

Alginate offers food products thermostability and the desired consistency

Bakery products

Alginate provides freeze-thaw stability and reduces syneresis

Fruit preserves

Alginate is usually applied as a thickening, gelling, and stabilizing agent in jams, marmalades, and fruit sauces. Alginate-pectin gels are heat reversible and offer better gel strength than the individual components

Ice cream

Alginate affords the perfect viscosity, prevents crystallization and shrinkage, and promotes homogeneous melting without whey separation. It is used in combination with other gums

Other

Alginate is applied in desserts, emulsions such as low-fat mayonnaise, sauces, and extruded foods (noodles and pasta). PGA is acid stable and resists loss of viscosity. It has unique suspension and foaming properties, which make it beneficial in soft drinks, milk drinks, sorbet, ice cream, noodles, pasta, etc.

Reproduced with permission from Brownlee IA, Allen A, Pearson JP, Dettmar PW, Havler ME, Atherton MR, Onsøyen E. Alginate as a source of dietary fiber. Crit Rev Food Sci Nutr 2005;45(6):497–510.

food, which resists digestion in the small intestine. However, the microflora in large intestine partially ferments it. The dietary fiber can be categorized into two classes including soluble dietary fiber (SDF) and insoluble dietary fiber (IDF) in which β-glucan is extracted from cereal and other sources and shows the features of both SDF and IDF. Thus, the improvement of β-glucan-rich products, which could decrease the incidence or slow progression of chronic diseases, is of great importance [132]. Although some researchers have incorporated β-glucan in cereal, meat, and dairy-based products; more examinations are still necessary for better understanding the role of this ingredient in other products [133–135]. For example, the molecular weight profile of β-glucan has a multidimensional result on the product improvement. It might affect the viscosity, gel formation, rheological properties, and other industrially important properties. On the other hand, it might also change particular health benefits, which are planned to achieve a particular goal [136]. Bread making with traditional methods has a lack of dietary fiber. However, there is always a request for high fiber white bread. Such kind of bread can be made with the inclusion of “Glucagel,” which is the trade name for β-glucan extracted from barley [137].

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(A)

(B) FIG. 2.12 Schematic representation of (A) structure of β(1!3) with ramifications β(1! 6) (B) β(1!3) with ramifications β(1!4) [120].

“Ricetrim” is another commercial soluble fiber brand in Asian markets. This brand is made up of rice bran and barley flour and is an excellent source of β-glucan. It can also replace fat in the manufacturing of coconut cream with good rheological properties. Other usages include cookies, pumpkin pudding, layer cake, dip for pot crust, taro custard, saut
e, and chicken curry [138].

2.8 Plant polysaccharides in food industry 2.8.1 Guar gum Guar gum is a nonanionic natural polymer from the polygalactomannan family, which is obtained from seeds of a plant of the Leguminaceae family, Cyamopsis tetragonolobus. The galactomannan molecule consists of chains of (1–4)-linked β-D-mannopyranosyl units with single α-D-galactopyranosyl units connected by

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(1–6) linkages to, on average, every second main chain unit. Guar gum is a water-soluble polysaccharide widely used in different industries since it gives high viscosities to aqueous solutions even at low concentrations (1%, w/v) [139, 140]. The thickening or high viscosity at a low concentration is the most appropriate functional property of guar gum for different food applications. The food industry is the major market for guar gum. The significance of this gum in food applications is due to its exclusive functional properties such as water retention capability, reduced evaporation rate, variation in freezing rate, modification in ice crystal formation, regulation of rheological properties, and involvement in chemical transformation. Another factor, which has led to the widespread use of gum in the food industry, is its low cost. The US Food and Drug Administration has given guar gum a status of generally recognized as safe; its maximum permissible limits in different foodstuffs have been listed in and are regulated by the Code of Federal Regulations Section 184.1339.8. According to this section, the maximum allowable limit for guar gum in any food material is 2% for fats, oils, processed vegetable and vegetable juices and 0.35% for baked goods and baking mixes. A summary of the different usages of guar gum is displayed in Fig. 2.13 [141]. Guar gum is widely used in the bakery industry to improve the physical properties and texture of baked goods, enhance shelf life by decreasing staling, prepare gluten-free breads, prepare bread by frozen dough, and as a dietary fiber

FIG. 2.13 Different uses of guar gum in the food industry [141].

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to produce products with a low glycemic index. The addition of guar gum through white bread preparation usually improves water absorption during dough preparation. The addition of a 1% guar gum in wheat flour increases water absorption by 8%. The improved water absorption capability of dough owing to the addition of guar gum is because of its hydrophilic nature and capability to absorb water [142]. There have been some reports on the use of guar gum in the production of low-fat biscuits and cakes [143, 144]. In addition, the use of guar gum in the preparation of gluten-free baked products has also been reported [145]. The addition of guar gum has also been displayed to decrease the rate of staling in different baked products such as chapatti bread and cakes [146–149]. Guar gum is a soluble dietary fiber, which is also effective in decreasing the glycemic index of different food products. Another example for the application of guar gum in the food industry is in dairy products such as ice cream (to avoid ice crystal growth and for textural enhancement), milkshakes (to avoid serum separation and add viscosity and shear resistance), yogurt (to improve texture and mouthfeel and avoid syneresis), aerated desserts (for gelation and foam stabilization), and slimming dietary products (for satiation and as a health-promoting dietary fiber). Guar gum is applied in the beverage industry as a thickener to enhance viscosity. Various properties of guar gum such as stability at low pH values usually found in beverages and solubility in cold water make it an excellent choice for the beverage industry. Since guar gum is an odorless and tasteless compound, adding it to beverages does not add any flavor or unnecessary taste [141]. In addition, by adding guar gum to the beverages, peak glucose levels significantly decrease. Therefore, guar gum also acts as a source of soluble dietary fiber in the beverage industry [150]. Guar gum is one of the most general hydrocolloids added to sauces and ketchups. The utilization of guar gum can prevent syneresis during freezing and afford stability during heating in cooking. There are several reports in the literature on the addition of guar gum to ketchup [151–154]. Guar gum is widely used in the production of noodles. Guar is the inexpensive and most widely used hydrocolloid for noodles. It acts as a water binder and decreases the decomposition of noodles in soup during preparation [141]. Guar gum is also used to produce gluten-free noodles and pasta [155–157]. Another application of guar gum in the food industry is in meat products as a thickener, providing syneresis control, preventing fat migration during storage, and controlling viscosity and rheology [158]. The other main application of guar gum in the meat industry is as a substitution for fat and in edible films to develop shelf life [159].

2.8.2 Starch Starch is composed of glucose units linked by α-(1,4)-glycosidic bonds and in some levels by α-(1,6)-glycosidic bonds. Starch owes its exclusive functionality to two basic structural units: amylose and amylopectin, which contain approximately 98%–99% granule dry matter [160, 161]. Starch is applied in the food industry as both a food product and additive for thickening, preservation, and

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quality enhancement in baked foods, confectioneries, pastas, soups, sauces, and mayonnaises. Starches formed by each plant type have particular structures and compositions such as length of glucose chains or the amylose/amylopectin ratio and the protein and fat contents of their storage organs might differ considerably. Therefore, starch is different depending on the source [162, 163]. The structural and compositional differences in starches from various sources govern its properties and manner of interactions with other components of foods, which provides the desired taste and texture for the final product. In the food industry, starch can be applied as a food additive to control the uniformity, stability, and texture of soups and sauces, prevent the gel breakdown through treating and increase the shelf life of the products [163]. Starch is simply extractable and does not need complex purification. It is accessible in large quantities in main plant sources such as cereal grains and tubers. These sources are usually considered cheap and economic and help as raw materials for commercial production [164]. Starch from Zea mays (corn, Fig. 2.14A) accounts for 80% of the world marketplace manufacture of starch. Maize starch is a significant ingredient in the manufacture of many food products and has been widely used as a thickener, stabilizer, colloidal gelling agent, water retention agent, and adhesive due to its exact adaptive physicochemical features [165]. Starches from tubers of roots such as potato tubers (Fig. 2.14B), which are considered nonconventional sources, have found usefulness in providing choices for extending the spectrum of desired functional properties, which are necessary for the development of value-added food products. Native starches are pure forms of starch. The stability of native starch under diverse pH values and temperatures differs unfavorably so there is a limit for functionality. To enhance the properties and functionalities such as solubility, texture, viscosity, and thermal stability, which are essential for the desired product or role in the industry, native starches are modified [162]. Starch has a range of roles in various foods, as presented in Table 2.7. An understanding of the mechanism underlying each effect is essential to make the best use of starch in these functions. To gain that understanding, it is helpful to

(A) FIG. 2.14 (A) Corn and (B) potato tuber.

(B)

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TABLE 2.7 Roles of starches in different food systems. Function

Food

Adhesion

Battered and breaded foods

Binding

Formed meat, snack seasonings

Clouding

Beverages

Crisping

Fried and baked foods, snacks

Dusting

Chewing gum, bakery products

Emulsion stabilization

Beverages, creamers

Encapsulation

Flavors, beverage clouds

Expansion

Snacks, cereals

Fat replacement

Ice cream, salad dressings, spreads

Foam stabilization

Marshmallows

Gelling

Gum drops, jelly gum centers

Glazing

Bakery, snacks

Moisture retention

Cakes, meats

Thickening

Gravies, pie fillings, soups

Reproduced with permission from Mason WR. Starch use in foods. In: BeMiller J, Whistler R, editors. Starch. Chemistry and technology. 3rd ed. Food science and technology. Academic Press, Elsevier; 2009. p. 745–95.

track the modifications, which starch undergoes during pasting and cooling, and the impact of these on the structures of foods. Furthermore, it is significant to know how the cooked starch paste changes through storage and the resulting effects on the texture and the form of the foods. Choosing starch for a specific consumption in the food industry depends on the desired food properties in addition to the processing and distribution stresses involved [166]. Starch granules are insoluble in cold water and must thus be cooked to achieve the desired homogeneity. The viscosity of cooked native starch is comparatively high for application in certain products. Furthermore, the rheological properties of some starch dispersions such as potato, tapioca, and waxy maize starch affect the final product features, providing a gummy, stiff structure, thus deteriorating their sensory properties. Many native starches tend to lose viscosity and thickening capability after cooking; particularly in the presence of acids. Dispersions of the starches, which comprise amylose such as corn and wheat starches, form a rigid, opalescent gel through cooling due to the retrogradation process. Upon storage, the gels may also lose their water-binding properties,

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resulting in syneresis or water separation. In comparison, waxy maize starch dispersions, which contain smaller amounts of amylose, form weak gels in which the linear association of amylopectin fragments happens [167]. Starch modification is used to develop one or more starch functional features, of which the most significant are [168]: l l l l

l l

Viscosity reduction. Enhancement in the stability of starch dispersion. Development of gel-forming ability and its rigidity. Modification of gelatinization parameters (reduction in gelatinization temperature, cooking time shortening, reduction in breakdown viscosity, enhancement of hot paste stability). Development of dispersibility in cold water. Introduction of novel starch features by substituting the molecule with various functional groups.

The most common, commercially modified starches are corn, tapioca, potato, and waxy maize [169]. Some of the most common physically modified starches are displayed in Table 2.8 [168]. The application of starch and starch derivatives as improvers in baked products is related to the role, which native starch plays as the main component of wheat flour. Most marketable wheat variations are composed of 75%–80% of starch, 6%–18% of protein, and other minor constituents such as water, lipids, sugars, nonstarch polysaccharides, fibers (arabinoxylans, β-glucans, glycoproteins), and minerals. In wheat, rye, and barley, starch is present in two different forms of semicrystalline granules: larger A-type and smaller B-type [168]. Through flour hydration, a primary step in bread making, starch absorbs up to about 46% water. The main role in the formation of dough structure is credited to wheat proteins; particularly gluten storage proteins while starch has been proposed to act as an inert filler in the continuous protein matrix. Nevertheless, according to some reports, dough represents a bicontinuous network of starch and protein [170, 171]. Starch is applied to thicken various foods such as soups, sauces, and pie fillings. Thickening usually includes granular starches swollen by thermal treatment. Modified waxy maize, potato, and tapioca starches are usually favored due to their relative stability to textural alterations through distribution. Various starches are applied for gelling. Dent corn starch is applied in puddings, lemon pie, and cheese goods for smaller texture and shape retention or set. Blends of gelling and nongelling starches can be applied to offer intermediate properties such as a slight cuttability in products such as salad dressings. In addition, starch is most usually applied to thicken, stabilize, and improve the mouthfeel of canned foods such as puddings, pie fillings, soups, sauces, and gravies. Starch is applied in frozen foods for the same purpose as in fresh, refrigerated, or canned foods, i.e., thickening, low-temperature stability, and control of the flow characteristics of the food [166]. Starch is applied in dressings to thicken and stabilize the dressing and provide the desired

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TABLE 2.8 Different modified starches and their properties. Types of modifications

Products

Properties

Acid converted/thin-boiling starch

Reduced hot paste viscosity, formation of strong gels upon cooling

Oxidized/bleached starch

High paste clarity, low paste viscosity, good paste stability

Pyroconverted starches/ dextrins: white, yellow dextrins, British gums

Low viscosity, good film-forming ability, high solubility, good hot paste stability

Cross-linking

Distarch phosphate Distarch adipate

High stability and resistance to processing conditions: increased temperature, shear, low pH

Stabilization (substitution) starch esters

Acetylated starch

Increased paste clarity and stability, reduced starch retrogradation, lower gelatinization temperature

Starch phosphate

Higher paste viscosity and stability, developed clarity, cohesive texture, high resistance to retrogradation, lower gelatinization temperature, high freeze-thaw stability

Octenylsuccinate starch

Increased peak viscosity, lower gelatinization temperature, good freeze-thaw stability, filmforming ability, emulsifying properties

Starch ether

Hydroxypropylated starch

Lower gelatinization temperature, increased clarity, stability toward pH and temperature, delayed retrogradation, good freezethaw stability

Physical

Pregelatinized (spray-cooked and drum-dried) starch

Granule hydration and swelling in cold water, at room temperature

Heat/moisture-treated starch

Higher gelatinization temperature, decreased swelling power, lower hot paste consistency

Annealed starch

Higher gelatinization temperature, decreased swelling

Conversion

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TABLE 2.8 Different modified starches and their properties—cont’d Types of modifications

Products

Properties power, altered susceptibility to acid, and enzymatic hydrolysis

Hydrolysis

Extruded starch

Increased solubility, paste formation at room temperature, and lower retrogradation tendency

Acid/enzymatic hydrolyzed starch (maltodextrins, corn syrups, etc.)

Reduced polymer molecular weight and reduced viscosity

Reproduced with permission from Hadnađev M, Dapcevi
c-Hadnađev T, Doki
c L. Functionality of starch derivatives in bakery and confectionery products. In: Grumezescu AM, Holban AM, editors. Biopolymers for food design. Handbook of Food bioengineering. Academic Press, Elsevier; 2018. p. 279–311.

cuttability and flow characteristic. Owing to the low pH, high temperatures, and high shear involved, the utilization in cook-up dressings requires the starch to be very cross-linked. The texture of fruit pulp or tomato paste can be achieved in nonstandardized products such as pizza sauces through the introduction of texturizer starches. Another use of starch in baby food is thickening and offering short texture. In addition, starch is applied in both the concentrate and finished beverage products to prevent creaming (phase separation), sedimentation, and loss in flavor and opacity. Starch derivatives are applied to encapsulate flavors, beverage clouds, creamers, and vitamins. In the confectionery industry, starch is applied for gelling centers and to offer attractive coatings. It is also applied as a dusting powder and an impressionable bed in which candies are cast [166, 172]. Starches have been applied by the cereal and snack industries to obtain exact textures, enhance crispness; particularly in high temperature and short time processes [166, 173]. Starch is applied in meats, containing those reduced in fat, to enhance moisture retention for succulence and purge (free package moisture) control, decrease shrinkage, and for the firmness of bite. Moisture retention is obtained by a highly stabilized, moderately cross-linked waxy maize or tapioca starch [174]. Modified food starches are applied in a wide variety of dairy goods to offer different effects, including improved viscosity, cuttability, mouthfeel, and stability. In puddings, starch is applied to impart viscosity and a smooth, short texture. Starches are applied in yogurts and sour cream to control syneresis, thicken, replace milk solids, and increase mouthfeel. In cottage cheese, dressing starch increases the cling on the curd. Other dairy products

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comprising starch include buttermilk, cheese, dips, and ice cream. Starch-based fat substitutions are generally applied in sauces, salad dressings, and dairy products to improve mouthfeel and provide products the flow characteristic of the full fat product [166].

2.8.3 Pectin Pectin is the main component of all plants and makes up about two-thirds of the dry mass of prime cell walls of plants. It offers structural integrity, strength, and flexibility to the cell wall and acts as a barrier to the external environment [175]. Pectin is also a natural constituent of all omnivorous diets and is a significant source of dietary fiber. Owing to the resistance in the digestive system and lack of pectin digestive enzymes, human beings are not able to digest pectin. However, the presence of microorganisms in the large intestine can simply assimilate the pectin and change it into soluble fibers. These oligosaccharides support useful microbiota in the gut and help lipid and fat metabolism, glycemic regulation, etc. [176]. Marketable pectins are extracted from citrus peel and apple fruit, which contain 20%–30% and 10%–15% pectin, respectively, based on the dry mass. Furthermore, pectin has been extracted in a higher amount from various other fruits and their by-products such as sunflower head, mango peel, soybean hull, passion fruit peel, sugar beet pulp, Akebia trifoliata peel, peach pomace, banana peel, chickpea husk, and many more [40, 177–196]. The composition and structure of pectin are influenced by the progressive stages of plants [197, 198]. Pectin is applied in various food products as a gelling agent, thickener, texturizer, emulsifier, and stabilizer. In recent years, pectin has been applied as a fat or sugar substitution in low-calorie foods. The multifunctionality of pectin due to the nature of its molecules, in which there are polar and nonpolar regions, allows it to be incorporated into diverse food systems [199]. To evaluate the performance of pectin, various factors such as degree of methoxylation and molecular size are used. However, since these factors are a bit complicated for the industrial use of pectin, the performance of pectin is measured with its grade for commercial use. Pectin grades are based on the number of parts of sugar, which one part of pectin will gel to an acceptable firmness under standard conditions of pH 3.2–3.5, sugar 65%–70%, and pectin at the limits of 1.5%–2.0%. 100–500 grades of pectins are available in the market [200]. Pectin is a natural hydrocolloid, which displays a various spectrum of functional properties. Owing to the gelling capacity of pectin, it is applied as a viscosity enhancer. Through the emulsification process, pectin molecules adsorb the good oil droplets from the O/W interface and shield the droplet from coalescing with adjacent drops (short term stability). The quality of an emulsifier is defined by its capability to offer long-term stability against flocculation and coalescence [201]. Fig. 2.15 shows the stages in long-term emulsion by pectin as an emulgent [40].

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FIG. 2.15 Emulsion formation and stabilization using pectin as an emulgent [40].

There are some examples of pectin-based emulsified products such as lowfat and low-cholesterol mayonnaise, low-fat cottage cheese, low-fat drinking yogurt, and flavored oil containing acidified milk drinks. These products are prepared by substitution of full fat milk with skimmed milk, emulsified oil, and whey proteins [202, 203]. In recent years, pectin has been used to make low-fat meat batter in combination with inulin [204]. The use of pectin in food goods as a gelling agent is a lengthy custom. Pectin has been reported to form various kinds of the viscoelastic solutions under appropriate conditions.

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This property of pectin is commercially exploited in the preparation of jams, jellies, and marmalades. Based on the gelling process, pectin is categorized as a rapid, medium, and slow set pectin [205]. The gelling process of pectin and its stabilization follows diverse mechanisms for different kinds of pectin [40].

2.9 Chitin and chitosan in food industry Chitin is the second most abundant natural polymer after cellulose and is a structural polysaccharide of the outer skeleton of crustacean animals such as crabs, shrimps, lobsters, insects, and cell wall of certain fungi and algae [206]. Chitin polysaccharide is a linear macromolecule including two subunits: D-glucosamine and N-acetyl-D-glucosamine at a ratio of 90:10 (N-acetyl-D-glucosamine: D-glucosamine). However, this ratio differs based on the chitin source [207–209]. Given the high degree of acetylation, chitin is a hydrophobic compound, which is insoluble in water and most organic solvents. Upon the deacetylation of chitin, less than 50% of chitosan is formed [210, 211]. Although chitin is considered hydrophobic, chitosan is a member of a family of reactive amphiphilic polymers with diverse physical, chemical, and biological properties [2]. The structure of chitosan with various properties such as solubility, viscosity, stability, film bonding, and antimicrobial properties is helpful in food applications. Both chitin and chitosan are biodegradable and biocompatible. Thus, most of the materials in food products with chitin [212, 213], such as unpeeled shrimp, Aspergillus niger, Agaricus campestris, and Schizophyllum commune, are considered safe. Chitin and chitosan could be applied as useful additives. Chitin has low toxicity and is inert in the gastrointestinal tract of mammals. Chitosan, unlike chitin, is very soluble under mildly acidic conditions and has exciting cationic properties. The behavior of chitosan as a food additive stems from its capacity to function as an antimicrobial and antioxidant agent. Chitosan can interact with food macromolecules such as lipids, proteins, and starch, which allows it to act as a texturizing and emulsifying agent. The additional advantages of chitosan are its potential to act as fiber and capacity to lower cholesterol [12]. Chitin and chitosan could be considered natural as part of the fibrous content of tempeh. Based on the degree of deacetylation, chitin and chitosan are appropriate for utilization in foods as stabilizers and thickeners in mayonnaise and peanut butter [214]. Moreover, chitosan has been related to robust hypocholesterolemic activity and a decrease in lipid adsorption [215, 216]. The amount of total dietary fiber in chitin and chitosan was detected to be 90.6% [217]. Chitosan and chito-oligosaccharides (COS) are known for their antibacterial and antifungal properties and evidence suggests that partial depolymerization may improve this result [218–220]. Chitosan can be applied as a clarifying agent due to its polycationic performance in acidic media since protonated chitosan electrostatically interacts with negative compounds.

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Chitosan, owing to its polysaccharide nature, can also interact with other haze active molecules such as polyphenols, proteins rich in proline, polysaccharides, and metal ions via hydrogen bonds and van der Waals forces. These interactions are governed by the nature and concentration of the dissolved molecules in beverages (Fig. 2.16A) [221–224]. Chitosan can be applied as a natural preservative owing to its antimicrobial activity against a variety of foodborne microorganisms such as gram-negative and gram-positive bacteria, yeasts, and molds, in addition to its antioxidant activity [225, 226]. A three-step mechanism has been suggested to describe the prevention of the growth of microorganism by

FIG. 2.16 Chitosan mode of action in beverages as: (A) clarifying agent and (B) preservative [221]. (Reproduced with permission from Rocha MAM, Coimbra MA, Nunes C. Applications of chitosan and their derivatives in beverages: a critical review. Curr Opin Food Sci 2017;15:61–9.)

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chitosan and its derivatives. The first step involves the interaction of the cationic form of chitosan with the anionic groups at the cell surface of microorganisms, which may block the transportation of necessary substances to their inner or result in cellular rupture. In the second step, prevention of RNA synthesis and disruption of protein synthesis allow the permeation to the cell nucleus, affecting disruptions, which may lead to cell death. In the last step, the complexation of metals, trace elements, and vital nutrients, which are accessible for the growth of microorganisms, inhibits the formation of toxins (Fig. 2.16B) [221, 225–227]. Chitosan has been used as a preservative in fruit juices [218, 228–231], wine [232–235], and milk [236]. However, the matrix composition might limit the revenue of chitosan. For instance, a higher performance is perceived in apple juice than in milk, probably due to the interaction of chitosan with milk proteins [236]. In addition, it seems that the molecular weight of chitosan affects microbial inhibition [221]. Chitosan has been applied as a substitution for meals in oil emulsions strengthened with nutrients [237]. The goal is to produce low-calorie products, which give the consumer a feeling of satiety without any negative effects [238]. In the baking industry, chitosan has been applied to simplify and stabilize the substitution of wheat flour with rice flour for use in gluten-free applications [239]. The properties of chitosan make it an appropriate substitution for fat. Furthermore, chitosan has many other qualities, which improve its effectiveness in food systems. The combination of chitosan and a low-fat pork sausage has many useful effects [240]. In addition, chitosan has been reported to decrease the generation of carcinogens in pork and batter systems [241, 242]. In another application, it has been observed that the substitution of gelatin with chitosan has also been tested in ice milk. In this case, the freezing point and ice cream ash increased with the addition of chitosan, presumably due to the molecular weight and higher fiber content of chitosan [243]. Chitosan can be used as an emulsion stabilizer by formation of interfacial complexes with emulsifiers and enhancement of the electrostatic repulsion forces between droplets. In addition, chitosan has established capabilities to increase the viscosity of samples in correlation with its concentration [244–246]. Chitosan can be applied as an additive in muscle products. This process has various advantages such as control of flavor loss, antimicrobial and antioxidant properties, and increased storage stability [12, 247, 248]. Chitosan is also used for seafood products affording many advantages to them including antimicrobial, antioxidant, and texturizing properties. Fishery products are highly perishable owing mainly to microbial spoilage. Additionally, unlike red meat, fish comprise major amounts of unsaturated fatty acids and are very sensitive to oxidation and associated flavor changes. Chitosan at a level of 1% (w/w) can control these variations to improve the shelf life of fresh fishery products. In addition, chitosan and chitin can be applied as food additives in cookies, noodles, and bread to improve texture due to the antimicrobial properties of chitosan and its capability to control starch retrogradation [12].

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2.10 Conclusion and future prospects Polysaccharide biopolymers have been gradually used in different fields such as food, material science, chemical, pharmaceutical, medical, and nanotechnology as they are derived from plentiful and renewable sources. In food treatment industries, these natural polymers have the capability of interacting with food to preserve the texture, gel formation, freezing, etc., of food materials. Physicochemical and thermodynamic properties of polysaccharides may affect the transport procedure and unit operations affecting the development of food products. Some polysaccharides are applied in traditional applications and others own unique features, which can be applied for the improvement of new commercial products. Polysaccharides in particular microbial sources play an important role in food processing industries. Polysaccharides improve the quality, texture, mouthfeel, and flavor of the food as thickeners, stabilizers, and texturizers and gelling agents. In this chapter, the application of various polysaccharides such as starch, alginate, gum, chitin, and chitosan, in the food industry has been discussed. In addition, in this chapter, major functions of polysaccharides in a food system have been reviewed. Although many polysaccharides have been used in the food industry so far and there have been improvements, there are still problems, which need to be addressed in the future: l

l

l

l

l

l

l

Development of physical methods for modifying polysaccharides such as starch to replace chemical or enzymatic routes. Mixing polysaccharides with other compounds to improve their performance. There are many dues for the health benefits of a number of food polysaccharides, but little concrete evidence at the molecular level for the claimed effects. Numbers of starches should be prepared from unexplored sources in the future. The use of chitosans in seafood is still limited because of the allergenicity of tropomyosin. Development of new techniques for using various polysaccharides in the food industry. The use of new fermentation strategies and the development of cheap isolation methods for the preparation of various polysaccharides.

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[143] Chugh B, Singh G, Kumbhar BK. Studies on the optimization and stability of low-fat biscuit using carbohydrate-based fat replacers. Int J Food Prop 2015;18(7):1446–59. [144] Chugh B, Singh G, Kumbhar BK. Development of low-fat soft dough biscuits using carbohydrate-based fat replacers. Int J Food Sci 2013;, 576153. [145] Zambrano F, Despinoy P, Ormenese RCSC, Faria EV. The use of guar and xanthan gums in the production of ‘light’ low fat cakes. Int J Food Sci Technol 2004;39(9):959–66. [146] Schiraldi A, Piazza L, Brenna O, Vittadini E. Structure and properties of bread dough and crumb. J Thermal Anal 1996;47:1339. [147] Shaikh IM, Ghodke SK, Ananthanarayan L. Inhibition of staling in chapati (Indian unleavened flat bread). J Food Process Preserv 2008;32(3):378–403. [148] Ghodke SK. Effect of guar gum on dough stickiness and staling in chapatti-an Indian unleavened flat bread. Int J Food Eng 2009;5(3). [149] Seyhun N, Sumnu G, Sahin S. Effects of different emulsifier types, fat contents, and gum types on retardation of staling of microwave-baked cakes. Food Nahrung 2003;47(4):248–51. [150] Wolf BW, Wolever TMS, Lai CS, Bolognesi C, Radmard R, Maharry KS, Garleb KA, Hertzler SR, Firkins JL. Effects of a beverage containing an enzymatically induced-viscosity dietary fiber, with or without fructose, on the postprandial glycemic response to a high glycemic index food in humans. Eur J Clin Nutr 2003;57(9):1120–7. [151] Sahin-Nadeem H, Ozdemir F. Effect of some hydrocolloids on the rheological properties of different formulated ketchups. Food Hydrocoll 2004;18(6):1015–22. [152] Gujral HS, Sharma A, Singh N. Effect of hydrocolloids, storage temperature, and duration on the consistency of tomato ketchup. Int J Food Prop 2002;5(1):179–91. [153] Torbica A, Belovi
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Chapter 3

Proteins in food industry Mahmoud Nasrollahzadeh, Zahra Nezafat, and Nasrin Shafiei Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

3.1

Introduction

The latest approaches in food technology are focused on the improvement of bio-based structures for different applications such as entrapment and shielding of bioactive compounds [1, 2]. Preferably, a bio-based material for food applications is generally recognized as safe (GRAS), biodegradable, biocompatible, and nontoxic and has appropriate physicochemical and mechanical properties. In addition, it does not cause any inflammatory reactions, which are frequently observed in synthetic polymers. Furthermore, bio-based structures can be prepared using various methods, including size reduction (e.g., nanostructures), gelation, and aggregation [3]. Protein is defined as a group of complex organic compounds, which basically includes combinations of amino acids in peptide linkages comprised of carbon, hydrogen, oxygen, nitrogen, and usually sulfur. Generally distributed in plants and animals, proteins are the main components of the protoplasm of all cells and are vital for life. Proteins play an important role not only in supporting life but also in foods derived from plants and animals [4, 5]. Proteins have been widely considered owing to their features such as dispersibility (as colloids), solubility in water, excellent biocompatibility, and biodegradability. Proteins play important roles in foods by providing taste, texture, and flavor, which are important criteria for food selection. Owing to their versatile functionality and complex molecular structure, proteins have also been developed for many industrial applications. Some recent examples include adhesives, protein plastics, gels, coating, additives, and biomaterials [6]. Proteins for industrial applications have been known for years. Generally, proteins are added directly to foods to increase their functionality. For example, proteins are applied as emulsifiers [7, 8]. In addition, proteins can be managed under various colloidal and physical states, such as films, capsules, gels, foams, porous systems, and fibers. Thus, there are many opportunities to exploit the advantageous features of natural proteins (Fig. 3.1) [9, 10]. In nature, proteins exist as constituents of biological matrices in combination with other compounds such as lipids, carbohydrates, minerals, Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00003-2 Copyright © 2021 Elsevier Inc. All rights reserved.

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Gliadin

ingredients

FIG. 3.1 Main plant and animal proteins applied in food industry and some of their food applications [9].

and other minor components. The presence of these composites in foods is perfect, as it allows different sources of nutrients to be supplied at the same time. However, in some cases, there are different advantages in separating protein fractions to achieve enriched or purified fractions for a particular food, nutraceutical, or industrial application [6]. These natural polymers show high nutritional value, stabilization, and elasticity in addition to the capability of shielding cells, tissues, and organisms. Proteins are typically present in fibrous and globular forms, which are either water insoluble or soluble in water, acids, or aqueous solutions of bases, respectively [11]. The physicochemical properties of proteins depend on the quantity and sequence of amino acid units in the polymer chain [12]. Once the protein is extended, chain-to-chain interaction can happen by hydrogen, ionic, hydrophobic, and covalent bonding [13]. In a scenario where healthy diet is of importance and the consumer wants rapid, easy, healthy, and

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environmentally friendly solutions, protein-based structures have attracted much attention in the food industry owing to consumer expectations [9]. Over the years, food processing has undergone changes such as transformation, destruction of pathogenic and spoilage microorganisms, stabilization, and extension of shelf-life to more complex prospects, for example, changing functionality and chemosensory properties (taste, flavor, and texture). These processes range from minimal to wide modifications by physical, chemical, thermal, and enzymatic approaches, which can be followed alone or in combinations [14]. Given the roles of proteins in nutrition, bioactivity, and health, the value of food proteins extends to contain functional properties, such as solubility, water holding, fat absorption, emulsifying, foaming, and gelation [14]. Furthermore, various protein-based structures, viz. coatings and films, hydrogels, fibers, and particles, can be made as a result of protein structural adaptability [15–18]. The food industry has changed from a service handling industry to a market-driven consumer product industry. The modern consumer is gradually demanding food products, which are compatible with a busy, healthy lifestyle of comfort, balanced calories, and nontoxic and healthy nutrients (less saturated fatty acids and cholesterol) with consistently high quality, suitable portioning, and attractive packaging. The quality attributes such as flavor, odor, color, taste, texture, and mouthfeel are expected [19]. Proteins are the most significant class of functional ingredients since they own a range of dynamic functional properties (Fig. 3.2). They display adaptability through

FIG. 3.2 Schematic representation of functional properties of proteins in foods [20].

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processing, can form networks and structures, offer vital amino acids, and fulfill functional and nutritional needs. In addition, they interact with other components and increase the quality attributes of foods [20].

3.2 Structure and chemistry of food proteins Proteins include extended chains of amino acid units, which fold into unique structures. These folds comprise one or more particular three-dimensional conformation driven by a number of covalent and noncovalent interactions, such as hydrogen bonding, ionic interactions, Van der Waals forces, hydrophobic packing, salt bridges, disulfide bonding, and posttranslational modifications. Proteins can be linear arrangements of amino acids (primary structure), regularly repeating local structures (secondary structure such as α-helix and β-strand/sheets), complex and irregular folding of the peptide chain in 3-D, which are the geometric shapes assumed by a protein (tertiary structure), and a cluster of protein molecules or polypeptide chains (quaternary structure) [14, 21]. The pure charge on a protein can be both positive and negative based on the pH of the liquid matrix surrounding the protein and the corresponding charges on the terminal amine (-NH2) and carboxyl (-COOH) groups, or other charged groups on the amino acid side chains. Basic and external (or environmental) issues such as protein concentration and the composition of the surrounding solution and interface affect the functional properties of proteins. In addition, proteins are categorized as globular, membrane, or fibrous. Among these, only globular proteins are soluble and are thus of most importance in determining the protein functionality in food. Furthermore, food proteins are useful owing to the properties of their globular constituents, particularly their solubility, which is due to the amphiphilicity of the molecules [7, 14, 22–24]. Most food products, particularly grains and pulses, are comprised of about 10%–30% proteins, which are mostly storage proteins [25]. The seed storage proteins are categorized based on their solubility in a sequence of solutions and contain albumins (soluble in water), globulins (soluble in salt and other isotonic solutions), prolamins (soluble in aqueous alcohol), and glutelins (soluble in acids, bases, detergents, chaotropic, or reducing agents). Prolamins such as gliadin, hordein, kafirin, secalin, and zein are proline and glutamine-rich storage proteins found in wheat, barley, sorghum, rye, and corn, respectively. These proteins are known to contribute to the intolerance and allergenicity in certain people. The selection of food preparation method can also remarkably increase the allergenicity of some of these proteins [14]. For example, dry roasting can convey flavor to peanuts, strengthen safety and amplify the formation or unveiling of new allergenic epitopes in peanut proteins [26, 27]. The single and combined features of proteins have been applied to modify their functional properties by various mechanisms [7, 22, 23, 28–31].

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Functional properties of proteins

Although it is obvious that proteins have a main function in many biological processes, they also play a major role as food additives and ingredients. The common feature is the capability of various proteins to form gels or films and stabilize emulsions and foams. A summary of the functional properties of proteins and their food applications is listed in Table 3.1. These properties make food proteins useful and beneficial ingredients in a varied range of product developments, formulations, and other applications. Gelling, foaming, and emulsifying properties will be discussed in more detail [14].

3.3.1

Gelation

Proteins are categorized as fibrous (such as collagen (gelatin), keratin, and elastin) and globular (such as albumins (whey and egg protein) and globulins

TABLE 3.1 Functional properties and fundamental mechanisms for the applications of proteins in food products [14]. Functionality

Mode of action

Application

Solubility

Protein solvation, pH-dependent

Beverages

Water absorption and binding

Hydrogen bonding of water, entrapment of water (no drip)

Meat, sausages, cake, bread

Fat holding

Binding of free fat

Meat, sausages, doughnuts meat products

Gelation

Protein matrix formation and setting

Meat, sausages, pasta, baked goods, cheese

Foaming

Formation of stable films to entrap gas

Whipped toppings, cakes, mousse, meringues

Emulsification

Formation and stabilization of fat emulsions

Salad dressing, soups

Viscosity

Thickening, water binding

Soups, gravies

Cohesionadhesion

Protein acts as adhesive material

Meat, sausages, baked goods, pasta products

Elasticity

Hydrophobic bonding in gluten, disulfide bridges in gels (deformable)

Meat, bakery

Flavor binding

Adsorption, entrapment, release

Simulated meat, bakery, etc.

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(soy protein)). Both kinds are capable of forming a gel, but the gelation mechanism is different and happens under various conditions [9]. Gels are diffused systems of not less than two constituents in which a solid phase (dispersed phase) forms a cohesive network in a liquid phase (continuous phase). There are two types of gels, namely “polymeric networks” and the “aggregated dispersions.” Examples of polymeric networks are the gels formed by gelatin or polysaccharides such as agarose or carrageenan. Examples of aggregated dispersions are the gels formed by globular proteins after denaturation by heat [32]. Globular proteins are usually detected on heating, and at appropriately high concentrations, the denatured chains will aggregate to form thermally irreversible gels. The properties of the gels will be influenced by various factors such as the degree of unfolding of the protein chains and the extent and kinetics of chain aggregation [33]. The capability of proteins to form gels is of main industrial application not only for food but also for cosmetic, medical, and pharmaceutical products [34, 35]. Nevertheless, protein gel formation is a complex process, which can affect diverse structures depending on the protein features, concentration, environmental conditions, and gelation process [36, 37]. The use of proteins in the food industry in gel design has gained much consideration in recent years owing to the fact that protein gels are frequently responsible for texture in various foods and food products [38]. Different methods have been used in the food industry to change the gel properties. These include, next to the protein concentration itself, the addition of other components such as polysaccharides through gel formation, difference of the heating rate, ionic strength, pH, and the kind of salts added to the proteins before gelation is carried out. Furthermore, gel properties can also be designed by the physical/chemical modification of the proteins [39]. With respect to their application in food, protein gels can be shaped into a large series of sizes from bulk gels (or macrogels) to micro- or nanoscale particles [36, 40, 41]. Bulk gels are usually responsible for the texture studied because of the biopolymer network formation through the gelation process. Many food products such as desserts, sausages, yogurts, cheeses, and confectionery products present a range of protein materials, which offer estimated sensorial and textural features. The structure of these products and its relation to physical properties determine the control of these features. Whey protein isolate (WPI), soy protein isolates (SPI), egg white, gelatin, pea, and wheat proteins, among others have been widely used. Various gelation mechanisms and methods have been developed to modulate the structure, functionality, and application of proteins in food systems. Some examples of systems made with dissimilar gelation mechanisms are shown in Table 3.2 [9]. Size reduction of protein-based structures could alter their food application and effects on food products. Microparticles or microgels might be essential to the food product owing to the process for food production, or they may be engineered for particular purposes [65, 69, 70]. Microgel suspensions have been applied in foods to increase the food texture and mouthfeel, replace fat, and control the delivery of compounds [65, 71].

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TABLE 3.2 Examples of protein-based structures of different sizes by dissimilar gelation approaches [9]. Scale

Protein

Gelation technique

References

Macro

WPI

Heat

[42]

Heat and enzymatic

[43]

Acid gelation

[44]

Salt-induced gelation

[45]

WPI + pectin

Acid gelation

[46]

WPI + caseinate

Heat

[47]

Egg white

Heat

[48]

Heat and salt-induced gelation

[49]

Acid gelation

[50]

Alkaline and salt-induced gelation

[51]

Acid and salt-induced gelation

[52]

Heat

[53]

Heat and high pressure

[54]

Heat and salt induced

[55]

Heat and acid gelation

[56]

Acid gelation

[57]

Heat

[58]

Acid gelation

[59]

Salt-induced gelation

[60]

Heat and pressure

[61]

Heat and chemical/enzymatic

[62]

Heat

[63]

Heat and salt-induced

[64]

Heat

[65]

Ultrasound and chemical reaction

[66]

Heat and acid gelation

[56]

Heat and salt-induced

[55]

Heat

[67]

Heat and enzymatic

[68]

SPI

Micro

WPI

Egg white

SPI

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3.3.2 Emulsifying and foaming Emulsifying and foaming properties are two significant protein functionalities in food products, such as beverages, ice cream, dressings, mousses, whipped toppings, and margarine [7, 24, 31]. Owing to their amphiphilic nature (presence of polar and nonpolar amino acid residues), proteins act as emulsifiers by adsorbing at the interface, coating oil or air droplets, increasing stable films, and stabilizing dispersions. Emulsions (oil-water interface) or foams (air-water interface) are prepared by dispersing oil droplets in an aqueous medium or a film or skin surroundings air cells, respectively. In both examples, the value of the film depends on prevention of coalescence, flocculation, and sedimentation in emulsions and the downfall of air bubbles in the foam. Protein properties such as the hydrophobicity-hydrophilicity ratio and the simplicity of protein folding-unfolding have a substantial effect on their emulsifying behavior [14]. The future of a protein to be applied as a food emulsifier is related to its amino acid sequence, structure, and properties at colloidal interfaces. Animal-based proteins, particularly those derived from eggs and milk, are usually applied to stabilize emulsions and foams [72]. The interfacial structures and properties of plant-based proteins have not been considered in details. However, plant proteins commonly form a moderately thicker interfacial layer at oil-water interfaces due to their low molecular size and structural limitation by disulfide cross links [73]. This compound, which is the result of weak protein interactions in which absorption occurs at the interfaces, contributes to the superior stability of emulsions stabilized by various plant-based proteins compared with, for example, dairy proteins. For example, soy proteins have been studied more than other plant-based proteins for their emulsification properties [74]. Some plantbased proteins, including those derived from peanut, rice, lentil, potato, and pea, have been evaluated for emulsifying properties [75–79]. In the case of foam properties, the capability of a protein to form stable foams is significant for the production of a large number of food products. However, proteins derived from egg white, soy, and milk together with gluten and collagen are the most commonly applied for forming foams in the food industry. Various plant-based proteins have been displayed to own good foaming properties and contribute to the uniform distribution of good air cells in foods [80]. Proteins perform as foam forming and stabilizing agents in different foodstuffs such as baked products, sweets, desserts, and beer. In summary, the perfect foam forming and stabilizing proteins are known by a low molecular weight, high surface hydrophobicity, excellent solubility, a small net charge at the pH of the food, and easy denaturability [32].

3.4 Factors affecting properties of proteins in food products The different properties of protein products such as hydrodynamic/rheological, surface, hydration, and biological properties affect their function in food

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FIG. 3.3 Examples of intrinsic and functional properties of food proteins and factors affecting them [4].

systems. Furthermore, these, in turn, are influenced by interactions with other food components such as salt, water, flavor compounds, food processes, and external conditions, such as heating, freezing, pH, redox status, and other processes, such as chemical derivatization or enzymatic modification (Fig. 3.3) [4].

3.4.1

Interactions of proteins with food components

The properties and function of proteins depend on their interaction with the main components of the food, such as salt, water, other proteins, lipids, and

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carbohydrates, or any number of minor components, such as salts, metal ions, acidulants, flavor/aroma components, and phenolic compounds [4]. In the next section, we explain some of these interactions.

3.4.1.1 Water Water molecules, containing hydrogens bonded to protein molecules, can be very significant for the structural stability of the protein. The equilibrium between protein-water interactions against protein-protein interactions is significant in functional properties, such as swelling, water-binding ability, and solubility of protein ingredients, in addition to their capability of forming network structures such as gels or films including those surrounding foam bubbles [81]. 3.4.1.2 Carbohydrates Carbohydrates have many hydroxyl groups, which can contribute to the structural stability of proteins both by the exclusion of the carbohydrate from the protein surface subsequent in special hydration of the protein and by the interaction of the carbohydrate with hydroxyl or ionic functional groups of the protein molecule. The influence of these carbohydrate-protein interactions on the stability of food proteins in processes such as thermal treatment, dehydration, or frozen storage is the basis for the addition of ingredients such as sucrose or sorbitol to stabilize fish muscle proteins through frozen storage or drying [4, 82]. 3.4.1.3 Salts Salts may favor both solubilization (salting in) and precipitation (salting out) of proteins by influencing the protein hydration properties and bulk water structure depending on the concentration and nature of the salt involved. Certain salts such as sodium salts of sulfate, phosphate, and fluoride are usually observed to have a stabilizing effect on proteins by increasing the hydrogen-bonded structure of water, whereas salts containing iodide, bromide, and perchlorate destabilize and denature proteins by breaking down bulk water structure [4]. Nevertheless, whether a specific salt will favor protein stabilization/solubilization against destabilization/precipitation is determined by its effect on bulk water structure as well as various other factors such as the properties of the specific cation-anion pair and protein-ion interactions [83]. 3.4.2 Food processes Protein structures can be favorably destabilized by comparatively negligible variations in pH, temperature, addition of oxidizing or reducing agents, different salts, or under the pressure or shear in addition to numerous combinations of these conditions. The properties of proteins can, consequently, be estimated to be changed because of food processing operations such as thermal or highpressure processing, freezing and frozen storage, dehydration, concentration,

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mixing, homogenization, extrusion, membrane processes such as ultrafiltration. Furthermore, through thermal processing, the amino groups in proteins can similarly react with reducing sugars by the Maillard reaction, causing structural changes, loss, or oxidation of some amino acids in addition to the formation of brown pigments. These different changes are not essentially unwanted, and the processing conditions may be controlled to deliberately modify the structure and functionality of food proteins. The word “denaturation” is generally defined as changes in the secondary, tertiary, and quaternary structures of a protein, without changing its primary structure. Furthermore, denaturation may cause alterations in the native structure of proteins, which affects their nutritional, functional, and bioactive properties. Both of these descriptions are significant in the context of understanding the properties of food proteins [4].

3.4.3

Other processes

The application of chemical and enzymatic techniques to deliberately modify the chemical and functional properties of food proteins has a lengthy history of utilization, as demonstrated by the enzymatic modification of milk proteins to yield yogurt and cheese [4]. Chemical techniques of derivatization, which have been reported in the literature, include acylation (acetylation, succinylation) or alkylation of amino groups, esterification or amidation of carboxyl groups, acylation or electrophilic substitution of phenolic groups, oxidation or alkylation of sulfhydryl, thioether, imidazole, or indole groups, oxidation or reduction of disulfide groups, and glycosylation or phosphorylation through hydroxyl (O-linked) or amino (N-linked) groups [81, 84]. By choosing the suitable derivatizing reagent, various factors such as charge, polarity, hydrophobicity, and, indirectly, even the molecular size or shape of protein molecules might be modified to produce appropriate functional properties. Conversely, most of these chemical modifications are not accepted or suitable for modification of proteins, which are envisioned for human consumption as they can result in the nutritional value or even lead to the formation of toxic amino acid derivatives [81]. Oxidizing and reducing agents such as sulfite, hydrogen peroxide, ascorbic acid, and cysteine are some of the generally applied reactants employed to modify food proteins in various applications such as in the baking industry to control dough properties. Enzymatic modification is usually considered slighter, more particular, and less prone to produce undesired side reactions. A diversity of enzymes from microbial, animal, and plant bases with different specificities and sites of action are commercially accessible for the modification of food proteins. Famous examples of the enzymatic modification of protein foods include the coagulation of milk by bovine rennet, recombinant chymosin, or microbial rennets; the improvement of cheese texture and flavor by proteolytic and lipolytic action of microbial enzymes; and the tenderization of meat by plant proteinases such as papain, ficin, and bromelain [85]. The functional properties of proteins can also be modified by the cross-linking

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action of microbial transglutaminase. This enzyme is commercially applied in the manufacture of various foods such as restructured meat and surimi seafood products [86].

3.5 Proteins used in food industry 3.5.1 Casein Casein is the main protein group in bovine milk and is the chief factor for the dairy family applied universally in the food industry. Caseins, which are naturally dispersed in an aqueous solvent, carry comparatively great quantities of calcium and calcium phosphate; show a low viscosity at
2.5% (w/w) concentration; and are a heterogeneous group of phosphoproteins (they comprise the amino acid phosphoserine). Owing to the liquid nature of bovine milk, the dairy industry has the ability of fractionating the components yielding an array of functional ingredients for application in the food industry. Different food systems are composed of variable parts of proteins, fat, sugars, salts, and water. The amount and concentration of these compounds determine the structure and texture of the compounds known as food. They may be liquid, semisolid, or solid, depending on the concentration and kind of ingredient. In addition, they may contain allowable additives such as emulsifiers, stabilizers, colors, and flavors. The structure, texture, and stability of any food compromising casein will be affected by pH, ionic strength, and temperature. This will also be true for emulsions stabilized by casein [87]. The major applications of casein in food products together with their functions in such foods are shown in Fig. 3.4 [88]. Casein can be used in bakery applications owing to its water-binding properties. The soluble forms of casein such as caseinates will bind to a high amount of water to form sticky or doughy foods. Therefore, insoluble or partly soluble casein products are frequently applied since they are less water binding than the fully soluble caseinates. Several bakery products, which have been made with caseins, include doughnuts, waffles, cake mixes, and bread. Several examples of the use of casein products in bakery are shown in Fig. 3.5 [88]. In the bakery industry, casein is applied to completely replace gluten with a functional, highly casein-based ingredient. The idea behind this method is that by enhancing the calcium concentration to an optimum level in the casein/caseinate ingredient, it will be possible to substitute highly functional (covalent) S-S bonds in a glutenbased dough with calcium-induced casein-casein complexes under the appropriate pH and ionic strength conditions [89]. In addition, casein has been applied as an extender and texture modifier in processed cheese to enhance the yield of cheese from cheese milk in Europe. However, the most important use of casein in cheese products has perhaps been in the manufacture of the so-called imitation or synthetic cheese (frequently referred to as cheese analogs). This product, which is similar in properties to processed cheese, is prepared from water, caseins such as acid casein, rennet

Ice cream

FIG. 3.4 Schematic representation of use and function of casein products in foods [88].

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casein in bakery products

FIG. 3.5 Schematic representation of use of casein products in bakery.

casein, or sodium or calcium caseinate, singly or in mixtures, vegetable fat, stabilizers, and emulsifiers. The food industry in the United States was the first to develop imitation cheese at least in the name, which could be considered a similar improvement in the cheese industry to the previous manufacture of margarine as an “imitation” butter. Imitation cheese originates its application as a cheap alternative for natural cheese, mainly in fast food outlets, frozen pizza, and hamburgers, for example. The main function of the casein product in this application is to offer the essential body and texture with emulsification of fat, in addition to the melting properties of the complete cheese in pizza. In addition, there are various applications of casein in the cheese food industry, including surface coating of whole cheese and cheese granules due to the natural film forming properties of casein products. Various applications of casein products in cheese-like food industry are listed in Table 3.3 [88]. In the United States, the so-called filled milk, which contains vegetable fat and skimmed milk solids, has been sold for several years. In the late 1960s and 1970s, a novel course of milk imitation was performed on the marketplace. This included vegetable fat and other different ingredients, counting protein as

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TABLE 3.3 Use of casein products in cheese-like foods. Examples

Casein product used

%

Use/function of casein product

Simulated cheese

Rennet casein

25

Texture, nutrition

Coating of cheese pieces

Casein

2

Free-flow agent

Fat-free cheese analogs

Rennet casein

15–35

Texture

Protective protein coating for cheese

Sodium caseinate/casein

3–14

Film coating

Imitation cheese

Calcium caseinate

12

Texture

Reproduced with permission from Southward CR. Casein and caseinates juses in the food industry. In: Encyclopedia of food sciences and nutrition. 2nd ed. Academic Press, Elsevier; 2003. p. 948–958.

sodium or potassium caseinate or from soybeans, and a carbohydrate source such as corn syrup solids. Casein products have also been applied to boost new milk, which was used earlier in Europe than in North America. Various examples for the application of casein products in beverages are presented in Table 3.4. Casein, in the form of sodium caseinate, has recently been applied in cream liqueurs, particularly in the United Kingdom and the Irish Republic,

TABLE 3.4 Application of casein products in beverages, coffee whiteners, and creamers. Examples

Casein product used

Use/function of casein product

Soluble tea product

Acid casein

Inhibits tea cream formation

Powder for cream liqueur

Sodium caseinate

Emulsion stabilizer

Iced chocolate

Calcium caseinate

Texture/fat replacer

Coffee whitener

Casein

Emulsion stabilizer

Stabilizer for wine

Alkali caseinate

Stabilizer against changes in color or taste

Foaming coffee whitener

Caseinate

Whiteness and foaming

Reproduced with permission from Southward CR. Casein and caseinates juses in the food industry. In: Encyclopedia of food sciences and nutrition. 2nd ed. Academic Press, Elsevier; 2003. p. 948–958.

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which have been, seemingly, two of the fastest growing markets for cream. Other ingredients can be sugar, alcohol, and trisodium citrate. In cream liqueur industry, sodium caseinate has been applied as an emulsifier or emulsion stabilizer. In addition, casein products can be applied in soups as a nutrient to enhance the resistance or viscosity of the mixture (perhaps in the form of sodium caseinate). Sodium caseinate is used in frozen desserts and ice cream as a stabilizer to increase the whipping properties of the mix and impart body (also recognized as consistency or thickening) [88]. A number of examples for the application of casein products in desserts and whipped toppings are presented in Fig. 3.6 [88].

3.5.2 Collagen and gelatin Collagen is the most abundant and universal protein of animal origin, containing about 30% of total protein. Collagen is mostly present in all connective tissues, including animal skin, bone, cartilage, tendon, and blood vessels [90–95]. Collagen provides excellent tensile strength and stable insoluble fibrils, helping the structural stability and integrity of tissues and organs [96–98]. Collagen can be obtained from animal skins, hides, bone extracts, offal meats, and skeletal muscle. Native collagen tissue from animal carcasses is of little usefulness in food [99]. The collagen kinds are categorized by their size, function, and distribution, which vary significantly in their amino acids’ composition [90, 93, 94, 98]. Types I, II, and III are the most abundant collagens responsible for tissue strength, elasticity, and water retention capacity [93]. Today, collagen has become in demand ingredient for healthy food improvement. With age, the amount of collagen in the body decreases, and since collagen injection is not common among people, the best way to get it is through diets. Consequently, collagen has been blended in various beverages [100]. Collagen and the corresponding health issues have led to the founding of collagen supplement industry. Owing to moisture absorption, collagen and its fractions mainly function as valued nutritive fibers and protein sources in composing human diets [101]. The local snack manufacturer, Munchy’s, has introduced “Wheat Krunch Collagen” to support the collagen quality. Baked crackers are added to marine collagen, which contains about 1200 mg collagen [100]. In addition, collagens are applied as food additives to improve the rheological properties of sausages and Frankfurters in addition to assure the presence of adequate amounts of animal nutritive fibers [101]. Meat comprising containing raw materials added with collagen or its fractions could improve its technological and rheological properties. The addition of collagen to liverwurst or pasta enhances the quality of products and decreases the occurrence rate of fat caps. The use of collagen in the beverage industry is another example of the utilization of collagen in the food industry. There are various products released by the producers such as soy collagen, cocoa collagen, cappuccino collagen, juice with collagen, and birds nest drink with collagen [100].

FIG. 3.6 Schematic representation of use of casein products in desserts, ice cream, and whipped toppings [88].

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As a significantly pure protein food ingredient, gelatin is obtained by the partial hydrolysis of collagen [33]. There are two types of gelatin including types A and B. Type A gelatin is formed by the acid process, which is generally applied with pigskin and fish skin and is not heavily cross-linked [102]. The alkali process, in which the raw material is subjected to alkali treatment, yields type B gelatin [33]. Type A gelatin is appropriate for a wide range of food applications, but type B has limited utilization in food and is mostly applied in nonfood applications [99]. Gelatin is a natural polymer, which is insoluble in cold water and swells or hydrates when stirred in cold water. Formation of thermally reversible gels is the most important property of gelatin [103]. In 1993, the Food and Drug Administration (FDA) of the United States confirmed that gelatin is considered a safe food ingredient “GRAS,” but it must be confirmed that the hides from animals show no neurological disease or allergic contractions. Furthermore, in 1970, the Joint Expert Commission on Food Additives (JEFCA) placed no limit on the use of gelatin as a food additive [104]. In the food industry, gelatin is generally applied by two major ways: in the production of the food as a stabilizing, emulsifying, or gelling agent and in the formulations of food coating to protect food and extend its shelf-life [105]. Gelatin is a useful hydrocolloid and is broadly applied in the food industry. The most significant properties of gelatin are shown in Fig. 3.7 [106]. Gelatins with exclusive properties have been improved particularly for the confectionery industry due to their thermoreversible gelling properties, foam formation, stabilization, binding, emulsification, and controlling sugar crystallization. There are several products containing gelatin such as fruit gums, mallows, meringues, caramels, bar products, and sugarcoated candies. Bloom strength, concentration, and function of gelatin applied in some confectionery products are listed in Table 3.5 [102, 106]. In the food industry, the most common application of gelatin has been in various products such as jams and jellies (for its reversible gelling properties),

FIG. 3.7 Schematic representation of properties of gelatin [106].

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TABLE 3.5 Examples of applications, bloom values, concentration, and function of gelatin confectionery products.

Application

Gel strength (g Bloom)

Concentration (%)

Fruit gums

200-280

Marshmallows

Principal function

Secondary function

6-10

Gel formation

Texture Elasticity Transparency Brilliance

160-260

1-3

Foam formation

Foam stabilization Gel formation

Pastilles

160-220

1-2

Binding agent

Texture Melting properties Prevents disintegration

Caramels

140-220

0.5-2.5

Emulsifier Foam stabilization

Chewability

Reproduced with permission from Haug IJ, Draget KI. Gelatin. In: Phillips GO, Williams PA, editors. Handbook of food proteins. Woodhead Publishing Series in Food Science, Technology and Nutrition, Elsevier; 2011. p. 92–115.

yogurt (as a stabilizer), dried soups (to provide mouthfeel), fruit juices (for its clarifying properties), and processed meat products such as aspics, canned hams, and canned sausages (to add flavor and improve appearance) [107–109]. The bakery industry is one of the main sources of ready food, where a significant amount of gelatin is used as stabilizing, foaming, and setting agents, particularly in the preparation of pies, cakes, and bread. The amount of gelatin necessary varies with the kind of bakery products. Furthermore, the application of gelatin in the production of table jellies owing to its thermally reversible properties with water must be pointed out as these products are correlated with exclusive thermally reversible properties of gelatin. Therefore, gelatin is remarkable for its exclusive properties in terms of its sensory aspects, more particularly flavor release, which is mainly necessary for some products such as canned ham. This property is also known as water-absorbing property. Here, the exudates from the meat are absorbed by the gelatin and seem like a gel when the can is opened. Generally, gelatin is also applied to organize glazed hams, head cheese, chicken rolls, sauces, and other types of meat products in the range of 1%–5% depending on the type, amount, and texture of the final product [104, 110]. Furthermore, gelatin is important in some dairy products and pastries to offer the quality of

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these storable products as necessary by consumers. The addition of gelatin to dairy products increases the emulsifying ability as gelatin molecules are connected to the surface of the fat droplets and thereby decrease the surface tension in the aqueous phase. Gelatin can be added to dairy products to bind whey, and thus hamper secretion of aqueous whey from, such as yogurts, curds, and cream cheese. The addition of gelatin to foamed milk-based desserts such as yogurt, curds, ice creams, and mousses reduces surface water tension, allowing the formation of foam by mechanical whipping or injection of gas. In the ice cream industry, the addition of gelatin affects the size and distribution of ice crystals and thus the texture and mouthfeel of the final ice cream. In addition, in meat, the processing industry applies gelatin to the products for various reasons, the most important of which is the capability of binding water and meat juices and assuring excellent texture and taste. Furthermore, gelatin is broadly applied in low fat (fat replacer), low carb (binding agent), and low calorie (fat replacer and binding agent) food products. The bloom strength and function of gelatin applied in some food products are shown in Fig. 3.8 [106].

3.5.3 Whey Whey is considered a by-product of cheese production, which is rich in proteins (β-lactoglobulin, α-lactoglobulin, immunoglobulin, and serum albumin), and widely applied by the food industry owing to its nutritional and functional properties [111]. On the other hand, whey is the fluid by-product causing the precipitation of proteins in milk. The precipitation can be simplified by the growth of various microorganisms (e.g., cheese whey), by the addition of acid (acid casein manufacture), or by the addition of enzymes (rennet casein manufacture). Therefore, whey is divided into two categories: sweet whey or acid whey. Acid whey results from the reaction of cottage cheese and acid casein. A majority of the whey manufactured globally is sweet whey. About 94% of

gelatin in

FIG. 3.8 Schematic representation of applications of gelatin in food products [106].

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the whey manufactured in the United States is sweet whey, and the remaining 6% is acid whey [112]. Whey proteins are globular proteins, which are soluble in their native forms in the ionic environment of milk, making them useful as inhibitors for coacervation method since they can contribute to the electrostatic interactions by a method similar to that of other natural polymers. Whey is insoluble at the isoelectric point (pH about 5) at extremely low ionic strength. The whey proteins denature at temperatures above 70°C, becoming insoluble and forming thermally irreversible gels of diverse quality [113]. Whey has low viscosities even at high concentrations. In addition, they have various properties such as emulsification and therefore, offer this functionality process where encapsulation is done by emulsification. Whey proteins can be applied in diverse encapsulation techniques [111]. Whey proteins have functional properties widely applied in the food industry. Their ability to stabilize interfaces is very important, giving foaming and emulsifying properties, and their gelling and water binding properties [114]. Whey and whey derivatives from cheese, casein, paneer, etc. can be applied in beverage preparation. Whey can be used by different pathways in the food industry. However, it is generally dehydrated to whey powder or applied for the production of whey protein concentrates and isolation of lactose or proteins [115]. β-Lactoglobulin (β-Lg) is the main protein in whey comprising about half of the total whey proteins in bovine milk. Though it can be established in the milk of several other mammals, whey is basically absent in human milk [116]. β-Lg can be applied as a functional ingredient in food and beverage applications with good gelling properties, making it applicable as structuring and stabilizer agents in dairy products such as yogurts and cheese spreads [117]. α-Lactalbumin (α-La) is the second maximum protein in whey containing about 20% of whey proteins and is abundant in breast milk [116]. α-La is comparatively heat stable and usually has poor gelling ability, but it can be applied as a source of vital amino acids. α-La is commercially applied in supplements for infant formula because of its similarity in structure and composition to the human milk protein [118]. Nanoparticulate whey proteins are applied as ingredients for fat substitution in various food products such as ice cream, fermented milk, cheese, sauces, and dressings. Whey particles can be made in diameters ranging from 1 to 10 mm. Furthermore, nanoparticulate whey protein can act as emulsifiers and fat substitutes, but display smaller particle sizes [119]. The application of whey protein as texture enhancers in yogurt has become a usual practice owing to its nutritional and functional properties [120, 121]. Whey proteins are multipurpose ingredients owing to their varied range of functionalities such as emulsification, water binding, and gelation, which make them appropriate for dessert formulations [122]. Designing better Panna cotta-like desserts targeted at weight management complicates the addition of more whey protein to a low cream formulation to make a denser, firmer matrix to increase satiety [123]. Incorporating extra whey proteins in cheese including fresh, natural, and processed cheeses can be considered according to cheese classification. Various styles of incorporation such as in situ incorporation of whey proteins through the course of cheese milk, UF, and

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preconcentration, addition of whey proteins developed from whey in both native and denatured forms to cheese milk through processing, and addition of MWP as a fat substituent to cheese milk are probable [124]. The effects of incorporating microparticulate whey protein (MWP) into reduced fat cheeses have been recognized for many diversities ever since Simplesse and DairyLobased MWP developed commercially accessible chesses such as Mozzarella, Kashar, Gouda-type, and Cheddar [125–129]. The incorporation of whey protein in crunchy snack processing can increase the nutritional profile of snack foods [130]. Additionally, whey proteins are commonly applied as protein supplements in different health foods [131].

3.5.4 Egg proteins Egg proteins are a significant source of amino acids, which display multipurpose functional and biological properties. Nevertheless, they only account for 2% of human consumption [132]. The egg white, or albumen, makes up about 63% of the whole egg [133]. The three most acknowledged functions of eggs are their gelation (for example, cakes and quiches), foaming properties (such as baked goods and meringues), and emulsifying components (such as batters and mayonnaise), all of which contribute to the textural properties of egg-containing food products. Fig. 3.9 exhibits the functional properties of egg proteins in various food products [134].

FIG. 3.9 Functional properties of egg proteins in food industry [134].

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There are various proteins in egg white such as ovalbumin, ovotransferrin, and lysozyme, including hydrolysates, which have several properties such as antihypertensive, antioxidant, antiinflammatory, and antidiabetic [135]. The proteins present in egg whites show multifunctional properties. Egg white proteins have a significant dietary role because of their high biological value. In addition, they have the main functional properties in foods [133]. The main functional properties of egg white proteins are coagulation or gel forming and emulsifying properties, but it possesses multiple functional properties such as foaming, emulsification, heat setting, and acting as a binder [136]. Lysozyme is one of the main bacteriolytic proteins, which originate in egg white. Lysozyme can control several foodborne pathogens such as Listeria monocytogenes and Clostridium botulinum, which are known as two main pathogens causing problems in the food industry [137]. Lysozyme efficiently controls toxin generation by Clostridium botulinum in fish, poultry, and some vegetables. It has been reported that modifications of lysozyme with chemical and thermal behaviors improve its antimicrobial properties. Not only can lysozyme prevent microbial growth but it also has antiviral, antiinflammatory, and therapeutic properties [138]. The World Health Organization and various countries allow the utilization of lysozyme in food as a protective agent, and it is presently applied in Kimchi pickles, sushi, Chinese noodles, cheese, and wine production [139]. The antibacterial properties of lysozyme-based preparations and their application for better control of fermentation and spoilage microorganisms in different food processing are listed in Table 3.6 [140–148]. Egg white, which is only famous for its exceptional foaming properties, is necessary in desserts, cakes, biscuits, and many aerated prepared dishes such as souffl
e and mousse. Spray-dried egg white is generally applied as a food ingredient for its foaming and gelling properties. Maximum dried egg white products are accessible in a whipping or nonwhipping type, depending on the functional properties necessary. For instance, there is a request for a good whipping of dried egg white for application in biscuits, cakes, and meringues [149]. Owing to its exceptional foaming properties, egg albumen is applied as a functional protein ingredient in a varied range of processed foods [150]. The foaming properties of egg white proteins are graded in the order of significance as globulins, ovalbumin, ovotransferrin, lysozyme, ovomucoid, and ovomucin. It has been proposed that the different charge behaviors of the constituent proteins are responsible for the good foaming properties of the egg [151, 152].

3.5.5

Soybean protein

Soybean has been a significant food in Asian countries and is established as a healthy ingredient in several countries such as the United States and some European countries. Soybean contains about 40% protein and 20% oil on an average dry matter base, and it has thus been the main source of protein in countries of its high consumption. It has an excellent potential to be a good protein source for

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TABLE 3.6 Properties of lysozyme-based products on the protection of food systems. Product

Effect

Dosage

References

Hard cheeses

Inhibition of Clostridium tyrobutyricum

50–350 mg/kg

[140]

Milk

Inhibition of Listeria monocytogenes

1000 μg/mL

[141]

Italian mozzarella cheese

Inhibition of Hafnia alvei and shelf-life prolongation in combination with disodium ethylenediaminetetraacetic acid

0.0078 g/L

[142]

Dairy products

Meat and meat products Chilled chicken breast muscle

Shelf-life prolongation

1 mg/mL

[143]

Processed ham and bologna

Inhibition of Brochothrix thermosphacta, Leuconostoc mesenteroides, and Lactobacillus sakei Inhibition of Listeria monocytogenes used in combination with nisin and ethylenediaminetetraacetic acid

25.5 g/L of lysozymenisin (1:3)

[144]

Ground beef

Inhibition of Bacillus anthracis strain Sterne

2 mg/g

[145]

Fish and fish products Raw cod fish fillets

Inhibition of Listeria monocytogenes

3 mg/mL of water

[146]

Raw minced tuna and salmon roe products

Inhibition of Listeria monocytogenes

3 mg/mL of water

[147]

Reproduced with permission from Silvetti T, Morandi S, Hintersteiner M, Brasca M. Use of hen egg white lysozyme in the food industry. In: Hester PY, editor. Egg innovations and strategies for improvements. Academic Press, Elsevier; 2017. p. 233–242.

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vegetarians and for people who do not consume animal proteins for moral or pious and environmental reasons [152]. Furthermore, soy proteins are capable of offering a high amount of vital amino acids to human beings and own a high Protein Digestibility-Corrected Amino Acid Score (PDCAAS), which is very close to that of the animal proteins such as meat, milk, and eggs [153]. This makes soy proteins an excellent substituent for protein products derived from animals. Owing to the amount and value of soy proteins, soy-based foods have been a significant source of protein intake for human beings, mainly the people in East Asia and vegetarians [154]. Soy storage proteins generally include globulins and albumins, globulins accounting for 0%–90% of total bean proteins. The albumins mostly exist in the 2S form including trypsin inhibitors and cytochrome, whereas 7S, 11S, or 15S fractions usually correspond to globulins. Soy glycinin and β-conglycinin (SG and SC) are the two main globulins in soy storage proteins. The comparative SG-to-SC ratio in soy proteins remarkably differs with the type of cultivars, thus determining their physicochemical and emulsifying properties [155–157]. By eliminating oil from soybeans, a defatted soybean meal is widely applied in the food industry. Completely aqueous extractable soybean proteins can be divided into soy protein isolate (SPI) and whey by acidification to pH 4.5–4.8. SPI is one of the significant soy protein products, generally containing 85%–90% protein (dry basis). Owing to the complexity of manufacture, the structure and functional properties of SPI remarkably differ with the starting materials, processing variables, and even the producer [158]. SPI is a cost effective and creditable protein source, which can be applied as an alternative to meat and dairy proteins to control prices and increase the nutritional value of different food products. Furthermore, soy protein offers both nutritional and functional benefits over animal-based proteins. It is a great quality and whole protein, which comprises all of the vital amino acids essential to support human nutrition and is supported by an FDA-accepted health claim defining its positive result on heart health. Functionally, soy protein ingredients can replace animal-derived protein (meat, dairy, and egg) and decrease prices without altering the taste and quality. Using soy protein ingredients to replace meat, poultry, egg, fish, and dairy proteins can improve the quality of food products, decrease prices of different food formulations, and increase environmental sustainability related with the supply of quality protein [159]. Fig. 3.10 presents several functional properties of soybean protein in various food products [160]. Soy proteins display great emulsifying properties compared with other plant proteins, which help the formation of emulsions, mostly by decreasing the interfacial strain between water and the oil and helping stabilize the emulsion by forming a physical barrier at the interface [152]. Several bacteria such as Lactobacillus acidophilus, Lactobacillus delbrueckii, Bifidobacterium breve, and Bifidobacterium longum in fermented milk or yogurt are recognized as probiotics, which control the gut flora in a healthy situation. Nevertheless, nondairy probiotic products have newly been attracting much attention for people

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food systems

FIG. 3.10 Schematic representation of functional properties of soybean protein in food systems [160].

suffering from milk proteins allergy or lactose intolerance. Since soybean is free from lactose and cholesterol, it has been expected as an excellent matrix for probiotics [161, 162]. The total solid content in yogurt ranges from 12 to 15 g/100 g, and lactic acid bacteria is generally applied as a yogurt starter culture [163, 164]. Meanwhile, the total solid content of communal commercial soymilk is lower than this requirement. Soymilk is frequently determined by membrane technology [163]. Another example for the utilization of soybean in food products is Petit-suisse or spreadable cheese-like products, which contain soy protein developed in Argentina and Brazil. The benefit of this product is presumably related to the health benefit of soy protein [152, 165–167]. To alter the tendency of consumers, processors, and regulatory agencies, soy protein products are applied at a growing rate in different processed meat systems. Nonetheless, the world’s soy landscape indicates that processed meats are still the main drivers for functional soy protein ingredients. About 1 million metric tons of functional soy proteins are made yearly, and 55% of which are applied in processed muscle foods, counting meat, poultry, and seafood [168]. The main area of current domestic food application is in emulsified meats (Frankfurters) and coarse ground meats (ground beef patties) [169]. Various emulsified meat formulations comprising soy protein products have good eye appeal, good texture, and no off flavor and are effective on substantial savings (reduced cooking losses and greater products), but at the same time preserving excellent nutritional quality. Soy protein isolates and functional (dispersible) concentrates

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are the most effective soy ingredients applied in emulsion type meats. Furthermore, soy protein ingredients (mostly textured) are applied in retorted products to absorb juices liberated through canning, resulting in a less sloppy or firmer final product. Today, soy protein ingredients are applied in emulsion-type cheeses to replace as much as 50% of sodium caseinate in some products. Soy protein concentrates and isolates are a perfect source of highly digestible protein in beverages. The viscosity of soy protein is low. Thus, it can be applied in beverages. Soy protein helps obtain a favorite mouthfeel. The low viscosity afforded by soy isolate makes it perfect for other nutritious liquid products, such as infant formulas, creamers, milk replacers, and spray-dried products. In addition, soy protein products, including soy isolate-whey blends, have been applied in pound, devil’s food, yellow layer, and sponge cakes, replacing 50%, 75%, or 100% of the nonfat dry milk, respectively, without damaging the quality. Textured soy proteins (based on SPI, soy protein concentrates, and soy flours) are common and significant ingredients of various meats and meat analog products. It is usual to replace 30%–40% of the meat in foods such as beef patties and chicken nuggets [159]. Fig. 3.11 shows the major food applications of soy protein products [160].

3.5.6

Gluten

Gluten can be defined as the rubbery form remaining when the wheat dough is washed to eliminate starch granules and water-soluble ingredients. Depending on the carefulness of washing, the dry solid contains 75%–85% protein and 5%–10% lipids; most of the residue being starch and nonstarch carbohydrates. On the other hand, the word “gluten” refers to the proteins since they play an important role in defining the unique baking quality of wheat by conferring water absorption capacity, cohesivity, viscosity, and elasticity on the dough. Gluten comprises hundreds of protein constituents as monomers or linked by interchain disulfide bonds, as oligo and polymers [170]. The proteins, which form gluten, are storage proteins, according to their function for the wheat grain [171]. Wheat gluten is the protein extracted from wheat flour using the byproduct of starch and gluten-free food production [172, 173]. Wheat gluten is fundamentally applied to develop the properties of flour for bread making and as an additive in the baking industry. However, the applications of wheat gluten are becoming more varied, both inside and outside the food industries, with the growth of wheat starch manufacture [174, 175]. Gluten is exclusive in terms of its amino acid structures, which are known by high contents of glutamine and proline and low contents of amino acids with charged side groups [170]. Today, “vital wheat gluten” is an important ingredient in the food industry and a significant item of world trade [176, 177]. The word gluten is likewise applied in the market (mistakenly) to show the protein residue after isolating starch from corn (maize) [178, 179]. Nevertheless, this “corn gluten” is functionally very different from wheat gluten. The maximum usual application of

FIG. 3.11 Schematic representation of functional properties of soybean protein in food industry [160].

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FIG. 3.12 Schematic representation of usage of gluten in various food products [173].

gluten has traditionally been in western countries and continues to be in baked goods of different kinds. Nevertheless, the enhanced knowledge of wheat gluten’s unique structural and functional properties is accompanied by its various growing applications. Fig. 3.12 shows various applications of gluten [173]. In various products, which contain wheat, gluten is applied to strengthen the flours of lower than desirable protein content. By the addition of gluten, the amount of protein increases and the quality of the flour is improved to one with higher protein content. This strengthening may be essential since the flour has a naturally low protein while higher protein content is required to make superior products, or since the addition of gluten offers a specific property sought in the food by improving the quality of the protein. Bakers also use gluten to strengthen their basic flours at diverse levels to achieve the preferred performance for the manufacture of specialty bread and diverse types of bakery goods. Gluten is applied at about 2% in presliced hamburger and hot dog buns to increase the strength of the hinge and offer appropriate crust features when buns are stored in a steamer. In addition, it can be applied to strengthen pizza crust, making it possible to be produced in both thin and thick crusts from the similar flour. The incorporation of gluten offers crust body and chewiness and decreases moisture transfer from the sauce to the crust. A favorable property of gluten is its capability to bind fat and water simultaneously increasing the protein content. This makes gluten attractive for different types of application in meat, fish, and poultry products. Gluten develops the application of beef, pork, and lamb meats by a rearrangement process, which changes less favorable fresh meat cuts into more palatable steak type products. In processed meat

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products, gluten is an exceptional binder in poultry rolls, canned “integral” hams, and other nonparticular loaf type products, in which it develops slicing features and minimizes cooking losses through processing. The main use of gluten in nonbakery food products is as a meat substituent in vegetarian foods and in the manufacture of artificial forms of luxurious foods such as seafood and crab analogs. The viscosity of gluten can be applied in making synthetic cheese with the specific texture and eating quality of natural cheese. Gluten has been applied alone or in combination with soy protein to replace about 30% of the more exclusive sodium caseinate in imitation cheese products. Furthermore, gluten can be applied in the preparation of soy sauce extenders and the production of monosodium glutamate. The high glutamine content of gluten makes it a perfect starting material for the latter product. Soy sauce prepared by gluten has various properties such as light color, slow browning rate, perfect flavor, and excellent body compared with traditional soy sauce [173]. Due to the fear of the bovine spongiform encephalopathy (BSE) disease, the substitution of gelatin by other food proteins has established applications for gluten lately in food products such as chew candy or fruit chew, or as a clarifying agent for musts and white wines [180, 181]. In terms of its nutritional value, gluten (or wheat protein) is considered to be less than proteins from animal sources, mainly since it is somewhat deficient in lysine and threonine vital amino acids. Nevertheless, gluten does comprise high levels of the amino acid glutamine, which is vital for strengthening muscle/body building. Therefore, the application of gluten proteins is mostly owing to their physical functionality and comparatively low price [173]. Wheat gluten offers not only the protein appropriate for nutritional claims but also helps to bind vitamin and mineral enrichment constituents to the cereal or grain in the process and contributes to the textural strength of flake cereals. Consumers have broadly established wheat gluten strengthened breakfast cereals since they are very nutritious and crispy textured, particularly when consumed with milk. Furthermore, gluten can be added to flours of lower proteins for the production of pasta and noodles. Although durum wheat is favored for pasta, because of its high protein content and color, other more accessible flour can be applied efficiently if wheat gluten is added. The addition of gluten can decrease the cooking loss and stickiness in cooked pasta and noodles, offering well-cooked firmness, enhanced resistance to breakage, and increased heat tolerance in canned retorted products. Japanese noodles such as udon-type are usually prepared from high gluten wheat flour such as bread flour [182].

3.6 Conclusion and future prospects Proteins play an important role in food and many health and industrial applications. Proteins are natural polymers obtained from inexpensive sources and are therefore widely used as a good candidate in the food industry. Proteins including primarily of combinations of amino acids in peptide linkages contain carbon, hydrogen, oxygen, nitrogen, and usually sulfur. Proteins play key roles

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in foods affording taste, texture, and flavor, which are the main criteria for food selection. Various proteins such as collagen, gelatin, and whey can be used in different food industries. Due to the different properties of proteins, they can have different functions in the food industry, the most important of which is the ability to form gels, foams, and emulsions. Various factors affect the properties of proteins in food products. One of these is the interaction of proteins with other substances in food systems. Although progress has been made in the use of protein in the food industry, some steps need to be taken in the future such as: Ø The relationship between protein structure and function in food systems is not entirely clear and should be further explored in the future. Ø Although many proteins have been used in the food industry, there are still a number of proteins not used in the food industry, which need to be addressed in more detail in the future. Ø The development of functional foods and functional ingredients. Ø Improving the performance of various proteins in food systems.

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Chapter 4

Food packaging applications of biopolymer-based (nano)materials Mahmoud Nasrollahzadeh, Zahra Nezafat, Nasrin Shafiei, and Nayyereh Sadat Soheili Bidgoli Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

4.1

Introduction

Packaging foods is a skill or science necessary for preparing foods for safe transport, storage, or sale somewhere else from the production point. Packaging provides protection via altering resistance and exceptional biological, physical, or chemical needs [1]. Chemical contaminants, microorganisms, light, oxygen, humidity, etc. are the most important factors affecting food quality. Therefore, it is vital to maintain the safety and quality of the foodstuffs during the transport and packing conditions. To control these factors, packaging materials provide suitable physiochemical conditions, thus supply physical protection for the crops, followed by improvement of durability and maintaining the quality and safety [2]. Primary packaging substances such as glass, metal, paper, plastic, paperboard, and a mixture of materials of many chemical natures and physical arrangements are utilized to satisfy the aims and requirements of packaged foods depending on their kind [1]. Nanotechnology plays an important role both in the food packaging industry and in maintaining and improvement of food quality (Fig. 4.1) [3]. Nanotechnology also plays a role in warning consumers about the presence of bacteria and contaminants in foods, provides stronger flavor and color quality, repairs ruptures in packaging, and releases preservatives to extend the shelf life of the packaged food (Fig. 4.2) [4]. To control packaging, the attention to nanotechnology has been rising quickly. Moreover, there is a concern that nanomaterials may penetrate the food and endanger the health of consumers. Thus, food packaging should be properly designed to address this concern [1]. In today’s modern world, the development of food packaging has had a dayto-day alteration. Through the 18th century, people started to use natural Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00004-4 Copyright © 2021 Elsevier Inc. All rights reserved.

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Nanotechnology

immobilization

FIG. 4.1 Developments in food packaging by the help of nanotechnology [3].

materials for stylish packaging to save foodstuffs. These materials can be related to food containers such as glass, paper, and pottery. Considerable improvement of new industrial materials for food packaging innovations occurred in 2008 [5]. In the past few years, there has been an excessive change in packaging systems usually referred to as “smart packaging,” as a new packaging concept [6]. Smart food packaging means, it can repair itself, react to the environmental conditions, or alert consumers about contamination [1]. To develop the food quality and extend the expiration date by decreasing the microbial growth in the product, it is necessary to know biopolymers [7, 8]. Biopolymers have generally been studied over the past two decades because they can replace plastic food packaging [9, 10]. Biopolymers are natural compounds, which are divided into three groups, namely natural biopolymers such as polysaccharides (starch, alginate, cellulose, etc.) and proteins (collagen, gelatin, keratin, etc.), synthetic biodegradable polymers such as poly(L-lactide) (PLA), and biopolymers made via microbial fermentation such as poly(hydroxyalkanoates) (PHAs) [11]. Biopolymers can be degraded by microorganisms, which produce organic by-products such as CO2 and H2O. Biopolymers are commonly biodegradable and have low tensile strength. Nanostructured materials possess different morphologies such as crystallites, clusters, or nanofibers. The incorporation of nanostructures with biopolymers affords some nanocomposite materials with great surface to volume ratios and exceptional physiochemical features such as strength, solubility, magnetism, toxicity, diffusivity, color, optics, and thermodynamics [12]. Many research efforts have been focused on bionanocomposite compounds. Bionanocomposites are a good option to prepare food packaging materials, which can preserve food in a variety of ways due to their antibacterial and

Food design

FIG. 4.2 Effects of nanotechnology applications in food processing [4].

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antimicrobial properties by eliminating some factors such as oxygen and water vapor [11]. Combination with biodegradable polymers affords a wide range of considerable improvements in mechanical, electrical, thermal, optical, and chemical properties of nanostructures [13, 14]. Some biopolymers such as chitosan, starch, cellulose, PCL, PHB, PLA, etc. can be used for food packaging purposes [15]. Some food packaging materials are based on edible materials. In this specific case, by law, all materials used must be edible, both in the primary (packaging ingredients) and in the ending (packaging) forms. Two kinds of edible packaging are typically obtained: coatings and films [16]. In the food industry, numerous synthetic compounds have been utilized as antimicrobial agents to stop the development of pathogenic microorganisms and deterioration of packaging. Usually, these agents have been used as organic, inorganic, or biologically active substances [17–20]. Metal nanoparticles (NPs) such as Ag and ZnO NPs have antimicrobial and antibacterial properties, respectively. A schematic representation of biocidal mechanisms induced by these nanoparticles is displayed in Fig. 4.3 [21]. There are several suggestions regarding the antimicrobial mechanistic performance of NPs. Nanomaterials are commonly believed to be ideally different from traditional plastics and have served as potential packaging materials to extend the shelf life of food products. Since the huge surface-to-volume ratio offers more direct interaction with bacterial surfaces, these nanomaterials

Cytoplasmic membrane

Nanoparticles Bind to cell wall

Cell wall

Ele

ctro n dam trans age port

DNA damage Inactivation of proteins

Damage to membrane/cell wall

Release of ions ROS Generation of reaction oxygen species (ROS)

FIG. 4.3 Schematic representation of antimicrobial mechanism of inorganic nanoparticles [21]. (Reproduced with permission from Hoseinnejad M, Jafari SM, Katouzian I. Inorganic and metal nanoparticles and their antimicrobial activity in food packaging applications. Crit Rev Microbiol 2018;44(2):161–81.)

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display good antibacterial properties. Basically, cationic NPs are strongly attached to the membrane of bacteria via negatively charged external layers with electrostatic interactions. In addition, nanomaterials can also prevent or overcome biofilm formation [21]. Nowadays, the use of natural polymers in the food packaging industry is of great interest to researchers because of their properties, including biodegradability and economic viability. In addition, nanocomposites have been found to be promising choices for developing barrier and mechanical properties. Nanocomposites contain a biopolymer matrix strengthened by particles with at least a nanoparticle material, which display greatly enhanced properties because of their high surface area and high aspect ratio. Nanoparticles have several shapes and morphologies, including one-dimensional discs such as clay platelets, two-dimensional nanofibers such as nanowhiskers or nanotubes, and three-dimensional polyhedral and spherical particles such as colloidal silica [22]. Clay minerals such as laponite, montmorillonite, sapnotite, and hectorite can improve the barrier and mechanical properties because of their unique structure and properties [23]. Biopolymers complete the natural cycle of materials; after completing one cycle, the next cycle begins (Fig. 4.4) [24].

FIG. 4.4 Life cycle of biopolymers used for food packaging [24].

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4.2 Properties of bionanocomposites for food packaging The materials used in food packaging must have suitable properties to preserve foodstuffs. The properties of bionanocomposites are closely correlated to their structure. Fig. 4.5 shows some of these properties.

4.2.1 Mechanical properties The structure of polymers plays a key role in their mechanical properties [6]. Nanocomposites improve the mechanical properties of biopolymers. Even if the filler surface inside them is low, it still improves their mechanical properties. The mechanical properties of polymer clay-nanocomposites depend on the amount of the filler [25]. For example, some researchers have made starchbased nanocomposites using different weight percentages of starch to determine their tensile properties. Their results showed that with increasing the filler content (more than 8%) their strength increased and tensile stress decreased [26]. The overall results show that improving the mechanical properties of polymeric nanocomposites increases their strength [25]. As another example, Maiti et al. synthesized bionanocomposites based on polyhydroxybutyrate (PHB), which exhibited considerable development in the thermal and mechanical properties of the bionanocomposites compared to the polymer alone in 2007 [27].

function Mechanical properties

properties

Food packaging materials

barrier

p

b

barrier Environmentalfriendly FIG. 4.5 Common properties necessary for food packaging materials.

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Barrier properties

In the common packaging system, the particular barrier properties depend on the structures. For example, the use of ordinary plastics for food packaging is not suitable because small molecules such as water vapor, oxygen, and gases pass easily and have no good barrier effect. The fundamental differences in the shelf life and quality of the food products mostly depend on the presence of water vapor and oxygen inside and outside the packaging [6]. Polymeric nanocomposites act as barriers against water vapor and gases (such as CO2 and O2). The reduction of gas permeability in nanocomposites depends on the type of filler and the structure of the nanocomposites. The results show that the best barrier properties are observed in clay nanocomposites, which have a large surface area ratio (Fig. 4.6) [28]. Therefore, researchers are looking for ways to increase the barrier and mechanical properties of biopolymers, one of which is the use of bionanocomposites to incorporate metallic nanoparticles. The bionanocomposites containing a biopolymer matrix supplemented by nanoparticles display much enhanced properties because of the great aspect ratio and high surface area of NPs [29–31].

4.2.3

Biodegradation properties

Biodegradation of biopolymers might happen through some paths, including solubilization, hydrolysis, enzyme catalyzed hydrolysis, or microbial degradation alone or in combination with one another. Bionanocomposite packaging materials are estimated to be degraded in the environment after being used [25].

FIG. 4.6 Paths for gas passage through clay nanocomposites.

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Clay nanocomposites also improve the biodegradability. For example, Sinha Ray et al. concluded that the biodegradability of PLA nanocomposites was greater than that of PLA alone in a series of experiments on polylactic acid (PLA) in 2002 and 2003. They declared that the improved biodegradability of PLA nanocomposite films can be attributed to the presence of terminal hydroxylated groups on the edge of the clay layers [32–34]. Similar effects were also observed in other bionanocomposite films.

4.2.4 Antimicrobial properties Antimicrobial packaging is one of the most important active food packaging applications. Antimicrobial packaging helps increase the shelf life and food safety via destroying the microorganisms, which destroy food [35–37]. Commonly, antimicrobial packaging films are formed via the linkage of antimicrobial materials to polymeric surfaces or blending them through the polymer processing stage. Nanocomposite antimicrobial systems are highly efficient owing to the great surface-to-volume ratio and improved surface reactivity of the nano-sized antimicrobial agents, which makes them capable of deactivating extra microorganisms compared to their larger scaled counterparts [25]. Nanocomposite or nanoparticle materials have been studied for antimicrobial action as inhibitors, antimicrobial carriers, and packaging films [38–42]. As an example, silver NPs have antimicrobial properties and extensive studies have focused on the nanocomposites based on silver NPs, which have many applications in food packaging. These nanocomposites, including silver NPs with biopolymers such as starch and chitosan, represent strong antimicrobial properties [40, 43]. Furthermore, metal oxides such as TiO2, ZnO, and MnO have antimicrobial properties and are thus suitable for food packaging [44, 45].

4.3 Polysaccharide-based (nano)materials for food packaging Polysaccharides and their derivatives are widely used in the fabrication of biodegradable packaging materials. Some of the most commonly used polysaccharides include cellulose and its derivatives, starch, alginate, chitosan, and pectin. Given the hydrophilic nature of these molecules, the application of these polysaccharides is limited since they display poor barrier properties against water vapor [46].

4.3.1 Cellulose-based packaging materials Cellulose is the most abundant biopolymer on the earth. Wood is known as the largest source of cellulose. During the past decades, significant progress has been made in the packaging of biodegradable plastics, particularly from renewable cellulose. These developments are focused on obtaining enhanced food quality and safe packaging [47].

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Cellulose is insoluble in water and includes crystalline and fibrous regions, which make it unsuitable for film making. However, it can be dissolved in a mixture of carbon disulfide and sodium hydroxide and then react with sulfuric acid to form cellophane films. Cellophane is the most usually used cellulosebased food packaging, which is also known as regenerated cellulose in film. Though cellophane film affords improved mechanical properties, it is sensitive to moisture. This problem can be solved by coating cellophane with polyvinylidene chloride and nitrocellulose wax to improve its barrier properties and make it applicable for packaging of different foodstuffs, including processed meat, baked goods, fresh products, candy, and cheese. Another limitation of cellphone is that it cannot withstand heat and is therefore nonthermoplastic [48]. To make cellulose films, researchers use cellulose derivatives such as methylcellulose, carboxymethyl cellulose acetate, ethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose [47]. NatureFlex is one of the types of cellulose-based films widely used in food packaging because of its long shelf life and excellent gas barrier properties. These improved features make it useful for many applications such as fresh foods, home products, meat, dairy, and tea packaging [47]. Cellulose-based materials are widely used because of their properties such as biodegradability, edibility, barrier properties, nontoxicity, and economic benefits [49]. The cellulose structure has crystalline and amorphous regions, which are linked by intra and intermolecular bonds (Fig. 4.7). Therefore, only the surface cellulosic chains are easily available to chemicals [47]. Hydroxypropyl methylcellulose (HPMC) edible films are appropriate for food-packaging applications since they are readily accessible, nonionic, edible plant-based compounds, which are able to form clear, neutral, tasteless, oil impervious, water soluble films with very effective oxygen, carbon dioxide, aroma, and lipid barriers, but present moderate resistance to water vapor transport [50]. HPMC has been applied in the food industry as an emulsifier, film-forming agent, colloid protecting agent, stabilizer, and suspending agent. For example, in 2010, Imran and coworkers developed a bioactive composite coating based on HPMC using nisin (Nisaplin) as a preservative compound and glycerol as a plasticizer material to improve the mechanical, barrier (O2, H2O), transparency, and

Microfibril

m

FIG. 4.7 Crystalline and amorphous regions of cellulose [47].

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microbiological properties [49]. The synthesized bioactive film can be applied for food packaging because of its many advantages such as stable structure with excellent stretchability, moderate water sorption, and excellent antimicrobial effects. In another study in 2012, Moura and colleagues developed the incorporated Ag NPs into the matrix of hydroxypropyl methylcellulose (HPMC) [51]. The synthesized HPMC/AgNPs nanocomposites have excellent mechanical and water vapor barrier properties, and thus they can be used as food packaging materials such as active antimicrobial inner coatings. Nanocellulose is a word referring to nanostructured cellulose. Nanocellulose can be of various forms, including cellulose nanofibers (CNF), cellulose nanocrystal (CNC), and microfibrillated cellulose or bacterial nanocellulose, which is nanostructured cellulose made by bacteria [52]. Cellulose nanofibers could be obtained from a various range of cellulose-rich sources, for instance, banana, cotton, kenaf, bamboo, oil palm, wheat, bagasse, and rice [53–55]. Recently, significant attention has been focused on the cellulose nanofibers due to their sustainable features and their applications in various fields, for example, membranes, composites, filtration, packaging, medicine, construction, cosmetics, and foods [47]. Cellulosic fibers have been applied in packaging for a wide range of food types, for example, dry food products, frozen or liquid foods, drinks, and fresh foods [56]. The main purpose of food packaging is to preserve food and maintain its quality and safety, and reduce food wastes [57]. Bacterial cellulose (BC) is the cleanest form of cellulose present in microbes. BC has many applications in packaging materials because of its biodegradability and biocompatibility.

4.3.2 Starch-based packaging materials Among biopolymers, starch is one of the most promising biodegradable and biocompatible materials, which has attracted attention because of its various advantages, including economic viability, availability, and nontoxic nature [58]. Starch is a commonly available renewable source and can be obtained from different by-products of harvesting and raw material industrialization. Starch can be used in packaging fruits and vegetables, snacks, or dry products in film form. Coating and biodegradable films not only protect food quality but they also increase food safety and sustainability [59]. About 50% of bioplastics are synthesized from starch. The fabrication of starch-based bioplastics is easy, and they are commonly used for packaging applications [60, 61]. In the starch polymer chain, there are hydroxyl groups, which are very suitable for complexation with metals. Hydroxyl groups afford active sites for metals, resulting in good control over the shape, size, and dispersion of nanoparticles [62]. The combination of starch with nanoparticles leads to enhanced properties such as mechanical and barrier properties [63]. Commonly, nanomaterials used in food packaging could be categorized into two groups: inorganic and organic materials. Organic materials include but not limited to phenols,

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halogenated compounds, quaternary ammonium salts, plastic polymers, natural polysaccharides, or protein materials. On the other hand, combinations of inorganic materials including metals, metal oxides, or clay nanoparticles with bionanocomposite films and nanofibers can be considered [21, 64]. Several works have focused on the development of starch-based (nano) materials. For example, in 2015, Abreu and coworkers successfully developed an efficient method for the synthesis of three types of bionanocomposite films including Ag nanoparticles, montmorillonite improved by a quaternary ammonium salt (C30B) and both Ag-NPs and C30B, namely Ag-NPs/ST-NC, C30B/ ST-NC, and Ag-NPs/C30B/ST-NC, respectively [63]. The synthesized films have antimicrobial activity and afford high efficiency as food packaging materials. Various studies have shown that the incorporation of metal oxide nanoparticles reduces the hydrophilic property of biopolymers and can protect the food against UV radiation, thereby improving the biopolymer efficiency in food packaging [65–67]. For example, many studies have shown that the addition of TiO2 nanoparticles improves the quality of the films used for food packaging. These nanoparticles combine with composites to form compounds with unique properties, which are suitable for food packaging [21]. In 2016, Oleyaei and coworkers reported that various concentrations of TiO2 NPs combined with potato starch films [68] increase the tensile strength and transparency of the film and reduce the water vapor permeability. The aforementioned advantages make TiO2 NPs improve the functional properties of potato starch film. The synthesized nanocomposite is used as a suitable compound for food packaging [68]. Starch films have low permeability to gases, which makes them attractive materials for food packaging. An example of this was reported in 2017 by Goudarzi and colleagues, who developed the synthesis of the bionanocomposite appropriate for food packaging using various contents of TiO2 NPs and starch [69]. In addition, they showed that the mechanical, physical, thermal, and water vapor permeability (WVP) properties of starch/TiO2 film also increased with increasing the amount of nanoparticle film, which reduces the water vapor permeability [69]. Starch-based films are inherently fragile and therefore lack the mechanical properties required for food packaging. Combining starch with some additives can improve its mechanical properties [70]. For example, in 2013, Ghasemlou investigated the incorporation of two types of oils, namely Zataria multiflora Boiss (ZEO) or Mentha pulegium (MEO) at three levels into the starch film using solution casting technique [71]. In this work, they increased the mechanical and water vapor permeability (WVP) properties. By incorporating these oils with the corn starch, they produced a biodegradable, antimicrobial film suitable for food packaging [71]. Sago starch is one of the types of starch, which is somehow unknown. Sago starch is obtained from the palm tree (Metroxylon sagu) and is the cheapest type of starch. For example, Alebooyeh and colleagues synthesized a film based on sago starch in 2012 [72]. They used zinc oxide nanoparticles to improve the

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antimicrobial and permeability to water vapor properties of sago starch. The synthesized sago starch films supported ZnO nanorods and were applied as active packaging for crops, and in food industry [72]. Quinoa seed (Chenopodium quinoa, Willdenow) is a grain usually found in the South American Andean highlands. Quinoa consists of considerable amounts of starch (up to 80%), has an amylose content of 10%–21% (depending on the diversity), and a small starch granule size (1 μm), which allows its easier dispersion and thus makes it a promising material for the film. This starch might be capable of producing transparent, biodegradable, edible films without any prior chemical treatment [73]. Pagno et al. conducted a study in this area. They synthesized active biofilms using quinoa (Chenopodium quinoa, W.) starch and Au nanoparticles. They used ionic silsesquioxane containing 1,4diazoniabicyclo[2.2.2]octane chloride group to stabilize gold nanoparticles. The active biofilms showed excellent antibacterial activity against food borne pathogens. The synthesized quinoa starch biofilms with Au NPs are very suitable as active food packaging compounds for the preservation of food safety and extension of the shelf life of packaged foods [70]. Starch consists of two types of amylose and amyloid pectin polysaccharides. The higher is the amount of amylose, the greater the tensile properties of the film [74]. Among starches in different plants, the starch in rice and maize has the highest amount of amylose and is, therefore, more suitable for food packaging. Marichelvam et al. developed the films produced from corn and rice-starch-based bioplastics [74]. The synthesized films have excellent tensile and biodegradability properties. The experimental results show that corn and rice starch films are suitable for food packaging.

4.3.3 Chitin and chitosan-based packaging materials Chitin, the second abundant biopolymer after cellulose, is obtained from the exoskeleton of crustaceans and the cell walls of several fungi. This natural polymer contains N-acetyl D-glucosamine units with (1–4) linkages [75]. Chitin is an amino polysaccharide with biological activities and is moderately attractive as a biodegradable natural polymer. Chitosan is obtained by the deacetylation of chitin, which is a hydrophobic polysaccharide made from acetyl glucosamine and glucosamine grafts and is found in the outer skeleton of shellfish such as shrimp, squid, lobsters, crabs, walls of algae, and so on (Fig. 4.8) [76]. Chitin and chitosan have some excellent properties such as biodegradability, nontoxicity, and antimicrobial properties. Thus, they have been widely considered for food packaging films, air, and water filtration, artificial skin, water engineering, etc. [77, 78]. The antimicrobial activity of chitosan depends on both intrinsic factors such as molecular weight, degree of polymerization, and deacetylation, and external conditions such as pH, temperature, target microorganism, and nature of the medium [79, 80]. The antimicrobial activity of chitosan is due to the positive charges of amino groups get in an acidic pH [81]. Chitosan-containing cationic

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FIG. 4.8 Paths for chitin and chitosan preparation.

groups shows antimicrobial properties against bacteria, yeasts, molds, and fungi [82]. Chitosan-based films consisting of metallic nanoparticles, chitosan nanoparticles, polymer blends, and bioactive compounds are very excellent choices for food packaging materials (Fig. 4.9). Today, chitosan nanocomposites, which consist of a combination of chitosan and organic/inorganic nanoparticles, have attracted significant attention [83]. Chitin and chitosan-based nanoparticles are common organic materials, which have recently been widely studied. For example, in 2014, Dehnad and coworkers developed the synthesis of chitosan-nanocellulose biocomposites. The synthesized bionanocomposite showed high inhibitory effects against gram-positive and gram-negative bacteria. This makes it a promising compound for food packaging [84]. Nano-reinforcement is more effective on the management of the price and improves the properties of chitosan biopolymers [85]. When isolated soy protein thermoplastics were added to the chitin whiskers, their tensile strength and water resistance were found to be enhanced [86]. Similarly, when chitosan films were added to chitosan whiskers, the whiskers improved the tensile strength and water resistance ability of the chitosan films [87]. In addition, chitin whiskers can be used as reinforcing fillers in polymeric matrices because of their high aspect ratios and crystalline nature [85, 88, 89]. Since there are fewer amine groups in chitin compared with chitosan, the combination of chitin with a chitosan matrix

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Based films nanoparticles

nanoparticles

FIG. 4.9 Strategies for the fabrication of chitosan-based films.

does not improve its antibacterial properties [90]. Based on the superior antibacterial activity of rectorite-chitosan composites and strength improvement of chitin whisker, Li and coworkers successfully developed a method for the synthesis of chitosan/chitin whisker/rectorite ternary films, which were then used as suitable food-packaging materials [81]. Montmorillonite (MMT) is a natural, layered silicate clay used as a suitable nano-reinforcement for chitosan films because of its high aspect ratio and huge surface area [25]. Beikzadeh Ghelejlu and colleagues reported the synthesis of chitosan/nanoclay nanocomposite active films using three different levels of sodium montmorillonite (MMT) and Silybum marianum L. extract (SME) [91]. The mechanical, barrier, thermal, and antioxidant properties of the synthesized film were greatly improved. By incorporation of MMT and SME, water vapor permeability and solubility of the films were reduced. The antioxidant properties of the film were enhanced by the participation of the MMT and SME, which makes the bionanocomposite an effective and antioxidant material for food packing [91]. By using nanoscience, novel forms of nanocomposites distributed with nanoparticles can be developed to minimize the migration of water over the polymeric package in addition to developing the mechanical properties [92, 93]. Chitosan NPs can be made by ionic gelation and addition of chitosantripolyphosphate NPs in hydroxypropionyl methylcellulose membrane and

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the mechanical and obstruction functions of the films can be increased [83,94]. In 2008, De Moura et al. reported the synthesis of novel hydroxypropyl methylcellulose films including chitosan nanoparticles [95]. By incorporating chitosan nanoparticles into the film, its mechanical and barrier properties are improved. The synthesized film can be used as a promising compound in food packaging in the future [95]. Biodegradable chitosan provides bacteriostatic and fungistatic activities. Thus, chitosan has been one of the significant biomaterials for food and biomedicine industries in the recent years [96]. Chitosan is soluble in an aqueous acidic medium due to the presence of amino groups. Chitosan derivatives have been commonly known as safe compounds (GRAS) by the US Food and Drug Administration (2011) for fixed use in foods and their application is gaining attention [83]. Furthermore, nanocomposites, which contain metallic NPs, show a high antimicrobial response and excellent mechanical and barrier properties. The experimental results show that the antibacterial activity of chitosan and the synergetic nanoparticles is due to the effects created by the action of each one and the change of the surface chemistry of NPs [97–99]. According to the organic antimicrobial materials, several noble metals, for instance, Ag, Cu, and Au NPs, in addition to the oxidized nanomaterials such as ZnO, TiO2, and MgO have been of much interest because of their resistance to the uneven processing conditions and improvement of strong biocidal impacts against foodborne pathogens [21]. The use of zinc oxide nanoparticles (ZnO) has been reflected as a sustainable solution to stop infectious illnesses because of the excellent antimicrobial properties of these NPs. Wang and coworkers used ZnO NPs as antimicrobial agents [100]. They synthesized composite nanofibers containing chitosan and ZnO NPs using polyvinyl alcohol as the support. The synthesized chitosan/nano-ZnO was used as an antimicrobial composite to improve food safety and shelf life. This technique can allow the rapid monitoring of the efficiency of the antimicrobial agents against foodborne pathogens [96]. Another example in this regard is the research by Almasi and his colleagues, who synthesized novel bionanocomposites using CuO and chitosan nanofibers (CHNF) [64]. The synthesized CuO-CHNF nanohybrid, which showed excellent antimicrobial activity, was used as a promising food packaging material [64]. In 2016, Zhang et al. developed a method for the synthesis of chitosan/whey protein isolated film by incorporating sodium-laurate-modified TiO2 NPs [101]. The mechanical, barrier, tensile strength, and water vapor permeability properties of the newly fabricated nanocomposite were improved. The synthesized nanocomposite was applied as a food packaging material. Moreover, chitosan NPs are more advantageous than bulk chitosan due to their greater surface area and charge density, which provide an excellent interaction with the surface of bacterial cells [102]. Scientists have assessed the result of chitosan NPs combined into gum films (Fig. 4.10) [103, 104]. The experimental results of these studies show that as the size of chitosan NPs increases, the antimicrobial properties of the films decrease. This is because large NPs do not allow efficient contact with the bacterial membrane and the

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FIG. 4.10 Coating chitosan particles by guar gum [103]. (Reproduced with permission from Nazarzadeh Zare E, Makvandi P, Borzacchiello A, Tay FR, Ashtari B, Padil VTV. Antimicrobial gum bio-based nanocomposites and their industrial and biomedical applications. Chem Commun 2019;55:14871–85.)

agglomeration reduces their surface charge. In addition, chitosan NPs can occupy the free volume in the system structure and improve hydrophobicity and vapor permeability. Other researchers also obtained similar results. Chang et al. developed the incorporation of chitosan NPs (CNs) with starch with improved tensile strength, storage modulus, glass transition temperature, water vapor barrier, and thermal stability [105]. This compound was used as a suitable food packaging material. Polymer blends are an excellent choice for film production for food packaging since the properties of each structure are used to make materials with high tensile properties and an appropriate barrier against moisture, gases, and water. Incorporated natural and synthetic polymers such as chitosan, starch, and PVA have shown to be excellent choices for food packaging materials. Another study in 2011 showed that chitosan and starch had good antimicrobial properties in addition to good chemical interactions [106]. Arora and coworkers developed a method for the synthesis of the ternary blend films of chitosan/starch/PVA (polyvinyl alcohol) using glutaraldehyde and PEG (polyethylene glycol) as cross-linking and plasticizer agents, respectively [107]. The synthesized blended films are stable up to 190°C and show excellent antimicrobial

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activities, making them great choices for food packaging [107]. The use of glutaraldehyde as a binding agent increases the stability of the materials [106]. In the studies performed by Zemljic and colleagues, the functionalization of the surface of polyethylene terephthalate (PET) by chitosan was reported [108]. The synthesized chitosan-based films were very effective because of chitosan properties, viz. biodegradability, antimicrobial activity, and nontoxicity. According to the reported results, the synthesized chitosan-based films have antimicrobial activity against food-borne microbes, which makes them beneficial as promising food packaging materials [108]. In addition, Lago and coworkers used chitosan, polyethylene, and polyethylene terephthalate to produce films with excellent mechanical properties and antimicrobial activity [109]. They applied the synthesized film for food packaging materials [109]. Similarly, PEGylated chitosan (Fig. 4.11) has displayed an excellent option for food packaging applications due to its antibacterial activity and formation of flexible films [110]. Similarly, the combination of oleic acid and chitosan matrices causes a decrease in their tensile and barrier properties [111]. In another study, Lei and coworkers reported the antimicrobial action of polyethylene terephthalate/polypropylene (PET/PP) films, which incorporate with chitosan to form (chitosan/PET/PP)-based films [112]. The experimental results show that the chitosan release rate increases with increasing temperature and acidity and decreases with decreasing ionic strength of the solution. The synthesized antimicrobial film can be used as a promising food packaging material in the future. Table 4.1 shows some results correlated to the antimicrobial activity and mechanical and barrier properties of chitosan-based films [106]. Incorporation of chitosan with bioactive materials such as Maqui berry, eugenol, phenolic compounds, natamycin, Aloe vera, pomegranate, grape seed extract, nisin (NS), and natamycin also affords a barrier against water vapor and improves the tensile properties of the films [106]. In studies performed by Genskowsky and colleagues, the incorporation of chitosan edible films (CH) with maqui berry extracts (MB) was reported [118]. The synthesized CH + MB displayed high antioxidant and antibacterial properties. These properties could be attributed to the bioactive compounds such as phenolic acids, flavonoids, or anthocyanins in the maqui berry extracts. CH + MB can be used as a food packaging material to delay the microbial growth and increase the oxidative stability of foodstuffs [118]. In another study, Aljawish et al. successfully developed a method for functionalization of chitosan particles by ferulic acid (FA) and ethyl ferulate (EF) oxidation products using Myceliophthora thermophila laccase [119]. The FA-chitosan derivative films are colored, while the EF-chitosan derivative films or chitosan films are colorless. Phenolic compounds in chitosan films improve barrier, water sorption, and mechanical, surface and antioxidant properties. Considering their higher phenol content, FA-chitosan films display remarkable functional properties compared to EF-chitosan films. These novel films can be applied as promising food packaging materials [119]. Table 4.2 represents some results of chitosan-based films, which incorporate bioactive materials [106].

FIG. 4.11 Schematic representation of PEGylated chitosan synthesis: (A) chitosan, (B) thiolated chitosan, and (C) PEGylated chitosan [110].

TABLE 4.1 Mechanical, barrier, and antimicrobial properties of chitosan-based films prepared using polymer blends [106]. Polymer blends of chitosan

Tensile stress

Water vapor permeability

Oxygen permeability

Solubility

CO2 permeability

References

ChPolyamide 66/6-Ch-PEaPET

40 MPa

–

–

–

–

[109]

Ch/PVA-TiO2

6.53–17.15

3.47–4.84  10

–

–

[113]

Ch-Fish gelatin

11.28  1.02 MPa

0.884  0.127 g mm/kPa h m2

–

65.19  2.32%

–

[114]

Ch-Fish gelatin

6.72–3.28 MPa

0.525–0.683 g mm/kPa h m2

–

–

–

[115]

ChCelluloseglycerol

60.8  5.17 MPa

8.591  10

–

–

–

[116]

Ch-FucoPol

–

0.75(0.05)  10

0.47(0.19)  10 16 mol m/m2 s Pa

–

5.8(0.7)  10 16 mol m/ m2 s Pa

[117]

a

Polyethylene.

10

12

g cm/cm2 s Pa

 2.1  10

11

11

g

mol/ms Pa

1

1.25– 1.59 cm3 m

s

1

Pa

1

2

s

1

Pa

1

TABLE 4.2 Properties of chitosan-based films that incorporate bioactive materials [106]. Chitosanbioactive compounds

Tensile stress

Ch-Ferulic acid (FA)

EF: 58.7  2.7 MPa

Ch-Ethyl ferulate (EF)

FA: 58.3  2.1 MPa

Water vapor permeability

Oxygen permeability FA: 0.6  (0.1)  10 10 cm3 Pa 1 s

1

m

1

EF: 3.6  (0.25)  10 10 g/Pa s m

EF: 0.8  (0.2)  10 10 cm3 Pa 1 s

1

m

1

FA: 3.9  (0.15)  10 10 g Pa 1 s 1 m

1

Moisture content

Solubility

Antimicrobial activity

References

–

–

–

[119]

Ch-Eucalyptus globulus essential oil

–

–

–

15.95  1.27%

13.19  1.03%

Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans, and Candida parapsilosis

[120]

Ch-PVAAnthocyanins

9.6 MPa

–

–

–

–

–

[121]

Ch-Galic acid

9–17 MPa

–

–

–

–

Escherichia coli and L. monocytogenes

[122]

Ch-Eugenol-TPF

153  0.23 MPa

4707.38  83.55 gmil/m2-day-atm

229.06  3.34 cc-mil/ m2-day-atm

–

–

–

[123]

Ch-Benzoic acid-Sorbic acid

–

–

–

–

–

Escherichia coli, Staphylococcus aureus, Bacillus cereus, and Ps. fluorescens

[124]

Ch-Cyclodextrin Carvacrol

–

–

–

–

–

Mesophiles, psychrophiles, Pseudomonas spp., Enterobacteria, lactic acid bacteria, yeasts, and fungi

[125]

Ch-Carvacrol

–

–

–

–

–

Bacillus subtilis, Escherichia coli, Listeria innocua, and Salmonella enteritidis

[126]

Ch-Gelatin-mint or thyme essential oils

–

–

–

–

–

L. monocytogenes

[127]

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4.3.4 Other polysaccharide-based packaging materials The application of natural polysaccharides in food packaging has been a topic of extreme investigations due to their biocompatibility and biodegradability [128, 129]. Galactomannans are heteropolysaccharides found in the endosperm of certain leguminous pips. They are used for storage, water retaining, and defense applications [130]. Galactomannans are water soluble and form highly viscous, stable aqueous solutions. They are broadly used as thickeners and stabilizers in food packaging applications [46]. The most common galactomannans are locust bean gum (LBG) (from Ceratonia siliqua) and guar gum (GG) (from Cyamopsis tetragonoloba) [131]. These gums are heterogeneous polysaccharides composed of β-(1–4)-D-mannan backbone and a single D-galactose branch linked α-(1–6). They differ from each other by the mannose/galactose (M/G) ratio. For example, the mannose/galactose ratios for LBG and GG are 3.5:1 and 1.5:1, respectively [46]. GG could be an excellent candidate for food packaging because of its high molecular weight, long polymeric chain, and extensive availability compared to other biopolymers [132, 133]. GG is very soluble in water and has excellent film-making ability. However, the applicability of GG in food packaging has been limited due to its low thermomechanical and barrier properties [132, 134, 135]. The dispersion of NPs in the biopolymer medium improves the favorite properties of biopolymer matrices including tensile strength, thermal stability, and rheological properties [136]. NPs can be used to improve the thermomechanical and barrier properties of the fragile guar gum films. Ag NPs have more antibacterial properties than other metal NPs (Ag > Cu > Au > Zn > Fe) [137]. Furthermore, bimetallic NPs such as AgCu have excellent optical, interfacial, catalytic, and antimicrobial properties compared with single metallic NP when combined in food packaging [138]. For instance, Arfat and his colleagues reported the synthesis of GG-based nanocomposite (NC) films using Ag-Cu alloy NPs in 2017 [139]. The synthesized NC films show improved mechanical strength, oxygen barrier, and antimicrobial properties. Some polysaccharides with film-making capacity can be formed by microorganisms (yeast, fungus, or bacteria), such as pullulan, gellan gum, xanthan gum, FucoPol, bacterial cellulose, or bacterial alginates, which are shown in Table 4.3 [140]. Xanthan gum is an exopolysaccharide formed by Xanthomonas campestris using glucose as a single carbon source. It is also the second commercialized microbial polysaccharide. This heteropolysaccharide contains repetitive pentasaccharide units composed of glucose, mannose, and glucuronic acid (2:2:1 ratio) and pyruvate and acetyl substituents [149–151]. Xanthan is water soluble and can be applied in an extensive variety of industrial applications such as food packaging [151]. Carboxymethyl guar gum/Ag nanocomposite films have been synthesized using reduction process for food packaging materials [103]. These bionanocomposite films display antibacterial activities and better tensile strength than pure

TABLE 4.3 Properties and applications of polysaccharides from microorganisms in food packaging [140]. Polysaccharide

Microorganism

Composition

Membrane properties

Main food applications

References

Pullulan

Aureobasidium pullulans

Maltotriose (three glucose)

Biodegradable, transparent, edible, oil and grease resistant, heat sealable, high water solubility, barrier to oxygen

Coating material, wrapping material, blends with other polymers to improvement of mechanical properties, inner package, seasoning bag of instant noodles, instant coffee

[141–143]

Gellan gum

Sphingomonas elodea

Glucose, rhamnose, glucuronic acid

Biodegradable, edible, lipid barrier, excellent gas barrier, good tensile strength

Edible, coatings in breading and batters for chicken, fish, cheese, vegetables and potatoes, encapsulation of flavor and bioactive ingredients

[144–146]

Xanthan gum

Xanthomonas campestris

Glucose, mannose, glucuronic acid, acetate, pyruvate

Biodegradable, edible

Edible coating‚ meet (prevent moisture migration during frying)‚ fruit (extend shelf-life)

[143, 147]

FucoPol

Enterobacter A47

Fucose, galactose, glucose, glucuronic acid, acetate, succinate, pyruvate

Biodegradable, transparent, high gas barrier, poor water resistance

Possible application as inner layer in multilayer packaging

[117, 148]

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carboxymethyl guar gum films [152]. In another study, researchers developed a method for the synthesis of nanocomposites by the incorporation of TiO2 NPs with gum polysaccharides. These nanocomposites might be applied for water treatment and food packaging due to the photocatalytic, antiultraviolet light, and antibacterial properties of the combined TiO2 NPs and the biodegradability and hydrophilicity of the gum constituent [153, 154]. In another experimental study, Kong et al. successfully synthesized gum arabic selenium nanocomposites (GA-SeNPs), in which GA was used as a stabilizer agent [155]. The synthesized nanocomposites are good candidates for food packaging applications because of the antibacterial activity, biodegradability, and antioxidant activity of Se NPs and acacia gum, respectively [103, 155]. In another example, researchers used a blend of two biopolymers with metal NPs. In this work, Kanikireddy and coworkers carried out the synthesis of carboxymethyl cellulose (CMC)-guar gum-silver nanocomposite films (CG-Ag0NC) [156]. Mentha leaves extract produced Ag NPs in the CMC-guar gum matrix through reduction process (Fig. 4.12). The shelf life of CG-Ag0NC films was confirmed using strawberries as the model fruit, and the results were compared with those of other nanocomposite packaging materials. The experimental results showed that CG-Ag0NC had a better protection effect and improved shelf life of fresh strawberries compared to the original CG and plastic films [156]. Another type of polysaccharide is alginate, which is derived from brown algae. Alginate is a green and good candidate for the preparation of food

FIG. 4.12 Schematic representation of preparation of CG-Ag0NC suitable for fruit packaging [156].

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packaging films due to its various advantages such as long polymeric chain, availability, biodegradability, and nontoxicity. Alginate is constituted from a linear block co-polymer of 1,4-linked β-D-mannuronic and α-L-guluronic [157]. Considering the properties of alginate, its application in the food packaging industry is common. Alginates are one of the effective polysaccharides, which are applied as edible coatings in food packaging. For example, in 2016, Shankar et al. developed an efficient and simple method for the synthesis of alginate/AgNPs composite films using different Ag NPs such as metallic silver (AgM), silver zeolite (AgZ), citrate reduced Ag NPs (AgNPC), laser-ablated silver nanoparticles (AgNPLA), and silver nitrate (AgNO3) [157]. The synthesized alginate/AgNPs films have excellent potential for application in antimicrobial food packaging films. In another example, Fayaz and colleagues performed the synthesis of bionanocomposite film by the incorporation of a sodium alginate thin film with Ag NPs [158]. This film increases the shelf life of carrot and pear. The experimental results showed that the Ag NPs incorporated with sodium-alginate-coated vegetables and fruits were appropriate for protection. In another study, sodium alginate was applied to produce a biocomposite coating to preserve the quality of Fior di latte cheese [159, 160]. Tang et al. conducted another experimental study in 2018 in which they successfully synthesized sodium alginate film containing functional Au-TiO2 nanocomposites (Fig. 4.13) [161]. The synthesized degradable Au-TiO2/sodium alginate composite film was applied as a promising food packaging material due to its antibacterial properties. Table 4.4 shows various applications of alginate in food packaging [179]. In general, the use of polysaccharides has become very

FIG. 4.13 Schematic representation of the fabrication process of the Au-TiO2 nanocomposite film [161]. (Reproduced with permission from Tang S, Wang Z, Li P, Li W, Li C, Wang Y, Chu PK. Degradable and photocatalytic antibacterial Au-TiO2/sodium alginate nanocomposite films for active food packaging. Nanomaterials 2018;8:930.)

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TABLE 4.4 Application of alginate in food packaging industry. Form of alginate

Additional compounds

Advantage of the process

Sodium alginate

Montmorillonite/cellulose NPs

Reduced water vapor permeability

[162]

Sodium alginate

Montmorillonite clay

Reduced water permeability and increased water solubility

[163]

Sodium alginate

Polyethyleneimine, biaxially oriented poly (lactic acid)

Enhanced oxygen barrier properties

[164]

Sodium alginate

Natamycin

Increased water soluble matter, water vapor permeability and opacity; decreased tensile strength

[165]

Sodium alginate

Partially hydrolyzed sago starch, lemongrass oil, and glycerol

Increased antimicrobial property, flexibility, and mechanical strength

[166]

Sodium alginate

CaCl2

Enhanced mechanical properties, water resistance; decreased water vapor permeability

[167]

Sodium alginate

Lysozyme, nisin, grape fruit seed extract, ethylenediaminetetraacetic acid

Antimicrobial effect against bacterial strains studied

[168]

Calcium alginate

Silver-montmorillonite nanoparticles

Prevents dehydration and microbial spoilage of fresh cut carrot; increased shelf life

[169]

Calcium alginate

Nisin

Suppression of bacterial growth

[170]

Calcium alginate

–

Lowered shrinkage loss, drip and degree of off odor in beef; prolonged muscle color

[171]

References

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TABLE 4.4 Application of alginate in food packaging industry—cont’d Form of alginate

Additional compounds

Advantage of the process

References

Food-grade alginate

–

Preserved quality of button mushroom and increased shelf life

[172]

Alginate cast film

Glycerol and sorbitol

Both plasticizers positively influence the mechanical properties

[173]

Alginate cast film

Enterocins and highpressure processing

Delayed growth of L. monocytogenes in cooked ham

[174]

Alginate cast film

Potassium sorbate

Potential use as systems for release of active substances

[175]

Gelatine/ sodium alginate blend

Corn oil and olive oil

Minimum water loss from sausages; manufactured sausages exhibited high oxygen barrier properties

[176]

Propylene glycol alginate

Soy protein isolate films

Increased tensile strength, decreased percentage elongation at break; decreased water vapor permeability and solubility

[177]

Biocomposite film of cellulose and alginate

Unmodified birch pulp, microfibrillated cellulose, nanofibrillated cellulose, nanofibrillated anionic dicarboxylic acid cellulose

Increased mechanical properties of alginate films, excellent grease barrier properties, and reduced water vapor permeability

[178]

Reproduced with permission from Theagarajan R, Dutta S, Moses JA, Anandharamakrishnan C. Alginates for food packaging applications. In: Ahmed S, editor. Alginates: applications in the biomedical and food industries. John Wiley & Sons; 2019. p. 205–32.

TABLE 4.5 Properties and food packaging applications of various polysaccharide membranes obtained from animals, plants, and algae [140]. Polysaccharide

Composition

Properties

Main food applications

References

Chitin

N-Acetylglucosamine

Biodegradable, antibacterial and fungistatic properties, biocompatible, and nontoxic highly transparent

Coffee capsules, food bags, packaging films

[143, 180, 181]

Chitosan

D-Glucosamine Nacetyl-D-glucosamine

Biodegradable, biocompatible, and nontoxic, antifungal and antibacterial properties, good mechanical properties, barrier to gases, high water vapor permeability, brittle-need to use plasticizer

Edible membranes and coatings (strawberries, cherries, mango, guava, among others), packaging membranes for vegetables and fruit

[181–185]

Starch

Glucose

Biodegradable, transparent, odorless and tasteless, retrogradation, high elongation and tensile strength

Flexible packaging: extruded bags, nets for fresh fruit and vegetables, rigid packaging, thermoformed trays and containers for packaging fresh food

[183]

Cellulose

Glucose

Biodegradable, good mechanical properties, transparent, highly sensitive to water, resistance to fats and oils, need to perform modification, use of plasticizer or polymer blend

Cellophane membranes

[183]

Galactomannans

Mannose, galactose

Biodegradable, edible semipermeable barrier to gases

Edible membranes and coatings: fruits and cheese

[185, 186]

Carrageenan

Galactose

Biodegradable, fragile and ductile behavior, usually blended with other polymers

Coatings, fruits, meet, encapsulation of aroma compounds

[183, 187]

Alginate

Mannuronic, glucuronic acid

Biodegradable, high water vapor permeability, poor water resistance, strong and brittle membranes, crosslink with calcium

Coatings, prevent water loss in fresh cut fruit (apple, papaya, pear, and melon), inhibition of microbial growth (turkey products), microwaveable food (increase warming efficiency)

[183, 185, 187]

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common in the food packaging industry. Table 4.5 summarizes the general properties of polysaccharides, which make them suitable for food packaging applications [140].

4.4

Lignin-based (nano)materials for food packaging

Lignin is the second most abundant plant after cellulose and the most abundant natural aromatic source [188, 189]. About 70 million tons of lignin are presumably obtained from the paper industry each year [190, 191]. In the 1940s, lignin was developed as a “green” renewable source for vanillin [192]. Due to its polyphenolic structure, lignin has interesting properties such as antioxidant activity. Natural antioxidants are very attractive for the protection of light or oxygensensitive goods and are applied in active packaging [193]. Many researchers have studied the utilization of lignin in biocomposites due to its abundance, excellent mechanical properties, biodegradability, and different modifications based on its chemical structure [194, 195]. Lignin is different from cellulose and hemicellulose and contains aromatic rings. It is a polyphenolic macromolecule containing three phenylpropane monomeric units, including coniferyl (G), p-hydroxyphenyl (H), and sinapyl alcohol (S) (Fig. 4.14) [196]. The lignin produced by the paper industry can be in two forms: lignosulfonate or Kraft lignin (KL). KL constitutes 85% of total world lignin manufacture, but lignosulfonates are the most significant commercially accessible lignin with a yield of about 1 Mt per year [196, 197]. Blending lignin with other natural polymers has been attractive owing to its wide accessibility, excellent mechanical and barrier properties, and biodegradability in addition to various potential modifications due to its chemical structure [198]. Many experimental studies have focused on the combination of lignin with biopolymers such as starch, cellulose, protein, chitosan, PLA, and PHB to form bioplastics [199, 200]. The utilization of lignin as a reinforcement usually reduces cost and water uptake and enhances the strength [201]. Furthermore, lignin significantly

alcohol alcohol FIG. 4.14 Three monomers of lignin [196].

alcohol

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affects antioxidant properties as a stabilizer since its phenolic hydroxyl groups can scavenge free radicals [202, 203]. Antimicrobial packaging is frequently accomplished by a combination of antimicrobial agents into the packaging materials. Some organic and inorganic materials have been applied as antimicrobial agents in antimicrobial packaging systems [204]. However, the low thermal stability of organic antimicrobial agents has restricted their wide use in food packaging applications. In comparison, the excellent thermostability of inorganic antimicrobial materials such as metallic NPs has created a new method for their use in the food packaging applications [205]. Among metallic NPs, silver nanoparticles (Ag NPs) have been the most widely applied for the preparation of nanocomposites in the food packaging systems because of their excellent surface area, unique optical, magnetic, electric, and catalytic properties, great thermal stability, and wide range of antimicrobial functions [2, 206]. One approach to organize nanoparticles is using biopolymeric materials. Lignin is an exciting compound since it can be used not only as a reducing and stabilizing agent for the preparation of nanoparticles but also as a filler for the preparation of nanocomposite films appropriate for food packaging [207]. For example, in 2017, Shankar and Rhim reported the synthesis of agar-based biodegradable films by the incorporation of lignin and Ag NPs, in which lignin capped silver NPs. The synthesized films were used as suitable materials for food packaging [207].

4.5 Protein-based (nano)materials for food packaging Proteins and their derivatives are generally used in the production of biodegradable packaging materials. Protein materials include gelatin, keratin, whey, soy, etc. In the next section, a general overview of protein-based food packaging will be given.

4.5.1 Gelatin-based packaging materials Gelatin is one of the biopolymers with animal protein origin, which is present in the bone and skin of animals. Gelatin has many advantages such as availability, economically, biocompatibility, and biodegradability. Gelatin films have exceptional barrier properties against gas and oxygen at low or intermediate moisture [208]. Gelatin has often been utilized as an appropriate starting material to yield biodegradable or edible films for effective food packaging [209]. Several reports have used gelatin-based metal nanoparticles as food packaging materials. For example, in 2014, Rhim et al. developed a method for the synthesis of gelatin/Ag NPs nanocomposite films by the solvent casting process [210]. For this purpose, they used aqueous solutions of gelatin and various amounts of Ag NPs. Increasing the amount of Ag NPs significantly reduced TS (tensile strength) and WVP (water vapor permeability) of the gelatin films. Gelatin/Ag NPs nanocomposite films displayed excellent antibacterial activity

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compared with food borne pathogens and are thus used as active food packaging systems, which that preserve packaged foods and extend their shelf life. In another research, Rhim and coworkers carried out the synthesis of gelatin-based zinc oxide NPs nanocomposite films in 2015 [211]. They synthesized ZnO NPs using two different zinc salts, namely zinc acetate and nitrate, which have different sizes and shapes. ZnO NPs incorporated nanocomposite films displayed improved thermal stability. The gelatin/ZnO NPs nanocomposite films showed remarkable antibacterial activity against foodborne pathogenic bacteria and can thus be applied for the food packaging materials. In another study, Rhim and colleagues developed a method for the synthesis of gelatin/Ag NPs/clay with antimicrobial properties [204]. For this purpose, they used gelatin, Ag NPs, and Cloisite 30B as organoclay. The combination of Ag NPs or clay with gelatin films can improve the mechanical properties of the film. For example, the tensile strength properties of composite films improve in the cases of gelatin/Ag NPs/clay or gelatin/clay. Gelatin/Ag NPs/clay shows strong antibacterial activity against foodborne pathogens and is thus applied for food packaging materials. Film making properties have been widely used to protect food during its shelf life, as an outer film, from dryness, exhibition to light and/or exposure to oxygen. Since gelatin has hygroscopic properties, it dissolves when exposed to foods with high humidity. Therefore, several researchers have studied the effect of adding various compounds such as strengthening agents, plasticizers, cross-linkers, or other compounds with antimicrobial and antibacterial properties to gelatin [212]. These materials are used to improve the properties of gelatin for use in food packaging [213, 214]. In another example, Arfat et al. developed the synthesis of bionanocomposite films using fish skin gelatin (FSG) and bimetallic Ag-Cu NPs [215]. The FSG/Ag-Cu nanocomposites were found to have enhanced mechanical and antibacterial properties and low transparency, thermal stability, and yellowness. FSG/Ag-Cu bionanocomposite was applied in the food packaging industry.

4.5.2

Zein-based packaging materials

Zein is a protein belonging to a group of prolamins of the corn family, which is commonly accepted as Safe (GRAS) food grade. Zein-based nanomaterials used in the food packaging industry have been developed due to their low water vapor permeability compared to other bio-based films [21]. Additionally, zeinbased nanomaterials embedded by inorganic Ag nanoclusters (NC) might have advantages. For example, Mei and coworkers successfully performed the synthesis of AgNCs embedded zein films by incorporation of AgNCs ( 2 nm in diameter) into zein films (Fig. 4.15). The synthesized films were appropriate for food packaging due to their antimicrobial activity, safety to human cells, and eco-friendly nature [216]. Generally, zein has many advantages as an effective ingredient in food packaging, but the problem with the use of the zein is the lack of homogeneous distribution in some cases for film making.

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FIG. 4.15 Schematic representation of synthesis of AgNCs-embedded zein films [216].

In another study, Aytac et al. investigated the synthesis of thymol (THY)/ γ-cyclodextrin (γ-CD) inclusion complex (IC) encapsulated electrospun zein nanofibrous webs (zein-THY/γ-CD-IC-NF) and used them as promising food packaging materials due to their antibacterial activity (Fig. 4.16) [217]. In 2016, Oymaci and Altinkaya reported the synthesis of bionanocomposite films using whey protein isolate (WPI) embedded with zein nanoparticles (ZNP) [218]. The results showed that the addition of zein nanoparticles improved the mechanical and water vapor barrier properties of the synthesized bionanocomposite. The WPI/ZNP nanocomposite films can be effective food packaging materials.

4.5.3 Whey-based packaging materials Whey is a by-product of the cheese-making process defined as the residual matter in the milk serum after coagulation of casein at pH 4.6 and temperature of 20°C. Whey protein contains some distinct proteins known as betalactoglobulin, alpha-lactalbumin, bovine serum albumin, and immunoglobulins [219]. The development of processing whey solid component helps decrease the organic pollution from whey wastes in addition to the ability to optimally utilize the nutritional and functional properties provided by whey protein [220]. The demand for whey protein among food and beverage producers is increasing as they benefit from the functional advantages of whey protein in different products such as sports, nutrition, confectionery, bakery and ice cream products, infant formula, and health foods. A recent study has reported the development of different applications of whey protein products to produce edible films and coatings on the surface of food products [221]. Whey-protein-based films are

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FIG. 4.16 Chemical structure of (A) THY; (B) schematic representation of γ-CD, (C) THY/γ-CDIC formation, and (D) electrospinning of nanofibers from zein-THY/γ-CDIC (1:1) solution [217]. (Reproduced with permission from Aytac Z, Ipek S, Durgun E, Tekinay T, Uyar T. Antibacterial electrospun zein nanofibrous web encapsulating thymol/cyclodextrin-inclusion complex for food packaging. Food Chem 2017;233:117–24.)

clear and odorless and show good barrier properties to oxygen and lipids [222]. They also afford good matrices, which allow the combination with other packaging materials to improve the film’s functionality against microorganisms or moisture [223]. According to the results of a study, whey-protein-based films along with oregano and garlic essential oil created high inhibitory zones on gram-negative (Escherichia coli and Salmonella Enteritidis) and gram-positive bacteria (Staphylococcus aureus, Lactobacillus plantarum, and Listeria monocytogenes) [224]. However, in another study, whey-protein-based films incorporated with oregano essential oil displayed antimicrobial activity against fungus species (Penicillium commune) [225]. There have been several reports on the use of whey protein in food packaging. For example, Porta and coworkers developed a method for the synthesis of chitosan/whey protein edible film for coating Ricotta cheese [226]. The synthesized chitosan/whey protein film had 35% and 21% lower oxygen and carbon dioxide permeability, respectively, and almost three times higher water vapor permeability than the film organized with chitosan alone. In another example, Badr et al. investigated the synthesis of antimicrobial packaging using whey protein edible films (WPEF) incorporated with 1%–2.5% cinnamon (CI), cumin (CU), and thyme (TH) essential oils [227].

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The examination of the synthesized antimicrobial packaging for fresh red meat during storage in the refrigerator for 12 days at 5°C showed considerable reduction in the number of total live bacteria during the 12 days’ storage period. In another study, Biliaderis et al. reported the synthesis of antimicrobial films by the incorporation of different amounts of sodium lactate (NaL) and 3-polylysine (3-PL) into sorbitol-plasticized whey protein isolate (WPI) films [228]. The humidity uptake performance and water vapor permeability (WVP) were affected only by the addition of NaL at all concentrations since an improved water uptake and permeability were observed by adding NaL into the protein matrix. The synthesized antimicrobial composite WPI films were tested on fresh beef cut portions [228].

4.5.4 Casein-based packaging materials Casein is generally found in mammalian milk or dairy products. Casein proteins consist of 80% of the total protein content in the milk precipitated from skim milk by acidification to produce acid casein to its isoelectric point of approximately 4.6 or the treatment of milk with rennet to produce rennet casein. The casein is then separated, washed, and dried [229, 230]. Considering their excellent functional properties and natural rich sources, caseins are applied in many industrial products such as those in bakery, beverages, milk products, snack foods, edible films, and so on [223]. Caseins and caseinates can afford edible films. Edible casein films are capable of providing a good barrier against oxygen and other nonpolar molecules since casein helps supply an excessive quantity of polar functional groups such as hydroxyl and amino groups in the film matrices. This property allows the casein film to be cast off as an active packaging compound and joined with other packaging materials to protect the products disposed to oxidation or moisture [231]. For example, in a research, Arrieta and coworkers developed a method for the synthesis of transparent active films by incorporation of carvacrol into plasticized caseinates [232]. The results showed that the combination of caseinates plasticized with glycerol and carvacrol as active agents afforded great potential for the improvement of transparent active films for food packaging with exceptional barrier properties and antimicrobial activity. In another example, Oussalah et al. reported that calcium caseinate and whey-protein-isolated edible films containing carboxymethyl cellulose by adding 1% oregano essential oil displayed inhibitory effect against gram-negative bacteria such as Escherichia coli and Pseudomonas spp. on the surface of beefsteaks [233]. Antimicrobial activity was generally shown by phenolic compounds (carvacrol and thymol), which exist in the essential oil. In another study, Picchio et al. investigated the synthesis of casein films using tannic acid as a cross-linking agent to prepare plasticized casein films (Fig. 4.17) [234]. The experimental results showed that tannic acid was an efficient cross-linking agent for casein protein. Thus, the prepared films displayed

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FIG. 4.17 Schematic representation of casein films cross-linked by tannic acid [234]. (Reproduced with permission from Picchio ML, Linck YG, Monti GA, Gugliotta LM, Minari RJ, Igarzabal CIA. Casein films crosslinked by tannic acid for food packaging applications. Food Hydrocoll 2018;84:424–34.)

improved physicochemical properties such as thermal stability, mechanical, water vapor, and viscoelastic properties and can thus be employed for food packaging applications.

4.6

Conclusion and future perspective

Bionanocomposite materials have been promising alternatives for conventional plastics, especially those made from petroleum. However, poor mechanical and water vapor barrier properties of these biodegradable materials limit their wide use in the food packaging industry. Techniques developed to improve the properties of these biodegradable materials include modification of biopolymers, polymer melt blending, and polymer nanocomposites, which make it possible to commercialize these biopolymer-based compounds [22]. There has been extensive research on packaging applications using polysaccharides, lignin, and proteins as discussed above. They offer possibilities to create eco-friendly and sustainable food packaging materials to replace nonbiodegradable materials. The need for high-quality, long-lasting, and safe food

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supply has catalyzed various novel techniques in packaging systems, the smart biodegradable packaging being the latest and most promising addition [30]. Blending biopolymers with other biodegradable polymers is the easiest method to prepare polymers with “tailor-made” properties (functional physical properties and biodegradability). Preparation of bionanocomposites is another promising approach to further improve material properties while maintaining biodegradability. The major challenge is to reduce the production and material cost of these bionanocomposites to make them cost-effective compared with synthetic polymers. To overcome this challenge, there is a need to improve bionanocomposite formulations and processing methods to produce these bionanocomposites at a lower cost. There is also a need for a better understanding of clay modification, nanocomposite structure formation, and interaction between the polymer and nanoparticles. More research is also needed to utilize different types of nanoparticles such as carbon nanotubes and nanocellulose to produce novel nanocomposite materials with improved properties [22]. The addition of nanofillers such as silver and ZnO to biopolymers such as starch opens up new potentials to form novel and innovative bionanocomposite materials with improved properties and performance. Nanofillers have the ability to improve the mechanical, thermal, and barrier properties and exhibit other desired functions and applications in food packaging such as antimicrobial activity, biosensing, and oxygen scavenging [11]. Studying the effect of types of biopolymer and nanofillers on the properties of bionanocomposite materials is crucial to investigate the maximum potential of the performance of bionanocomposite materials for food packaging applications. In conclusion, nanomaterial-based biodegradable packaging has great potential as smart packaging to further improve consumer benefits and convenience, and ensure a healthier environment. Regardless of the many benefits of bionanocomposite materials, the use of nanofillers to produce the materials needs proper considerations in terms of safety for end use because there are limited studies done on the toxicological effects and migration of nanofillers into food from the packaging films [11]. To improve environmental sustainability, future developments in food packaging should be directed toward the “ultimate” packaging, which will combine all the benefits of intelligent or smart (IOSP), active (AP), and sustainable or green packaging (SOGP) [235]. IOSP is the factor, which monitors the condition of packaged food or the environment surrounding the food and conveys food quality and safety information. Intelligent packaging does not directly improve the quality and safety of foods or extend shelf life. Therefore, AP is intended to extend the shelf life of packaged food, maintain or improve its properties based on the interactions between active compounds and food, and/or packaging headspace [235]. AP leads to the development of stimuli-responsive polymers. These unique materials offer amazing, innovative, and functional features, which fully comply with the existing environments and regulate the release of molecules in response to external stimuli [236]. The combination

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of intelligent packaging and AP will be an important issue for food packaging innovations in the future [235, 237]. An important concern in food packaging is safety. The migration of active and intelligent compounds, accidental leakage of active components from a sachet, and human ingestion of active and intelligent substances should be considered. Natural resources are one of the options, which improve food safety in addition to availability and will open up potential economic benefits to farmers and agricultural processors [235, 238]. The utilization of these resources, which are mostly biodegradable, also imparts value addition to the biomasses. Natural resources can afford edible films and coatings, which offer a wide future potential to satisfy the consumer desire for environmentally friendly and natural foods. However, they do not completely replace traditional food packaging materials [236]. In 2012, Williams et al. found that 20%–25% of household food wastes are related to food packaging. Therefore, an efficient packaging system can affect the food waste. Additionally, secondary shelf-life extension (after package opening) should receive future research attention because it is very helpful for reducing food wastes [239]. Furthermore, it is necessary to assess the equilibrium between technological innovation and environmental protection. The environmental impact of packaging innovations and food losses should be examined by using the life cycle assessment (LCA) methodology (including raw material extraction and processing, packaging manufacture, transport, and retail, and disposal of food and packaging, even at the household level) in addition to evaluating the impact on food shelf life or packaging characteristics such as optical, physical, thermal, and mechanical properties [235].

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Chapter 5

Biomedical applications of biopolymer-based (nano)materials Mahmoud Nasrollahzadeha, Nayyereh Sadat Soheili Bidgolia, Fahimeh Soleimania, Nasrin Shafieia, Zahra Nezafata, and Talat Baranb a

Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran, bDepartment of Chemistry, Faculty of Science and Letters, Aksaray University, Aksaray, Turkey

5.1

Introduction

Biopolymers as renewable natural resources are often biodegradable, nontoxic, abundantly available, eco-friendly, and biocompatible, which have caused them to attract a great deal of interest in various medical and biological applications [1]. Despite the known advantages and wide applicability of biopolymers, there are also some limitations such as low stability in aqueous media and poor mechanical properties, which limit their applications [2, 3]. However, biopolymers possess a wide variety of functional groups, including amino, carboxylic acid, and hydroxyl groups, which can be further cross-linked and conjugated with cell-targeting ligands. Covalent cross-linkers interconnect molecules, enhance the molecular weight, and usually provide higher mechanical strength and improved stability. However, cross-linking may also reduce the availability and degradability of functional groups in the biopolymer and change the rheology of the biopolymers, leading to subsequent processing difficulties and a potential increase in cytotoxicity [2]. Naturally occurring biopolymers include polysaccharides, proteins, etc. Typical examples are cellulose, chitosan, alginate, pectin, collagen, gelatin, etc. These biopolymers also play major roles in the improvement of biomedical science at molecular to the nanoscale range. Biopolymers are advantageous in a variety of areas because of their fascinating properties [4]. Nanostructures have been developed from a concept to organize molecules to particular structures with a wide spectrum of properties. They integrate nanotechnology to medicine to develop the medical results of various diagnostics and therapeutics by improving the accumulation of the embedded active species into the target sites of tissues by passive and/or active targeting [5]. The synergism between biomedical and nanotechnology sciences has been affected by shifts in the research Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00005-6 Copyright © 2021 Elsevier Inc. All rights reserved.

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proposal containing multidisciplinary science; changing the significance of data, knowledge, and information; the necessity for data sharing and transparency; and disruption of funding streams. The main research challenge of the field of biopolymer nanoparticles is to improve appropriate biocompatibility, barriers, surface properties, and functional properties, which are vital for synthetic reproducibility, scale-up process, in vivo assessment, imaging, and tracking. Many biopolymer nanoparticles have been used as medicinal compounds in clinical routine practices over the last decades without taking into account their particular structure or the resulting complexity of their pharmacological, mechanical, and chemical properties. Biopolymer nanoparticles have unique chemical and physical properties, which potentially offer enormous promises. However, these properties may necessitate further investigation to determine product quality and safety [6]. Nanotechnology, which offers easy preparation of metal-based nanomaterials, has received interest since its discovery and has been widely utilized in different fields such as mechanical, biomedical, and electronics applications. In particular, one of the most important utilization application areas of metal-based nanomaterials is in biology and biomedicine. In addition, natural biopolymer-based metal nanoparticles (MNPs) play important roles in these areas due to their biocompatibility, low immunogenicity, and biodegradability. Biopolymers show very significant properties in different applications compared with conventional micro- and macroscale compounds due to their large surface area and high metal affinity against different metals [7]. In particular, renewable or biodegradable polymers (such as polysaccharides) have recently gained more importance with the development of nanotechnology, which is known as a multidisciplinary scientific field, because they serve as ideal supports/stabilizers in the production of different MNPs [8, 9]. Additionally, biopolymers facilitate the synthesis of MNPs due to their mechanical durability, wide surface area, and high metal-loading capacity. MNPs immobilized on biopolymers show both high stability and good physicochemical features. Recently, biopolymer-based MNPs have received great attention in different biomedical and biological applications due to their particle sizes, surface properties, and controllability or adaptability [10]. Therefore, different types of MNPs (Au, Pt, and Ag) have been stabilized on various biopolymers, such as agar, cellulose, chitin, chitosan, alginate, dextran, pectin, starch, and guar gum, and utilized in different biological, medicinal, and biomedical applications. While Au and Pt NPs are usually used in the diagnosis of heart disease, drug delivery, and cancer therapy, Ag NPs are efficiently used in woundhealing antioxidant and antibacterial applications [11]. Fig. 5.1 displays some biological and biomedical applications of MNPs. Developments in medical devices, carriers, structures, and artificial organs for tissue engineering are more and more supported by functionalized compounds, which have the benefit of combining structural properties with a predetermined, good response to the environment. Among such compounds,

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FIG. 5.1 Schematic representation of some biological and biomedical applications of MNPs.

stimulus-responsive compounds have become a great design platform for a range of biomedical applications, from cardiovascular devices to drug delivery systems [12–16]. Stimulus-responsive compounds are functional compounds in which macroscopic, reversible modifications of their specific behaviors are triggered by small environmental variations. The persistent interest in this group of compounds is mainly because of the fact that many of the most significant compounds in living systems are macromolecules with properties and structures, which respond to their surroundings in a smart or intelligent way [17–19]. Different stimulus-responsive compounds can be found in the nature, and different biopolymers display smart behavior and significant changes in one property upon an external trigger [20]. Despite the ever-increasing use of adjectives related to materials, namely smart, intelligent, and adaptive, it is generally agreed that no clear, broadly accepted definition of these terms exists [21]. A starting point toward a general definition might be the identification of smart materials as functional compounds capable of (1) sensing a specific environmental stimulus, (2) responding in a predetermined method, and (3) returning to their original state when the stimulus is removed [14]. Nevertheless, smart materials may also be defined as structural materials, which inherently contain sensing, actuating, and controlling capabilities built into their microstructures [22]. It is important to clarify that biopolymers inherently possess a strictly nonlinear response to external stimuli. The understanding of the mechanism of cooperative interactions involved in this response has opened the floodgates to attempts at mimicking them in synthetic systems [20]. However, under specific conditions can biopolymers be effectively used to design biomedical solutions encompassing smart behavior. It is thus important to base the understanding of the use of biopolymers upon a practical classification. Different approaches have been proposed based on the class of compound (alloy, ceramic, and polymer) [23], its physical form, activating stimuli or modes of polymer response (thermal, chemical, and electromagnetic) [24–26], response to the stimulus (shape, permeability, and elastic modulus modifications) [27], or

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even on the possible applications of the compound [28]. Vague boundaries and the superimposition of properties and applications make it particularly problematic to define categories and reach a comprehensive and well-defined classification in this field. Fig. 5.2 presents functional biopolymers for biomedical applications based on the activating stimulus [29]. In this chapter, the biomedical applications of biopolymers are focused on. Among different biopolymers, chitin and chitosan are well-known and widely used. Chitin, poly (β-(1 ! 4)-N-acetyl-D-glucosamine), is a natural polysaccharide of major importance, first identified in 1884. An enormous number of living organisms synthesizes chitin. Therefore, it is the second most important biopolymer in the world after cellulose. The main sources exploited are two marine crustaceans, that is, crabs and shrimp. Chitin occurs in nature as ordered crystalline microfibrils forming structural components in the cell walls of yeast and fungi or in the exoskeleton of arthropods. A number of other living

FIG. 5.2 Activating stimuli and macroscopic response in biopolymers for biomedical applications [29].

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organisms in the lower plant and animal kingdoms, serving in many functions where reinforcement and strength are required, also produce chitin [30]. Chitosan (CS) is a cationic biopolymer obtained from chemical or enzymatic partial deacetylation of chitin [31]. Chitosan is a linear copolymer comprising of randomly distributed N-acetyl-D-glucosamine and D-glucosamine groups linked by β-(1–4)-glycosidic bonds [32]. Because of the larger number of D-glucosamine groups on the chitosan structure with a pKa of approximately 6.5, the amine groups of chitosan are highly protonated under acidic conditions [31]. This ensures chitosan solubility in acidic media and makes it more suitable for biomedical applications compared with chitin [33]. Furthermore, chitosan is well known for a number of favorable properties, such as biodegradability, biocompatibility, low immunogenicity, low toxicity, mucoadhesivity, membrane formation ability, and the possibility of derivatization. These features motivate the extensive study of chitosan in various research areas. Chitosan has good mechanical properties and provides the advantage of being easily processed into fibers, gels, beads, scaffolds, membranes, and micro- and nanoparticles. The amino and hydroxyl groups on the chitosan backbone allow for various chemical functionalizations to impart the desired properties and interesting characteristics for specific applications. These chitosan functionalities allow numerous chemical reactions such as chelation of metals, alkylation, acetylation, and grafting [32]. For instance, chitosan hydrophobicity can be enhanced by its derivatization with hydrophobic side chains (alkyl, polyester, and fatty acids), whereas its hydrophilicity may be improved by the introduction of glycol and ethylene oxide groups [34]. Due to these features, chitosan is used in numerous applications such as wound healing, biosensing, tissue engineering, and drug delivery [31]. The adhesive nature of chitosan and chitin, their bactericidal and antifungal characteristics, and permeability to oxygen are very important properties associated with the treatment of burns and wounds. Different derivatives of chitosan and chitin have been fabricated for this purpose in the form of hydrogels, membranes, fibers, scaffolds, and sponges [35]. The unique properties of chitin NPs such as their renewable and biodegradable characteristics, low density, biological activity, very small size, chemical stability, and noncytotoxicity make them exceptional candidates for use in a wide range of applications, in particular, medical applications [36, 37]. Cellulose is the main component in lignocellulosic biomass and the most abundant biopolymer on earth [38]. Cellulose is made up of a D-glucose unit at one end and a C4-OH group, the nonreducing end, while the terminating group is C1-OH, the reducing end with aldehyde structure. The molecular structure of cellulose is responsible for its significant properties: degradability, chirality, hydrophilicity, and chemical variability due to high reactivity from the – OH donor group [39]. Recent studies have led to the development of new and functional biomaterials by chemical modification of cellulose, derivatization of cellulose, or combining it with other compounds to form composites. The excellent properties of cellulose make it an important material for a plethora of

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applications in the biomedical field. Biocompatibility is the single most important aspect, which makes cellulose an ideal biomaterial. Cellulose has shown remarkable drug-carrying potential. The limited biodegradable nature of cellulose makes it suitable for different types of prosthesis and implants, such as cartilage, artificial blood vessels, and meniscus. Furthermore, cellulose has good potential for wound healing because it can maintain a moist wound environment and absorb the exudates. Cellulose has been developed as a scaffold for tissue reconstruction in spite of its nondegradability within the body due to the lack of degrading enzymes [40]. Alginate is an anionic, linear polysaccharide, extracted mainly from brown seaweeds and marine algae, composed of alternating (1,4)-linked β-D-mannuronic acid and α-L-glucuronic acid residues in varying proportions. Alginate has demonstrated great utility and potential as a biomaterial for many biomedical applications, particularly in the areas of wound healing, tissue engineering, and drug delivery [41]. The most attractive properties of alginate for these applications include mild gelation conditions, biocompatibility, and easy modifications to prepare alginate derivatives with novel features [42]. Alginate has a track record of safe clinical uses as a wound-healing dressing material and pharmaceutical compound safely used in a variety of applications, including transplantation for treatment of type 1 diabetes [43] and chondrocyte transplantation for treatment of vesicoureteral reflux and urinary incontinence [44]. The antioxidant capacity of alginates is an important characteristic for their applications in food and pharmaceutics. A chemically modified alginate has also been widely applied as a carrier to promote periodontal regeneration. Like other hydrogels, however, alginate gels have very limited mechanical stiffness, and more generally, physical properties. A continuing challenge is matching the physical properties of alginate gels to the need in a specific application. Consideration of different available cross-linking strategies, using molecules with various molecular weights, chemical structures, and cross-linking functionality, will often yield gels suitable for each application [42]. Pectin is a branched macromolecule with high molecular weight, extracted from the cell walls of most plants, which can be converted into hydrogels. It can swell but do not dissolve in water. Highly concentrated pectin solutions and low pH facilitate the formation of coil entanglements, resulting in the formation of physical gels [45]. Pectin is composed of at least three polysaccharide domains: homogalacturonan, rhamnogalacturonan-I, and rhamnogalacturonan-II [46]. The promising aspects of pectin gels for biomedical applications are related to their easily tunable physical properties, high water content, and the ability to homogeneously immobilize drugs [47–49]. There are many different biomedical applications suitable for such gels such as wound healing, drug delivery, and tissue engineering [45]. Gelatin is composed of carbon (50.5%), oxygen (25.2%), nitrogen (17%), and hydrogen (6.8%) and with a high percentage of α-chain possesses high gel strength. It is a mixture of α-chains (one polymer/single chain), β-chains

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(two α-chains covalently cross-linked), and γ-chains (three α-chains covalently cross-linked). The amino acid composition of gelatin is characterized by the structure of Ala-Gly-Pro-Arg-Gy-Glu-4Hyp-Gly-Pro- [50]. Due to the presence of a large number of functional side groups, gelatin readily undergoes chemical cross-linking. This property of gelatin in conjunction with its performance in cell adhesiveness and plasticity collectively defines gelatin as a widely utilized biomaterial [51]. Lignin is the second most abundant biopolymer of lignocellulosic biomass after cellulose [52]. Due to its hydrophobic nature, lignin makes the cell wall impermeable to water and ensures a well-organized water and nutrition transport in the cells [53]. The chemical structure of lignin has not been completely established although most of the functional groups and units, which make up the molecule, have been identified. Thus, lignin is an amorphous biomacromolecule consisting of phenylpropanoid units, namely p-coumaryl, coniferyl, and sinapyl alcohols. Phenylpropane units are cross-linked to each other by various chemical bonds such as β-O-4-aryl ether linkages, 4-O-5-diaryl ether, α-O-4aryl ether, β-5-phenylcoumaran, β-1-(1,2-diarylpropane), 5-5-biphenyl, and β-β-(resinol) [54]. Lignins can be used in medicine and pharmacy to improve human health because of their antimicrobial and antioxidant characteristics. Additionally, lignins have biological activities such as the capability of reducing cholesterol by binding to bile acids in the intestine. These activities of lignins make them applicable in the treatment of various diseases such as thrombosis, diabetes, obesity, viral infections, and cancers [55]. Chemical structures and sources of some of these biopolymers are given in Table 5.1.

5.2 Biopolymer-based (nano)materials for biomedical applications Biomedical applications of biopolymers date back thousands of years [56]. Polymeric biomaterials are quickly replacing other classes of compounds such as metals, ceramics, and alloys as biomaterials due to their versatility. Within the global implantable biomaterial market, the polymeric biomaterial sector is anticipated to show the highest growth at a CAGR of 22.1%, because of the promising potential of these materials in a wide range of applications [56– 58]. A critical requirement for biomaterials is biocompatibility. Some factors such as solubility, molecular weight, surface energy, hydrophilicity/hydrophobicity, lubricity, mechanism of degradation and/or erosion, and structure and shape of the implant can influence the biomaterial biocompatibility [59]. In addition, several other properties must be considered when choosing a biodegradable biomaterial. First, the degradation time should coincide with the regeneration or healing process to ensure proper remodeling of the tissue. Second, the biomaterial must maintain suitable processability and permeability for its intended application. Finally, the biomaterial mechanical properties should

TABLE 5.1 Sources and chemical structures of some biopolymers. Biopolymer

Source

Chitin

Crabs, shells, krill, and shrimp

Chemical structure

References [30]

n

Chitosan

Deacetylation of chitin of crabs, shells, krill, and shrimp

[31]

n Cellulose

[38]

Plants n

Alginate

[41]

Brown algae and kelp

n m

Pectin

Plants

[46]

Gelatin

Animals

[50]

Continued

TABLE 5.1 Sources and chemical structures of some biopolymers—cont’d Biopolymer

Source

Lignin

Plants (wood)

Chemical structure

References [38]

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be sufficient to promote regeneration during the everyday activities of the patients, and any changes in these properties due to degradation should preserve compatibility with the regeneration or healing process. Given the complexity of the human body, which polymeric biomaterials are currently used for, no single polymeric system can be considered a suitable biomaterial for all medical applications. Thus, recent developments in biodegradable biomaterial fabrication have been focused on synthesizing and developing polymers with properties tailored for biomedical applications. Since biodegradable biomaterials exhibit a variety of physicochemical and biological properties and, therefore, can replicate the properties of different tissues, these materials are recognized for use as (1) large implants including bone plates and screws, and contraceptive reservoirs; (2) small implants in the form of staples and sutures; (3) plain membranes for guided tissue regeneration; and (4) multifilament meshes or porous structures for tissue engineering [60]. In addition, by properly engineering the structure and degradation parameters, these biodegradable compounds can be employed to produce micro- or nanoscale systems for controlled drug delivery in a diffusive or erosive manner or as a combination of both [56]. Herein, the most often studied biopolymers as polymeric biomaterials are highlighted and their immense potentials in the areas of wound healing, tissue engineering, drug delivery, etc. are discussed.

5.2.1

Drug delivery

Extensive efforts have been made to develop formulations for better stabilization of drugs over sufficient storage times. The therapeutic effect of a drug is most effective when its concentration in the blood is below the toxic level and above the minimum effective level. However, every drug has its own biological half-life and can be maintained at an appropriate concentration for only a short and specific time. One solution to this problem is to increase the drug dose. However, it is important not to reach the toxic response region. Another solution is to take the drug several times for a period of time, which is less convenient for the patient. Significant efforts are consequently being made to improve dosage forms, which prolong the biological activity of a protein in the body or assist in targeting it to a particular tissue. One possible method to achieve these aims is to incorporate the drug into a suitable matrix. Drug-controlled release carriers offer several advantages compared with conventional dosage forms, including improved efficacy, maintenance of the desired drug concentration in the blood for a long period of time without reaching a toxic level or dropping below the effective level, reduced toxicity, and improved convenience and compliance of the patient [61]. Drug delivery is the technique to administer pharmaceutical compounds to accomplish the therapeutic impact in animals or humans [62]. Drug delivery is a broad field of research on the improvement of materials or carrier systems for effective therapeutic delivery of drugs [63]. In spite of the advantages of the

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drug delivery, the patient can be harmed if the controlled drug delivery system is not well created. Therefore, the ideal drug delivery system must be biocompatible without harmful degradable products, mechanically strong with the ability to load large amounts of drug without concern of accidental release, simple to sterilize and fabricate, easy to place and remove, and comfortable for the patient [64]. The development of a novel drug is costly and time consuming. The safety efficacy ratios of conventional drugs are improved by the use of various techniques, such as therapeutic drug monitoring, dose titration, and individualizing drug therapy [65]. The drug delivery may be steady, controlled, or targeted. Several preclinical and clinical studies have been conducted for improved understanding of the role of pharmacodynamic and pharmacokinetic precepts to govern the biopharmaceutical disposition characteristics of the drugs belonging to major therapeutic categories, such as opioid analgesics, muscle relaxants, inhalation anesthetic agents, and sedative/hypnotics. As far as the current drug delivery perspective is concerned, such therapeutic agents can be administered to the body via multiple routes, such as buccal, skin, and nasal mucosal membranes. In this regard, a plethora of novel devices and technologies have been popularized known as controlled-release technology (CRT) [66]. Such CRTs have gained considerable attention for transdermal and transmucosal drug delivery applications with the help of nasal and buccal aerosol sprays, encapsulated cells, drug impregnated lozenges, oral soft gels, and ionotophoretic devices for administering drugs through the skin [67]. Since the advent of medical application systems, numerous drugs have been administered through various conventional drug delivery forms, such as solutions, lotions, mixtures, creams, pastes, ointments, powders, suppositories, suspensions, injectables, pills, immediate release capsule, and tablets, to treat various diseases [68]. Biopolymers have the ability to carry bioactive compounds to target tissues, cells, and cell compartments even though they have many problems in preparations, including low drug loading capability and wide size distribution. Moreover, biopolymer-based nanoparticles can be modified into tailor made sizes, which are sustainable for a long period of time, making them very interesting tools as therapeutic agents for the researchers [69].

5.2.1.1 Chitin and chitosan-based (nano)materials in drug delivery The different properties of chitin such as ability to bind with organic materials, biocompatibility, susceptibility to enzymatic hydrolysis, and intrinsic physiological activity combined with heavy metal ions and nontoxicity are particularly amenable to a wide variety of biomedical applications in targeting and drug delivery, tissue engineering, wound healing, and in the area of nanobiotechnology. The mucoadhesive property of chitin provides an intimate contact with mucus membrane and prolonged residence time of the polymers at the absorption site, thereby reducing the degradation of drug [70]. A group of researchers

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have developed a combination of in silico and in vitro approaches to check the drug delivery property of the polymeric NPs viz. chitosan and chitin. Two different therapeutic agents (insulin [a therapeutic protein] and curcumin [a hydrophobic drug]) were used to study the delivery potential of chitosan and chitin NPs. The drug-loaded chitosan and chitin NPs were synthesized and characterized. The schematic representation of encapsulation of curcumin and insulin in tripolyphosphate (TPP) cross-linked chitosan and chitin NPs is shown in Schemes 5.1 and 5.2. In the in vitro drug delivery experiments, chitosan NPs exhibited better encapsulation efficiency, drug loading capacity, and prolonged release of the drug molecules than chitin NPs to both insulin and curcumin. Meanwhile, the in silico experiments such as molecular dynamics and molecular docking predicted the molecular interactions and binding energy involved between the drug molecules and the nanoparticles. This work suggests that chitosan NPs could be used as carriers for both insulin and curcumin [71]. Chitosan has some great potential applications in the pharmaceutical industry owing to its biocompatibility and biodegradability, nontoxicity, excellent drug loading capacity, mucoadhesion, and high charge density. Chitosan can be used to enhance bioavailability and applied in the drug delivery system of phytochemicals due to the interaction of positively protonated amino groups in it [72]. Chitosan is not soluble in organic solvents and water, but it is soluble in mildly acidic solutions. Acidic soluble chitosan has been used in the preparation of natural hydrogels for effective drug delivery [73]. The application of chitosan as a carrier has previously been reported. Acteoside (Ac) is a phenylethanoid glycoside belonging to water-soluble polyphenolic compounds, which is abundant in the Olea europaea L. fruit, Osmanthus fragrans flower, Striga asiatica, and Cistanche deserticola. Acteoside shows antiinflammatory, antioxidant, antibacterial, neuroprotective, and antiandrogen activities, but has a short half-life and low bioavailability because of its poor intrinsic permeability and instability [74, 75]. Zhou’s group synthesized chitosan-coated acteoside liposomes to improve the bioavailability and stability of acteoside (Fig. 5.3) [76,77]. Liposomes (Lip) are composed of phospholipid bilayer membranes similar to cell membranes. However, traditional liposomes are poorly stable and have a tendency to leak the entrapped drug during storage [78, 79]. The applicability of liposomes can be extended by modifying their surface via polymer coating. Chitosan-modified liposomes interact with negatively charged cell membranes and open epithelial cell tight junctions, thereby enhancing hydrophilic drug transport. Chitosan-coated liposomal (CS-Ac-Lip) surfaces can enhance the bioavailability and stability of liposomes and overcome the above-mentioned drawbacks. Chitosan coating increases the diameter, encapsulation efficiency, zeta potential, in vivo release time, bioavailability, and stability of the Ac-Lip, and the chitosan-liposome is a promising delivery system for transporting acteoside or other bioactive components [76, 77].

202 PART

II Biomedical and biological applications HO

HO

H3CO

H3CO

O O HO

OCH3

OH OCH3

Curcumin

O

O

O

O

H3CO CH3

OH O HO

O

O HO O O NH

O HO O O NH

OH

NH

O O HO OH O

CH3

CH3

CH3 NH O OH

TPP O

OH O HO

O HO O O NH

O

CH3

n

Chitin

H3CO

HO

HO

CH3

CH3

OH

NH O O HO

OH

O HO O O NH

O

CH3

NH O

O

OH n

Chitin/Curcumin complex In vitro drug release O

HO

O OH OCH3

OCH3

O HO

Curcumin

OH O NH

O

O HO O

CH3

(A)

CH3

OH

NH

O O HO OH O

CH3 NH O OH

O

CH3

n

Chitin nanoparticles HO

HO

H3CO

H3CO

O O HO

OCH3

Curcumin

OH OCH3

OH O

HO O

NH2

OH NH2 HO O O O O HO NH2 OH

O

O

O

O

H3CO

H3CO

HO

TPP

O HO

O HO O O NH

OH

NH2 O O OH

O HO

O

HO O

NH2

NH2 O O HO OH

OH O

HO O

NH2

NH2 O OH

O n

Chitosan/Curcumin complex

n

Chitosan

HO

In vitro drug release O HO

(B)

OCH3

O

Curcumin

OH OCH3

O HO

OH O

HO O

NH2

NH2 O O HO OH

OH O

HO O

NH2

Chitosan nanoparticles

NH2 O OH

O n

SCHEME 5.1 Schematic representation of encapsulation of curcumin in TPP cross-linked chitosan and chitin NPs [71].

Insulin is commonly administered by subcutaneous injection for the treatment of diabetes mellitus. However, daily injections of insulin have many disadvantages, such as unwanted pain, peripheral hyperinsulinemia, hypoglycemic events, discomfort, allergic reactions, and other side effects. Therefore, noninvasive routes of insulin therapy including nasal, transdermal, oral, pulmonary,

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Insulin Insulin

OH O HO

O HO O O NH

O

CH3

CH3

OH

NH O O HO

OH

O HO O O NH

O

CH3

CH3 NH O

OH

TPP O HO

O

OH

O

n

O HO O O NH CH3

Chitin

O HO

(A)

OH O O

NH

O HO O

CH3

O O HO

OH

O

O HO O O NH CH3

CH3 NH

O

O OH

n

In vitro drug release

CH3

OH O

NH

O O HO OH O

NH

O HO O

CH3

CH3 NH O OH

O

n

Chitin nanoparticles Insulin

Insulin

OH O

HO O

NH2

NH2 O O HO OH

OH

Chitosan

O

HO O

NH2

NH2 O

OH

TPP O HO

O

OH

O

HO O

NH2

NH2 O O HO OH

OH O

HO O

NH2

NH2 O

O

OH n

n PBS pH 2.5/7.4

OH

Insulin O HO

(B)

OH

PBS pH 2.5/7.4

Insulin

O HO

CH3 NH

O

HO O

NH2

In vitro drug release

NH2 O O HO OH

OH O

HO O NH2

Chitosan nanoparticles

NH2 O OH

O n

SCHEME 5.2 Schematic representation of encapsulation of insulin in TPP cross-linked chitosan and chitin NPs [71].

and buccal routes have been extensively investigated. Of these routes, oral delivery has several advantages such as absence of pain, good patient compliance, convenience, and favorable glucose homeostasis [80–82]. Based on the cationic nature of chitosan, the negatively charged nanocomposites coated with cationic polymers have been studied to produce nanocarriers. Insulin loaded into chitosan coating of zein-carboxymethylated short-chain amylose (IN-Z-CSA/CS) nanocomposites was found to have stronger hypoglycemic effect compared with insulin loaded Z-CSA without chitosan. The internalization of IN-Z-CSA/CS0.2% nanocomposites into Caco-2 cells was mediated via paracellular pathway and endocytosis. Relative bioavailability of 15.19% was obtained in orally administered IN-Z-CSA/CS0.2% nanocomposites [83]. In another study, to realize the long-term administration of insulin level, injectable nanogels including

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FIG. 5.3 Schematic representation of the fabrication of CS-Ac-Lip [76].

carboxymethyl-hexanoyl chitosan and lysozyme were formulated to load insulin. Lysozyme performed as a biodegrading carboxymethyl-hexanoyl chitosan via hydrolyzing the 1,4-beta-linkages, which could control the biodegradation and insulin release rate. The results show great potential as a long-acting insulin delivery system for glucose management [84]. Chitosan has also been widely applied in brain drug delivery [85]. Chitosan NPs can be absorbed on the negatively charged cell membrane because of the positive charge on their surface and raise the residence time on the nasal mucosa. The delivery of drugs from the nasal cavity to the brain can thus be improved. Ropinirole-dextran sulfate nanocomplex loaded, flaxseed oil-based neuronanoemulsions and N,N,N-trimethyl chitosan modified mucoadhesive neuronanoemulsions have been improved for direct nose-to-brain drug delivery with the objective of providing controlled drug release for the treatment of Parkinson’s disease. Direct nose-to-brain drug delivery in a mouse model has resulted in high drug concentrations in the brain chamber [86]. The most common neurodegenerative disorder to cause dementia is Alzheimer’s disease. Saxagliptin is a dipeptidyl peptidase-4 enzyme inhibitor molecule studied for its activity in Alzheimer therapy. The dipeptidyl peptidase-4 enzyme grows the level of glucagon like peptide-1 and ameliorates type-2 diabetes [87]. Owing to its extreme hydrophilicity, Saxagliptin is unable to permeate the blood-brain barrier by conventional therapy modalities. Chitosan-L-valine-based NPs loaded with Saxagliptin have been developed using large amino acid transporters at the blood-brain barrier, which aid in the transport of amino acids and amino acid like molecules into the brain cells [88]. Paclitaxel (PTX), an antineoplastic agent initially extracted from the bark of the Pacific yew tree, has a powerful antitumor activity against various cancers such as colon, refractory ovarian, small, metastatic breast and non-small-cell lung, and neck cancers [89]. It blocks cell replication by hyperstabilizing the cellular microtubules. Thus, it inhibits cellular growth and leads to apoptosis. Theoretically, oral administration of PTX is a preferable choice with several advantages, including less cost, better patient compliance, more convenience,

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and more chronic treatment regimens. However, oral administration is restricted due to some aspects such as limited dissolution and aqueous solubility, P-glycoprotein (P-gp), multidrug efflux pump, and high affinity to intestinal and liver cytochrome P450 metabolic enzymes. Polymeric micelles can act as drug carriers to enhance the bioavailability of PTX [90]. N-octyl-O-sulfate chitosan (NOSC), an amphipathic derivative containing octyl and sulfated groups as hydrophobic and hydrophilic moieties, respectively, was shown to be a good choice. Zhang and coworkers studied the effect of NOSC micelles on increasing the oral absorption of PTX in vitro and in vivo and identified the mechanism of this action of NOSC (Fig. 5.4) [90]. In the Caco-2 uptake investigation, NOSC micelles were shown to bring about a meaningfully higher amount of PTX accumulated in Caco-2 cells by both caveolae and clathrin-mediated endocytosis. In addition, NOSC affected the inhibition of paclitaxel secreted via P-glycoprotein (P-gp), which was proved by the analysis of rhodamine 123 incorporated in NOSC and fluorescence-labeled micelles. According to the obtained results, it is suggested that NOSC micelles might be a potentially applicable tool for increasing the oral absorption of P-gp substrates [90]. Decoration of metal nanoparticles with biopolymers is a novel area of research. Studies have shown that nanoparticles demonstrate better biological activities when conjugated with biopolymers. Ag NPs have become efficient vehicles to store and deliver medicines. They are used for the controlled release of drugs and albumin drug complexes, in which NPs act as carriers of drugs and liberate them on a selective basis, at the right speed and in the intended environment within the organism. They can be applied as magic “bullets,” which go directly to cells of a particular tissue [91]. In a study, researchers developed chitosan-stabilized Ag NPs by a green method, conjugated them with azathioprine as an immune suppressive agent, and utilized them to treat the inflammation in rheumatoid arthritis. The in vitro studies performed to determine the percentage of drug secretion and its toxicity on the NIH3T3 fibroblast cell line showed that the formulation of these nanoparticles had a dual role, targeting the site of disease and releasing the drug in a controlled manner and producing a synergistic effect to inflammatory sites [92]. Furthermore, tuberculosis (TB) is an ancient lung infectious disease caused by Mycobacterium tuberculosis intracellular pathogen [93]. Long treatment time, poor patient compliance, adverse side effects, and the emergence of multidrug-resistant strains need an ideal system to shorten TB therapy [94]. For a few decades, pyrazinamide (PZA) and rifampicin (RF) front-line drugs were applied as combination chemotherapy in the battle against TB. RF is a small hydrophobic molecule, which inhibits the activity of DNA-dependent RNA polymerase [95]. The activity of PZA is not clearly understood. Due to the numerous complications of TB chemotherapy, TB management may be improved by loading TB drugs into the polymeric materials, which reduces the dose level and time period compared with the standard protocol [96]. In an experimental study, amphiphilic chitosan grafted-(cetyl alcohol-maleic

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FIG. 5.4 Scheme of (A) the effect of NOSC micelles on improving the oral absorption of PTX and (B) inhibition of PTX absorption by the effect of the multidrug efflux transporter P-gp in the intestinal epithelium cells [90]. Reprinted with permission from Mo R, Jin X, Li N, Ju C, Sun M, Zhang C, Ping Q. The mechanism of enhancement on oral absorption of paclitaxel by N-octyl-O-sulfate chitosan micelles. Biomaterials 2011;32(20):4609–20.

anhydride-pyrazinamide) (CS-g-(CA-MA-PZA) was prepared via multistep reactions. The incorporation of RF and entrapment of Ag NPs on CS-g-(CAMA-PZA) were carried out by the dialysis method (Fig. 5.5). The in vitro cell viability, cellular uptake experiments, and cell apoptosis display that a multidrug delivery system could improve the biocompatibility and increase the influence of cytotoxicity on the cells [97]. Other uses of chitosan-based materials in drug delivery are given in Table 5.2.

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FIG. 5.5 Schematic representation of the fabricated micelles loaded with RF, INH, and Ag NPs [97]. Reprinted with permission from Praphakar RA, Jeyaraj M, Ahmed M, Kumar SS, Rajan M. Silver nanoparticle functionalized CS-g-(CA-MA-PZA) carrier for sustainable anti-tuberculosis drug delivery. Int J Biol Macromol 2018;118:1627–38.

5.2.1.2 Cellulose-based (nano)materials in drug delivery Cellulose and cellulose-based products can also be applied in drug release systems [136]. One reason for utilizing cellulose and its derivatives as drug carriers is because they are porous materials, which can facilitate the liquid uptake. Cellulose can interact strongly with water, thus swelling readily in water. In turn, the swelling of the cellulosic polymer network is positively related to the capillary action. It is well known that a fast swelling drug will have a quick dissolution process [137]. Cellulose has unique rheological, mechanical, and optical properties and is easy to be chemically modified and reconfigured for drug delivery. The typical modifications of cellulose are etherification and esterification at its hydroxyl groups and the oxidation of cellulose chain/surface groups, which will impart hydrophobic and hydrophilic properties to the drug delivery system [138]. An increasing number of investigations on cellulosebased drug delivery systems have been carried out. For example, in a study, researchers developed a drug delivery method based on magnetic cellulose nanocrystals/alginate hydrogel beads. They observed that the presence of magnetic cellulose nanocrystals could improve the integrity of the alginate hydrogel beads and the swelling percentage. Additionally, the rate of in vitro drug release

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TABLE 5.2 Applications of chitosan-based materials in drug delivery. Entry

Chitosan-based materials

Drug

Disease

References

1

Chitosan/ocarboxymethyl chitosan NPs

Doxorubicin hydrochloride

Cancer

[98]

2

Thiolated chitosan NPs

Insulin

Diabetes

[99]

3

Fe3O4carboxymethylated chitosan

Genistein

Gastric cancer

[100]

4

N-Trimethyl chitosan chloride-coated polylactide-coglycoside nanoparticles

Insulin

Diabetes

[101]

5

Chitosancarboxymethyl-βcyclodextrin-Fe3O4 NPs

5-Fluorouracil

Cancer

[102]

6

N-Octyl-N0 -phthalylO-phosphoryl chitosan micelles

Paclitaxel

Cancer

[103]

7

Chitosan NPs

Chlorotoxin and transferrin

Brain tumors

[104]

8

Chitosan coated oligomerized ()epigallocatechin-3O-Gallate NPs

Lycopene

Cancer

[105]

9

Chitosan NPs

Pramipexole

Parkinson

[106]

10

Chitosan oligosaccharide

Chitosan oligosaccharide lactate

Depression

[107]

11

Lauryl succinyl chitosan

Insulin

Diabetes

[108]

12

Chitosan hydrogel NPs

Dextrandoxorubicin

Cancer

[109]

13

Chitosan NPs coated with polysorbate 80

Tacrine

Alzheimer

[110]

14

Folic acid-conjugated chitosan/chondroitin sulfate self-assembled NPs

Bortezomib

Colorectal cancer

[111]

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TABLE 5.2 Applications of chitosan-based materials in drug delivery—cont’d

Entry

Chitosan-based materials

Drug

Disease

References

15

Peptide(TNYLFSPNGPIA, TNYL) modified chitosan-g-stearate polymer micelle

Doxorubicin

EphB4overexpressing tumors

[112]

16

Low-molecularweight chitosan

5-Fluorouracil

Cancer

[113]

17

Self-assembled lecithin/chitosan NPs

Insulin

Diabetes

[114]

18

Chitosan-grafted HPβCD NPs

Efavirenz

Neuro-AIDS

[115]

19

Chitosan-coated liposome dry-powder formulations

Ghrelin

Cachexia

[116]

20

Chitosan NPs

Carvedilol

Hypertensive

[117]

21

Polylysine/L-cysteine/ chitosan-based multifunctional NPs

Paclitaxel

Cancer

[118]

22

Chitosan-quercetin micelles

Doxorubicin

Cancer

[119]

23

Poly-lactide-coglycolide/chitosan NPs

L-pGlu-(2-propyl)-

Epilepsy

[120]

L-His-L-ProNH2

and L-pGlu-(1benzyl)-L-HisLProNH2

24

Chitosan-poly (aminopropyl/ phenylsilsesquioxane)

5-Fluorouracil

Cancer

[121]

25

Chitosan NPs

5-Fluorouracil

Cancer

[122]

26

Pluronic F127/N,N, N-trimethyl chitosan hydrogel system

Docetaxel

Malignant glioma

[123]

27

Chitosan coated lipid microparticles

Resveratrol

Central nervous system diseases

[124]

28

Chitosan NPs

Ropinirole hydrochloride

Parkinson

[125]

29

Chitosan-Au hybrid hydrogel

Doxorubicin

Cancer

[126]

Indomethacin

Inflammatory

[127]

30

Continued

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TABLE 5.2 Applications of chitosan-based materials in drug delivery—cont’d

Entry

Chitosan-based materials

Drug

Disease

References

Polyacrylamidegrafted chitosan 31

Carboxymethyl chitosan NPs

Carbamazepine

Epilepsy

[128]

32

Methoxy poly (ethylene glycol)grafted carboxymethyl chitosan NPs

Doxorubicin

Malignant glioma

[129]

33

Poly--caprolactone nanocapsules coated with chitosan

Simvastatin

Brain tumors

[130]

34

Glycol chitosancoated nanostructured lipid carrier

Asenapine maleate

Schizophrenia and bipolar disorders

[131]

35

Chitosan-based mucoadhesive microemulsions

Diazepam

Epilepsy

[132]

36

Chitosan glutamatecoated niosomes

Pentamidine

Alzheimer

[133]

37

Chitosan NPs

Rotigotine

Parkinson

[134]

38

Chitosan NPs

Cyclovirobuxine D

Cardiovascular disease

[135]

reduced because of the introduction of cellulose nanocrystals [139]. As shown in Fig. 5.6, Lin et al. developed a drug delivery system containing doublemembrane hydrogels from anionic alginate and cationic cellulose nanocrystals. Cationic cellulose nanocrystals in the inner membrane hydrogel could offer the continued drug release of epidermal growth factor from day 4 to day 12, while anionic alginate in the outer hydrogel could achieve rapid drug release of ceftazidime hydrate within the first 3 days. Thus, the double-membrane hydrogels were expected to achieve the synergistic release results or possibly provide the solution to drug resistance in biomedical applications [140]. Bacterial cellulose (BC) is a naturally derived hydropolymer with high potential in both medical and pharmaceutical applications. This unbranched

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Swelling

First and quick release (antibiotics)

5

211

Antibiotics

1-Layer Complete disintegration

1-Layer Partial disintegration

Swelling

2-Layer Skeleton disintegration

Cationic CCNC

2-Layer Complete disintegration

2-Layer Partial disintegration

Second and slow release (growth factor)

Swelling

Growth factor

FIG. 5.6 Proposed complexing drug release typical for the double-membrane hydrogel with the design of anionic alginate and cationic cellulose nanocrystals [140].

polysaccharide composed of linear chains of β-1,4-glucopyranose residues is produced by many microorganisms [141]. BC has been used for the delivery of drugs to the wound with its efficient physical barrier properties to external infection [142]. The porosity of BC is simply exploited to load drugs with various features, ranging from anticancer properties to antibacterial activity [143, 144]. Moreover, BC can be improved more by chemical modifications with other polymers or fabricating BC-based materials to enhance the control of drug release. For the first time, oral administration BC capsules were synthesized by Ullah et al. Capsule shells were made of pure BC or BC conjugated with starch, carboxymethyl cellulose, or hydroxypropyl methylcellulose and used for encapsulation of salbutamol sulfate. The capsules of pure BC confirmed a burst release of the drug, whereas the ones prepared with other polymers presented controlled drug release. In addition, the capsules made with carboxymethyl cellulose demonstrated improved prevention of drug leakage at lower pHs. This research exhibited the versatility of BC for burst or controlled release of a contained drug [145]. Furthermore, another study investigated the association of metal nanoparticles with biopolymers, which shows significant properties in drug delivery. In this study, porous nano gold embedded cellulose grafted polyacrylamide (PAM/ C/Au) nanocomposite hydrogel has been synthesized for sustained release of antibiotic ciprofloxacin model drug (Fig. 5.7) [146]. The PAM/C/Au nanocomposite hydrogels are nonhazardous and exhibit greater thermal stability with substantial development in swelling ratio compared with PAM/C. This study showed that a sustained and controlled long-term drug release has been obtained [146]. Fluorouracil (5-Fu), an anticancer drug, containing polylactic acid-co-ethyl cellulose nanocapsules, has been fabricated in the absence and presence of Au

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FIG. 5.7 Schematic representation of release of ciprofloxacin by PAM/C/Au nanocomposite hydrogels [146].

NPs via solvent evaporation process. The pH of the dissolution medium affected the rate of drug release from the nanocapsules. In addition, the results indicated that the drug release for nanocapsules containing Au NPs was controlled and slower compared with that of 5-Fu incorporated into polymeric nanocapsules without Au NPs [147]. In another work, novel nanohybrid hydrogels were prepared by L-histidineconjugated chitosan, dialdehyde cellulose, and zinc oxide nanoparticles as sustained drug delivery carriers for various polyphenol drugs, including naringenin, quercetin, and curcumin. The imidazole group of L-histidine conjugation played the main role in the development of the overall functionality of the improved carrier. Furthermore, anticancer investigations of A431 cells demonstrated excellent cytotoxicity with a 15- to 30-fold rise (compared with the free polyphenol drugs) using the hybrid carrier [148]. Novel magnetic and zinc oxide nanocarriers based on microcrystalline cellulose were developed via the combination of the grafting and reversible addition fragmentation chain transfer polymerization techniques. Methotrexate (MTX) was attached to a nanocarrier to enhance the anticancer efficiency of this drug in MCF-7 breast cancer cells (Fig. 5.8) [149]. Based on the results, these nanocarriers are appropriate for active targeted delivery of MTX to cancer tissues [149]. Some types of drug delivery systems containing cellulose-based compounds are shown in Table 5.3.

5.2.1.3 Alginate-based (nano)materials in drug delivery Alginate (ALG), which is a water-soluble linear polysaccharide, is composed of the irregular blocks of β-D-mannuronic acid (M) and 1–4 linked α-L-guluronic (G) residues [160]. The nonantigenicity, extraordinary biocompatibility, bioavailability, and chelating ability of alginate make it an appropriate compound for biomedical applications [161]. The drug delivery and rheological performance of ALG are also conditioned by the molecular weight, G/M ratio, pH, and concentration of the medium. The physical and mechanical stability of

Biomedical applications of biopolymer-based (nano)materials Chapter

S

MCC

O

CH3

CH3 S

H2 C

C C

n

O

O

OH

(H2C)3 Si

N CH3 CH3

O

O

O

(CH2)2

H3C

CH3 H2 C n

C C

213

5

O

O O

ZnO, Fe3O4

MTX

HO pH O Nu c leus

HO

O

H

OH

Chemotherapy O

O

OH HO

OH

OH

n

Microcrystalline cellulose

FIG. 5.8 Schematic representation of the MTX-loaded zinc oxide and magnetic nanocarriers for chemotherapy of MCF7 cells [149].

alginate depends on the G content. The greater the G content, the more brittle and rigid is the matrix [162, 163]. Several studies have reported that alginate can be effectively used as a ratecontrolling excipient or stabilizing agent in drug delivery formulations [164, 165]. Microencapsulation is a common method to deliver drugs and control the rate of drug release. Drug encapsulated microspheres can be utilized to improve the stability and bioavailability of drugs, target the drugs to the specific sites in the body, and offer controlled or prolonged drug release. Different drugs can be microencapsulated into alginate gels for oral administration. In a study, alginate microspheres were applied in the encapsulation of isoniazid for oral sustained drug delivery. Isoniazid is an antimycobacterial agent for first-line treatment in tuberculosis. However, the long-term continuous therapy of isoniazid can produce hepatotoxicity and peripheral neuropathy. Therefore, it is advantageous to have a drug formulation with a controlled and prolonged

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TABLE 5.3 Various drug delivery systems based on cellulose-based materials. Entry

Cellulose-based materials

Drug

Disease

References

1

Cellulose-based supramolecular NPs

Doxorubicin

Cancer

[150]

2

Carboxymethyl cellulose/magnetic graphene oxide@mesoporous silica

Ibuprofen

Inflammation

[151]

3

Bacterial cellulosealginate

Doxorubicin

Cancer

[152]

4

Graphene oxide/ carboxymethyl cellulose

Doxorubicin

Cancer

[153]

5

Bacterial nanocellulose/ poloxamer

Octenidine

Dermal wound

[154]

6

Cellulose nanofibrils/chitosan transdermal film

Ketorolac tromethamine

Inflammation

[155]

7

Bacterial cellulose membranes

Ibuprofen

Inflammation

[156]

8

Bacterial cellulose membranes

Diclofenac sodium

Inflammation

[157]

9

Carboxymethyl cellulose-rosin gum hybrid NPs

5Aminosalicylic acid

Bowel disease

[158]

10

Graphene oxide/ carboxymethyl cellulose bionanocomposite hydrogel beads

Doxorubicin

Cancer

[159]

enteric release. Alginate microspheres containing isoniazid were prepared by an emulsification process in which smooth and spherical particles were obtained. Investigations showed the release of 26% of isoniazid in a simulated gastric fluid of pH 1.2 in 6 h and complete release of the remaining 71.25% in the simulated intestinal fluid of pH 7.4 in 30 h [166].

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FIG. 5.9 Preparation process of TP@SiO2@SA@CaCO3 microspheres [167]. Reprinted with permission from Chen Z, Lv X, Zhao M, Zhang P, Ren X, Mei X. Encapsulation of green tea polyphenol by pH responsive, antibacterial, alginate microgels used for minimally invasive treatment of bone infection. Colloids Surfaces B Biointerfaces 2018;170:648–55.

Furthermore, in a study by Chen and coworkers, sodium alginate (SA) microgel spheres (MSs) were prepared to encapsulate a lot of tea polyphenol (TP)-loaded SiO2 nanospheres (NSs) for the slightly invasive therapy of osteomyelitis. Green tea extracted polyphenols have strong antibacterial and antioxidative properties. In this research, polyphenols extracted from green tea were encapsulated in porous silica NSs, which were then encapsulated in ALG microspheres (Fig. 5.9). The final formulation was then covered with pH-sensitive CaCO3 to provide a conductive environment for polyphenol delivery at the site of act killing Staphylococcus aureus, thus promoting the proliferation of osteoblasts [167]. Myocardial infarction (MI) represents the major cause of death worldwide with an increasing burden over the last decade [168]. Therefore, understanding how cardiac tissue is injured and regenerated is of prime importance to global health. From a clinical point of view, particle-based systems are considered a suitable choice for the delivery of an arsenal of therapeutic agents to patients, who have experienced a cardiac ischemic event [169]. In a study, adipose tissue-derived stem cells were encapsulated in alginate-poly-L-lysine-alginate microcapsules and then injected in the ischemic myocardium of pigs. Microencapsulation improved cell retention in the cardiac tissue. However, treatment failed to improve heart rate, infarct size, and cardiac output. An enhancement in the cell loading of the particles may help improve therapeutic results [169]. In another work, Shtenberg and colleagues developed a suitable hybrid of liposome and alginate as a carrier in the oral mucoadhesive drug delivery system (Fig. 5.10). Liposome induces the absorption of the drug into the cells and

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FIG. 5.10 Fabrication of mucoadhesive alginate pastes with embedded liposomes for local oral drug delivery [170]. Reprinted with permission from Shtenberg Y, Goldfeder M, Prinz H, Shainsky J, Ghantous Y, El-Naaj IA, Schroeder A, Bianco-Peled H. Mucoadhesive alginate pastes with embedded liposomes for local oral drug delivery. Int J Biol Macromol 2018;111:62–9.

prevents degradation, while alginate improves adhesive property and local release of the drug. To study the release kinetics of liposome-loaded doxorubicin (DOX), three alginate/liposome combinations were investigated. A hybrid paste with great adhesive features, but fast burst release (90% after 2 h); a hybrid hydrogel with controllable release rate (5%, 30%, or 60% after 2 h), but weak mucoadhesive ability; and lastly, a hybrid cross-linked paste with controllable release rate of 20% after 2 h were developed [170]. As it is known, alginate NPs combine several advantages for drug delivery. As NPs without a covering may be uptaken by the immunological system, modifications of the surface with hydrophilic polymers or surface coating with cellspecific receptors promote targeting and improve drug bioavailability. Alginate NPs have been exploited for numerous administration routes, including oral, pulmonary, intravenous, ocular, and nasal [171–175]. These compounds have also been exploited for carrying several drugs, such as ethionamide, doxorubicin, metformin, and many biotech drugs [171, 176, 177]. The cross-linking of alginate can be obtained using cationic polyelectrolytes during the fabrication of NPs or between alginate with cationic drugs to be loaded [161]. Other uses of alginate-based compounds in drug delivery are shown in Table 5.4.

5.2.1.4 Pectin-based (nano)materials in drug delivery Given its significant pharmacological properties such as the ease of dissolution in common environments, mucus, and the capacity to yield gels in acids, pectin is of promising applied and fundamental interest [201]. In a recent work, the potential of chitosan and pectin as microspheres for the controlled release of

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TABLE 5.4 Applications of alginate-based materials in drug delivery. Entry

Alginate-based materials

Drug

Disease

References

1

Chitosan-alginate

Crocin

Cancer

[178]

2

Calcium alginate microspheres containing metformin hydrochloride niosomes and chitosomes aimed

Metformin

Diabetes

[179]

3

Hybrid nanogels of alginate and G5.0 poly(amidoamine) dendrimer

Epirubicin

Cancer

[180]

4

Alginate coated chitosan core-shell nanoparticles

Naringenin

Diabetes

[181]

5

Chitosan-alginate microspheres

Azelastine

Conjunctivitis

[182]

6

Polyurethanealginate

Insulin

Diabetes

[183]

7

Wheat germ agglutininfunctionalized CSCa-ALG microparticles

5-Fluorouracil

Cancer

[184]

8

Chitosan-alginate

Doxorubicin

Cancer

[185]

9

Chitosan-alginate

Insulin

Diabetes

[186]

10

Alginatecyclodextrin nanogel

5-Fluorouracil

Cancer

[187]

11

Chitosan-Ca-alginate microspheres

Celecoxib

Cancer

[188]

12

Kefiran-alginate gel microspheres

Ciprofloxacin

Bacterial infections

[189]

13

SA-HAP-iron oxide NPs

Curcumin and 6-gingerol

Cancer

[190]

14

Lipid/alginate

Dexamethasone

Inflammation

[191]

15

Alginate-g-poly(Nisopropylacrylamide)

Doxorubicin

Cancer

[192] Continued

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TABLE 5.4 Applications of alginate-based materials in drug delivery—cont’d

Entry

Alginate-based materials

Drug

Disease

References

16

Alginate microspheres

Ranitidine

Gastrooesophageal reflux

[193]

17

Alginate microspheres

Ropinirole hydrochloride

Parkinson

[194]

18

Magnetic alginate/ chitosan

Curcumin

Cancer

[195]

19

Metal ion-induced alginate-locust bean gum interpenetrating microspheres

Aceclofenac

Inflammation

[196]

20

Folate-conjugated hyaluronic acid coated alginate nanogels

Oxaliplatin

Cancer

[197]

21

Alginate/high methoxyl pectin/guar gum alkyl amine

Ciprofloxacin

Bacterial infections

[198]

22

Alginate-keratin composite nanogels

Doxorubicin

Cancer

[199]

23

Alginate nanogel platform

Cisplatin

Cancer

[200]

acetaminophen was investigated. The microspheres of both biopolymers were synthesized using solvent evaporation technique and emulsion. The method used was effective for the fabrication of both microspheres yielding uniform, spherical, and nonporous microspheres. The average diameters of acetaminophen-loaded chitosan and pectin microspheres were 0.62  0.24 μm and 24.98  13.67 μm, respectively, making them good for nasal, oral, ocular, and subcutaneous administration or implantation in combination with a threedimensional matrix scaffold. Various analyses showed that there were no interactions between acetaminophen and pectin, but there was an interaction at the molecular level between the drug and chitosan. The encapsulation efficiency percentage was greater for chitosan microspheres with a value of up to 64%. The results showed that acetaminophen, which was the model drug encapsulated in the microspheres, was released for approximately 420 h in the case of chitosan

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microspheres and 250 h for pectin microspheres, and drug release was continued in both cases [202]. In another work, 3-aminopropyltriethoxysilane-modified nanocarbon sphere (MNCS) was added into pectin-Ca2+ film to enhance the controlled release properties of a pectin-based oral colon specific drug delivery system (OCDDS). 5-fluorouracil was applied as the drug model, and the controlled release properties of the corresponding OCDDSs were determined. The values of encapsulation efficiency ranged from 30.1% to 52.6%, which indicates the benefit of adding MNCS. All composite film-based OCDDSs exhibited higher encapsulation efficiency than single pectin-based OCDDS. The cytotoxicity assay showed good biocompatibility of the composite carriers [203]. In another study, Li and coworkers reported the fabrication of quaternized pectin-montmorillonite (QP-MMT) composite film containing 5-fluorouracil by simple blending. The results of the characterization showed that the intercalation reaction occurred in the blending process. The optimum film presented a high value of drug loading efficiency (80.30%) and encapsulation efficiency (36.50%). The in vitro drug release analyses showed that MMT significantly improved the sustained release performance in all the simulated media. Cytotoxicity assay was carried out to show the great biocompatibility of QP-MMT hybrid film [204]. Furthermore, in another study, pectin was extracted from Akebia trifoliata var. australis fruit peel wastes by water and its physicochemical properties were evaluated. The pectin was employed as a wall material to coat curcumin-loaded zein NPs for the first time. The electrostatic attraction, intermolecular interaction, and hydrogen bonding were responsible for the formation of curcuminloaded core shell nanoparticles (CLCSNs). The acquired nanoparticles presented a core (zein)-shell (pectin) structure and spherical shape with an average diameter of 230 nm. High encapsulation efficiency (89.65%) and loading capacity (10.35%) of CLCSNs were achieved for the curcumin. The stability, solubility, antioxidant activity, and in vitro bioavailability of the curcumin were considerably improved after loading into the CLCSNs [205]. In another example, a self-assembled nanoparticle system based on pectindihydroartemisinin (DHA) conjugated for the codelivery of anticancer drugs was designed by Liu and coworkers. A pectin-based nanocarrier was prepared as a combined simultaneous multiple cargo containing hydrophobic drugs such as 10-hydroxycamptothecin (HCPT) and dihydroartemisinin to be carried to the tumor sites (Fig. 5.11). Pectin-dihydroartemisinin/hydroxycamptothecin nanoparticles (PDC-H NPs) with a small particle size of 70 nm were formed. The in vitro tests exhibited the higher cellular uptake, more cell apoptosis induction, and cell viability inhibition capacity of PDC-H NPs in comparison with dihydroartemisinin and HCPT. PDC-H NPs could effectively capture mammary carcinoma cells by confocal microscopy imaging [206]. In a study, pectin-coated gold nanoparticles (GNPs) were applied for curcumin drug delivery (Fig. 5.12). The researchers estimated the best size of the

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FIG. 5.11 Schematic strategy of PDC-H NPs. PDC prepared by the direct introduction of DHA drug molecules into pectin, and self-assembly into PDC-H NPs with free HCPT being encapsulated [206].

FIG. 5.12 Schematic of curcumin-pectin@GNP system [207].

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prepared GNPs as well as the encapsulation efficiency and release percentage of the drug. Furthermore, an antibacterial investigation was conducted. The results showed that 100 nm GNPs had the highest encapsulation efficiency. A study of the release rate of curcumin drug at 37°C for 2 days revealed that the amount of drug released was higher in acidic pH than at pH 7.4 with a slow release rate. The electronic structure and adsorption properties of pectin@GNPs complex were examined by the density functional theory method [207]. Recently, pectin-graft-poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (Pec-g-PAMPS) gel was prepared in the form of beads by subjecting the solution containing 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), pectin, and ammonium peroxodisulfate to microwave irradiation, followed by ionic cross-linking in CaCl2 solution. Gel beads including Ag NPs were also synthesized by the same process, but with the addition of AgNO3 and trisodium citrate solution prior to microwave irradiation. The in vitro drug release profiles of the parent gel and its composite were considered using ketoprofen to investigate the effect of incorporation of Ag NPs on the drug release performance of Pec-g-PAMPS. The presence of Ag NPs significantly improved both swelling of the gel beads and the extent of drug release [208]. In another study, pectin was employed for the one pot aqueous preparation of GNPs. Pectin performed as both stabilizing and reducing agents. The crystalline nature and spherical morphology of the Pec-GNPs were confirmed by TEM analysis. Furthermore, Pec-GNPs were found to be stable under different pH and electrolytic conditions. The in vivo safety of the Pec-GNPs was confirmed through zebra fish toxicity studies. DOX cationic drug was positively loaded on the anionic Pec-GNPs by ionic complexation interaction. The in vitro release investigations established the pH-dependent, sustained release of doxorubicin. DOX-loaded Pec-GNPs showed enhanced in vitro cytotoxicity on the breast cancer cells compared with free doxorubicin, indicating that PecGNPs are effective vehicles for the transfer of DOX [209]. Other applications of pectin based-materials in drug delivery are shown in Table 5.5.

5.2.1.5 Gelatin-based (nano)materials in drug delivery Gelatin properties can be adjusted to maximize drug loading efficiency [220]. The isoelectric point of gelatin can be adjusted to the electrostatic properties of the chosen drug molecule by acidic or alkaline treatment [221]. Furthermore, the gelatin hydrophilic nature facilitates the penetration of body fluids into the particles and thereby increases the diffusion-mediated release of bioactive molecules. Drug release profiles from gelatin can also be optimized by changing the gelatin source, the degree of cross-linking, and molecular weight [222]. Furthermore, modification of gelatin to different types of carriers and addition of natural or synthetic polymers can be optimized, and the drug profile release can be

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TABLE 5.5 Applications of pectin-based materials in drug delivery. Entry

Pectin-based materials

Drug

Disease

References

1

Cetyltrimethylammonium bromide@pectin

Curcumin

Cancer

[210]

2

Calcium pectinate

Indomethacin

Inflammation

[211]

3

Pectin/chitosan

Indomethacin

Inflammation

[212]

4

Pectin hydrogel

Doxorubicin

Cancer

[213]

5

Zinc-pectin-chitosan composite microparticles

Resveratrol

Colon diseases

[214]

6

Zinc-pectinate beads

Theophylline

Asthma

[215]

7

Pectin/ethylcellulose

5Fluorouracil

Cancer

[216]

8

Amidated pectin hydrogel matrix patch

Insulin

Diabetes

[217]

9

Chitosan/pectin polyelectrolyte complexes

Tacrine hydrochloride

Alzheimer

[218]

10

Pectin-gold nanoparticles

Zidovudine

HIV

[219]

specified to a broad range of cancer therapy, tissue engineering, and therapeutic angiogenesis applications [223–226]. In various biological and physiological functions, the bioactive materials promise the achievement of therapeutic effects in humans or animals as a key procedure. Medicinal and biological features of 5-aminopyrazole (5-AP) make it a potential bioactive molecule, which has recently attracted widespread attention. To design diverse synthetic plans, 5-AP is highly potential owing to the presence of nucleophilic carbon and nitrogen atom, and –NH2 functionality in its scaffold. Accordingly, to prepare novel conjugated heterocyclic compounds, 5-AP offers neoteric opportunities in the field of biomedicinal applications [227–229]. In a study, 5-AP-conjugated gelatin hydrogel (5-AP/G) was prepared to load anticancer 5-fluorouracil drugs through soaking in the drug solution. The in vitro drug release study was carried out to stimulate the rectal conditions for establishing the productivity of the prepared novel anticancer agent. 5-AP/G showed a predictable drug release behavior in the rectal conditions with notable cytotoxicity against human colon adenocarcinoma HT29 cells. Based on the results obtained, 5-AP/G hydrogel as the rectal administration of 5-FU could potentially be proposed in drug delivery systems for the treatment of rectal cancer [230].

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As previously indicated, PTX shows significant anticancer activities against various solid tumors, but great limitations such as poor solubility and severe side effects hinder its clinical applications. Thus, nanocarriers have been designed to deliver PTX to overcome these obstacles [231]. Tumor-responsive nanocarriers are highly valuable and required for smart anticancer drug delivery, in which a quick release of chemotherapeutic drugs in tumors is preferred. In a recent work, a redox and metalloproteinases (MMP-2)-sensitive nanoparticle has been designed for the targeted delivery of PTX. Bovine serum albumin, a targeting ligand, gelatin, a hydrophilic carrier, and MMP-2-sensitive reagents were used to construct the nanoparticles. Disulfide containing prodrug (PTX-SS-COOH) was grafted to the sulfhydryl-modified gelatin to form the redox-sensitive amphiphilic polymer. The nanoparticles were prepared by the self-assembly of amphiphilic polymer and BSA covering. Furthermore, the modified sulfhydryl group on the gelatin can form a disulfide bond by selfcross-linking in the air, which endows the nanoparticle with a stable structure. The nanoparticle was sensitive to changes in MMP-2 concentration and redox potential, resulting in multiple responsive drug delivery to the tumor microenvironment [232]. A study was carried out to examine the possibility of using insulin orally with gelatin encapsulation to enhance the usefulness of the drug and increase the lifespan of insulin in the body using polylactic-co-glycolic acid (PLGA) NPs alongside gelatin encapsulation. In this regard, PLGA was prepared via ring-opening polymerization, and PLGA/insulin NPs were synthesized via a modified emulsification diffusion process. The resulting NPs with various amounts of insulin indicated the interaction between PLGA and the insulin. The process efficiency of encapsulation was higher than 92%, while the encapsulation efficiency of NPs, based on an insulin content of 20%–40%, was optimized at 93%. Based on the thermal studies, PLGA encapsulation increases the thermal stability of insulin. Based on the release studies and kinetics, particle size analysis, and in vitro degradation, the sample loaded with 30% insulin showed optimum overall properties and was thus encapsulated with gelatin, followed by coating with aqueous methacrylate. Release studies at pH values of 3 and 7.4, standard dissolution test at pH 5.5 and Kjeldahl method, and glucose uptake assay tests clearly showed that the capsules had 3–4 h biodegradation resistance at a lower pH along with the sustained release, making these gelatin encapsulated NPs promising alternatives for oral applications [233]. Gelatin can also be conjugated to gold Au NPs by different methods such as physical adsorption [234]. In a study, Au NPs were first fabricated and then coated with gelatin by a simple method. Subsequently, the resulting nanocomposites were used as curcumin drug carriers. The results clearly demonstrated that the largest Au NPs (100 nm) showed the highest encapsulation efficiency. In addition, studying the release profile of curcumin at different pHs (7.4 and 5.4) at 37°C for 2 days revealed that the amount of drug released at pH 5.4 was greater than that at pH 7.4. In addition, the release rate is slower at pH 7.4 [235].

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In another work, gelatin natural biopolymer was cross-linked with citric acid in the presence of Ag nanoparticles. Interestingly, Ag NP formation and gelatin cross-linking simultaneously occurred during the annealing of samples without the need for any toxic chemicals. In addition, the potential of the citric acid cross-linked-gelatin/Ag nanocomposite hydrogels was appropriate for drug delivery applications using cefixime as a model drug. It was found that these hydrogels had pH-dependent swelling and drug release behavior with higher drug release at pH 7.4 compared with pH 1.2. Furthermore, an antibacterial effect against E. coli and S. aureus microorganisms was obtained by the incorporation of Ag NPs into hydrogels. These hydrogels can be considered stimuli-responsive compounds for oral drug delivery and wound dressing applications [236]. In another research, magnetic iron oxide NPs (IOPs) were coated with gelatin A and B, and the drug loading efficiency of the resulting products was investigated using DXR as a model drug to evaluate their potential as a carrier system for magnetic drug targeting. Drug loading onto coated IOPs was performed using adsorption and desolvation/cross-linking techniques to determine their role. Drug loading by adsorption technique was carried out by incubating a mixture of coated IOPs and drugs at various conditions of pH, DXR-to-coated IOPs ratio, gelatin types, and IOP amounts. Drug loading by desolvation/ cross-linking technique was performed by adding glutaraldehyde (GTA) and acetone to the mixture of DXR and coated IOPs. The results indicated the involvement of electrostatic interaction during the loading of DXR to coated IOPs. Compared with the adsorption, the desolvation/cross-linking technique improved the efficiency of drug loading regardless of the type of gelatin used for coating. The DXR-loaded particles showed pH-responsive drug release, leading to the acceleration of the release of drugs at pH 4 compared with pH 7.4 [237]. In another research, using cryochemical synthesis, systems of prolonged release of gentamicin sulfate modified with silver (2–30 nm) and copper (1–9 nm) nanoparticles from cryostructured biopolymer matrices based on gelatin with a pore size of 10–50 μm were obtained. The composition and structure of the systems were confirmed by IR, UV, and 1H NMR spectroscopy, TEM, SEM, and thermo-analytical methods. In addition, the rate of drug release was determined by conductometry. Hybrid composites based on metals and gentamicin sulfate showed greater activity in suppressing the growth of S. aureus and E. coli than their components separately [238]. Other applications of gelatin-based materials in drug delivery are shown in Table 5.6.

5.2.1.6 Lignin-based (nano)materials in drug delivery Lignin has biodegradability, antioxidant activity, antibacterial activity, and low biotoxicity. Hence, self-assembled lignin-based materials are highly attractive for drug delivery systems. Lignin has a large number of active phenolic

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TABLE 5.6 Applications of gelatin-based materials in drug delivery. Entry

Gelatin-based materials

Drug

Disease

References

1

Chitosanpolylacticacidpolyethylene glycolgelatin NPs

Rifampicin

Tuberculosis

[239]

2

Poly-(ethylene glycol)modified gelatin NPs

Ibuprofen sodium

Inflammatory

[240]

3

Gelatin nanoparticles

Indomethacin

Inflammatory

[241]

4

Amphiphilic gelatiniron oxide core/ calcium phosphate shell NPs

Doxorubicin

Cancer

[242]

5

Gelatin NPs

Paclitaxel

Cancer

[243]

6

Mannosylated gelatin NPs

Isoniazid

Tuberculosis

[96]

7

Gelatin NPs

Rifampicin

Tuberculosis

[244]

8

Gelatin NPs

Pilocarpine HCl

Eye disorders

[245]

9

Macrocycle cucurbit [7]uril-gelatinpolyvinyl alcohol (PVA)

Cisplatin

Cancer

[246]

10

Gelatin-coated gold NPs

Doxorubicin

Cancer

[247]

11

Gelatin-dopamine nanogels

Doxorubicin

Cancer

[248]

hydroxyl groups, which allow flexible chemical modification. For example, a novel pH-responsive drug loaded polymeric nanoparticle system including aminated lignin-histidine conjugate and 10-hydroxycamptothecin (AL-His/HCPT NP) was synthesized [249]. Based on the acidic microenvironment of tumor cells such as pH 5–6 and 4–5 for endosomes and lysosomes, AL-His/HCPT NPs effectively imparted pH responsiveness by histidine, a pH-responsive small molecule to reach triggered drug release. The NPs have small particle sizes (40 nm), which is important to antitumor nanocarriers. The NPs have excellent biocompatibility, active cellular uptake, and great drug loading behavior. A schematic representation of AL-His/HCPT NP preparation and its performance in vivo is shown in Fig. 5.13 [249].

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DETA

His

HCPT

Self- assemble

L

AL

AL-Hits

AL-Hits/HCPT NPs

(A)

-7

:5

pH

Tumor sites

(B) FIG. 5.13 (A) Schematic representation of the construction of nanoparticles by self-assembly. (B) Explanation of the pH-responsive release route of AL-His/HCPT NPs in acidic microenvironment of tumor cells in vivo [249]. Reprinted with permission from Zhao J, Zheng D, Tao Y, Li Y, Wang L, Liu J, He J, Lei J. Self-assembled pH-responsive polymeric nanoparticles based on lignin-histidine conjugate with small particle size for efficient delivery of anti-tumor drugs. Biochem Eng J 2020;156:107526.

Nowadays, some approaches such as PEGylation, derivatization, emulsification, and micro/nanonization have been found to efficiently enhance the stability and dispensability of natural product-based drugs [250–253]. In particular, Pickering emulsions stabilized by NPs are among the most studied systems due to their excellent emulsion droplet stabilization, high activity retention of the drug molecules, and easy fabrication [254, 255]. In addition, the presence of NPs at the interface between the aqueous phases and oil affords superior stability, stimuli responsiveness, low toxicity, and other functions of Pickering emulsions compared with classical emulsions stabilized by surfactants. These advantages make Pickering emulsions more attractive in biomedicine [256– 258]. In a work, Dai et al. designed a new multifunctional Pickering emulsion stabilized by lignin-based NPs. They applied the industrial waste lignin to make

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thermoresponsive lignin copolymer by grafting poly(N-isopropylacrylamide) (PNIPAM) onto lignin via atom transfer radical polymerization and formed self-assembled NPs (AL-g-PNIPAM NPs). AL-g-PNIPAM NPs well-stabilized trans-resveratrol (trans-RSV) having palm oil emulsion droplets in water. The results displayed the good potential of this method to prepare green functional lignin-based nanoparticle stabilized Pickering emulsion for storage and thermally controlled release of light unstable and weakly water-soluble drugs [259]. In a similar study, Liu and coworkers reported a novel drug-loaded film for blending poly(L-lactide) (PLLA) with lignin-based functional filler, which improved the stability and sustained release of trans-resveratrol (Fig. 5.14) [260]. The trans-resveratrol loaded PLLA/lignin films presented good anticancer and antioxidant properties. The combination of the optimized amount of lignin-based filler with PLLA matrix was important to obtain the desired functions. Benefitting from the stereocomplex formation (PLLA and poly(D-lactide) (PDLA) side chains), similar polyphenolic structures between trans-RSV and lignin, and UV chromophoric groups of lignin, trans-RSV loaded PLLA/ lignin-graft-PDLA films (R/P/LGPD) have suitable performances on uniform distribution of drug, mechanical property, and light barrier effects [260]. In another study, Frangville et al. utilized a simple process, in which lignin was dissolved in ethylene glycol and precipitated with HCl to prepare lignin nanoparticles (LNPs) with sizes ranging from 100 nm to a micrometer scale, depending on the initial concentration of lignin and HCl added. The LNPs did not have any apparent cytotoxicity for microalgae and yeast. Therefore, they were considered promising tools for drug delivery [261]. Alqahtani reported a new nanoparticle formulation, which increased the bioavailability of orally administrated lipophilic molecules such as curcumin. The utilization of lignin-based nanoparticles for this work was shown to be possible in vivo and in vitro. The developed LNPs have an ideal size, great encapsulation efficiency, sustained pattern of curcumin release in the simulated intestinal fluid, and superb stability under gastric conditions. Pharmacokinetics data exhibited that curcumin-loaded LNPs caused an important increase in the bioavailability of curcumin and its half-life in comparison with curcumin suspension after oral administration. The results showed that the effect of LNPs on the bioavailability of curcumin after oral administration can be related to the enhanced curcumin stability, solubility, sustained release, improved absorption by enhanced intestinal permeability, and inhibition of P-gp-mediated efflux [262]. Furthermore, Qian et al. synthesized colloidal lignin spheres by the selfassembly system via dissolving acetylated lignin in tetrahydrofuran (THF) and gradually adding water to the solution. This caused the lignin molecules to start connecting with each other due to hydrophobic interactions. The route was completed by adding water to 67% by volume of the solution. The NPs formed in water after the THF evaporation had an average size of 106 nm and could be applied as drug delivery systems [263]. Biomass enzymatic hydrolysis lignin (EHL) was employed as an emulsifier to fabricate oil in water high

FIG. 5.14 Preparation of trans-RSV loaded PLLA/lignin-graft-PDLA film from PLLA, LG-g-PDLA filler and trans-RSV [260].

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internal phase emulsions (HIPEs) with the support of sodium dodecyl sulfate (SDS). The effects of SDS dosage, EHL concentration, oil/water ratio, and pH of water phase on the stability, microstructure, and rheological properties of the HIPEs were studied by optical microscopy and rheometry. In addition, the HIPEs showed an outstanding protection on UV-induced curcumin degradability. The residual level of curcumin encapsulated in the HIPEs reached 60.3% after 72 h of UV irradiation. The curcumin-loaded HIPEs exhibited rapid drug release and thermal stability in the phosphate buffered saline solution [264]. Another group used the bio-renewable EHL combined with alkyl polyglucoside (APG) as an emulsifier to stabilize oil in water HIPEs under neutral conditions by adjusting the polarity and conformation through sulfomethylation modification. The results show that lignosulfonates (LS) could not stabilize HIPEs because of their high hydrophilicity. However, by using EHL-XS with sulfonation degree between 0.89 and 1.05 mmol g1, up to 2.0 wt% of EHL-XS with the help of 3.5 wt% APG could stabilize HIPEs containing 80 vol% of the internal oil phase, which were highly stable and displayed no important microstructure changes over 1 month. Moreover, these EHL-XS stabilized O/W HIPEs could be applied as encapsulates for the protection and delivery of the environmentally sensitive curcumin [265]. In another study, lignin hollow nanoparticles (LHNPs) were made and used as promising carriers for the doxorubicin hydrochloride (DOX) antineoplastic antibiotic drug. Hydrogen bonding and π-π interactions contributed to the encapsulation of hydrophilic DOX by LHNPs with hydrophobic cavities. DOX encapsulation was improved by the surface area and pore volume. Additionally, the NPs contributed to the cellular uptake and the accumulation of the drug within HeLa cells. These sustainable LNPs with a spherical hollow structure could be employed as potential vehicles for compounds with benzene rings because of their exceptional absorption capacity, biodegradability, and nontoxicity [266]. Wang et al. prepared sodium lignosulfonate grafted poly(acrylic acid-copoly(vinyl pyrrolidone)) hydrogels by radical polymerization aided by ultrasonication. They applied amoxicillin as a model drug, which showed a promising pH sensitivity and controllable release behavior in vitro. The amoxicillinloaded hydrogels showed better release rates in simulated intestinal fluids than in simulated gastric fluids [267]. Furthermore, Figueiredo et al. developed three LNPs: pure lignin nanoparticles (pLNPs), iron(III)-complexed lignin nanoparticles (Fe-LNPs), and Fe3O4-infused lignin nanoparticles (Fe3O4-LNPs) with narrow size distribution, reduced polydispersity, round shape, and good stability at pH 7.4. In relation to the drug loading, pLNPs exhibited the capacity to well load poorly watersoluble drugs and other cytotoxic agents, e.g., benzazulene (BZL) and sorafenib, and enhance their release profiles at pH 5.5 and 7.4 in a sustained manner. Furthermore, BZL-pLNPs showed enhanced antiproliferation effect in various

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cells compared with the pure BZL and presented a maximal inhibitory concentration ranging from 0.64 to 12.4 μM after a day incubation [268].

5.2.2 Tissue engineering Tissue engineering is an emerging multidisciplinary research area at the interface of engineering sciences, biology, and medicine for the formation of new tissues for the therapeutic reconstruction of the human body [269]. Tissue engineering facilitates the preparation of biological substitutes to repair or replace failing tissues or organs. One of the most promising methods in this regard is to grow cells on scaffolds acting as temporary support for cells in the regeneration of the target tissues, without losing the 3D stable structure [270]. This field has many limitations such as the selection of biocompatible and bioactive materials for the purpose of repairing or regenerating the target tissue, optimizing mechanical properties to produce a well-developed scaffold appropriate for soft or under load tissues, utilizing factors, which can stimulate the production and secretion of angiogenic (the biological process preexisting vessels form new ones) factors in the target tissue, identification of angiogenic factors in each tissue, the technique used to construct the appropriate engineered scaffold or structure, and how to transfer angiogenic factors to the tissue in the absence of the native factors [271]. The biocompatibility of the materials is essential. That is, the substrate materials should not produce an inflammatory response or exhibit immunogenicity of cytotoxicity. The scaffolds must be simply sterilizable in both the bulk and the surface to prevent infection [272]. For scaffolds mainly in bone tissue engineering, a usual porosity of 90% with a pore diameter of about 100 μm is required for cell penetration and a proper vascularization of the ingrown tissue [273]. As scaffolds are serious elements of tissue engineering, various methods have been utilized to design them. These methods include freeze-drying, gas foaming, solvent casting, electrospinning, micromolding, etc. [274]. Lyophilization or freeze-drying is one of the most commonly used techniques. This process works on the sublimation principle in which the polymer is mixed with a solvent and frozen. This solvent is later removed by the lyophilization process, which reduces the system pressure and allows the water in the frozen polymer solution to sublimate directly from the solid to gas phase, thereby yielding interconnected and porous structures [275]. Polymeric scaffolds play a key role in tissue engineering via cell seeding, proliferation, and new tissue formation in three dimensions. Porosity, surface area, and pore size are broadly recognized as significant parameters for a tissue engineering scaffold. Other architectural characteristics such as pore wall morphology, pore shape, and interconnectivity between pores of the scaffolding materials are similarly suggested to be significant for cell seeding, mass transport, growth, migration, and tissue formation [269]. Natural polymers have been used as scaffolds to stimulate specific cell functions and direct cell-cell interactions both in implants, which are initially cell free, possibly loaded with growth factors to promote tissue regeneration and support cell growth [276].

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These materials have been patterned in three and two dimensions to generate multicellular tissue architectures, which may regenerate healthy tissues in a pathological site. Different biopolymers such as agarose, isolated from red purple seaweed, have been widely used in the fabrication of scaffolds due to properties such as biodegradability, soft tissue like mechanical property, and porosity, which helps in cell spreading and proliferation [59]. One of the main disadvantages of agarose is the fact that it lacks the potential of cell attachment, which reduces its role in this area [277]. Therefore, many blends of agarose and other polymers, including chitosan, gelatin, etc., have been employed for tissue engineering purposes [278, 279]. Furthermore, in combination with other polysaccharides, agarose gel offers a moist environment and improves the system stability. The following shows some examples of the application of biopolymer-based materials in tissue engineering.

5.2.2.1 Chitin and chitosan-based (nano)materials in tissue engineering In the orthopedic applications, chitin has been applied in native form and in combination with mineral (mostly Ca based) phases. Maeda et al. reported the application of chitin in the form of rods, powders, and braided filaments. It was shown that these forms were potentially appropriate for temporary synthetic ligaments and sutures for the knee joint [280]. The method of calcium deposition onto the porous chitin scaffold by precipitation of the calcium phosphate directly on the chitin scaffold was further reported by Wan and coworkers [281]. Around 55% by mass of Ca was adsorbed on the chitinous scaffold. This method might be a useful process for the fabrication of materials comprising of chitin and calcium for tissue engineering applications. In another research, Mutsenko et al. reported a novel method to produce “ready-to-use” tissue engineered products based on the chitin extracted from I. basta and A. aerophoba demosponges [282, 283]. Such 3D scaffolds (Fig. 5.15) showed exceptional biocompatibility and were cytocompatible with human mesenchymal stromal cells (hMSCs) in vitro. Cells cultured onto chitin scaffolds were able to differentiate into the osteogenic, chondrogenic, and even adipogenic lineages [284]. Applications of chitosan in tissue engineering and drug delivery fields widely range from cartilage, bone, vascular grafts, and skin to substrates for cell culture. Chemical engineers and biotechnologists have taken advantage of chitosan as a good biopolymer and produced new materials for bone regeneration to replace the damaged tissue and restore proper functioning of the damaged parts [285]. As a tissue engineering scaffold material, chitosan has the following desirable properties [286–288]: ✓ Biocompatibility: Chitosan mimics the extracellular matrix (ECM) of mammalian cells due to the presence of glucosamine residues, which makes it biocompatible. It is observed that the biocompatibility of chitosan is increased with increase in degree of deacetylation (DD).

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FIG. 5.15 Brief overview of step-by-step (a–c) isolation of ready to use 3D chitinous scaffold (d) from Aplysina archeri marine demosponge [284]. Reprinted with permission from Wysokowski M, Machałowski T, Petrenko I, Schimpf C, Rafaja D, Galli R, Ziętek J, Pantovi
c S, Voronkina A, Kovalchuk V, Ivanenko VN, Hoeksema BW, Diaz C, Khrunyk Y, Stelling AL, Giovine M, Jesionowski T, Ehrlich H. 3D chitin scaffolds of marine demosponge origin for biomimetic mollusk hemolymphassociated biomineralization ex-vivo. Mar Drugs 2020;18(2):123.

✓ Biodegradability: Because of the presence of breakable glycosidic bonds, which are susceptible to lysozyme present in the mammalian system, chitosan can be degraded into amino sugars, which can be easily eliminated from the body. ✓ Hemostatic property: The cationic nature of chitosan favors its hemostatic property by facilitating the attachment of chitosan to the negatively charged erythrocyte cell membrane. This hemostatic property of chitosan will be

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✓

✓ ✓

✓

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helpful in accelerating blood coagulation in wounds and reducing blood loss. Antimicrobial activity: Chitosan has been proved to possess antimicrobial activity because of its interaction with the negatively charged cell surface of the microorganisms. Another mechanism of the antimicrobial property of chitosan is its ability to bind with microbial DNA, thus inhibiting RNA fabrication, which eventually leads to the death of the microorganism. This property is important in wound-healing applications. Mucoadhesiveness: Chitosan is a good mucoadhesive material because it binds with the negatively charged sialic acid group present in the mucous membrane. The mucoadhesion property of chitosan is found to increase with an increase in its DD. Nonimmunogenicity and nontoxicity: It has been proved that chitosan is nonimmunogenic and nonallergic. When chitosan is topically applied or orally taken, no adverse inflammation reactions are observed in the host. Cytocompatibility: Chitosan promotes proliferation, adhesion, and differentiation of different lineages of cells, such as fibroblasts, keratinocytes, osteoblasts, and chondrocytes. The cytocompatibility of chitosan was also found to be dependent on its DD value. Processability: Chitosan can be processed into a variety of structures, such as films, hydrogels, nanofibers, micro/nanoparticles, sponges, and 3D porous scaffolds, because of its flexibility during the fabrication process.

Cartilage tissue is made of chondrocytes, which yield ECM proteins [289]. Chitosan has been employed in cartilage tissue engineering owing to its various forms, such as sponges, fibers, and hydrogels [290, 291]. Shen and coworkers prepared a strong, tough, and porous chitosan-gelatin hydrogel, capable of exhibiting a Young’s modulus of 3.25 MPa and a compressive strength of 2.15 MPa, which are similar to or higher than those for human cartilages. Moreover, this hydrogel degraded by 65.9% over 70 days, which implied a good match with the regeneration rate of cartilage, making them potential candidates for cartilage tissue engineering [292]. Chitosan has been widely combined with silk fibroin (SF), a protein-based biopolymer [293, 294]. SF, usually extracted from Bombyx mori cocoons, has gained attention in cartilage tissue engineering because of its biocompatibility, slow degradation, superb mechanical properties, and cell adhesion and proliferation [295]. Li et al. fabricated a SF and carboxymethyl chitosan (CMCS) hydrogel by chemical cross-linking with horseradish peroxidase (HRP) and H2O2 [296]. Tyramine (TA)-substituted CMCS was synthesized by the coupling reaction of amine groups of TA with the carboxylic acid groups of CMCS using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS) activation. SF/CMCS composite hydrogels were prepared by chemical cross-linking with HRP/ H2O2, followed by physical cross-linking by ethanol treatment (Fig. 5.16). The physicochemical properties of hydrogels, their degradation rate, and good biocompatibility are beneficial scaffolds for cartilage tissue engineering.

(A)

(B) FIG. 5.16 (A) CMCS decorated with TA. (B) SF/CMCS composite hydrogel produced with chemical cross-linking by HRP/H2O2, followed by physical crosslinking by ethanol treatment [296].

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Furthermore, chitosan has been linked with synthetic polymers such as polylactic acid [297], polycaprolactone [298], and polyethylene glycol (PEG) [299, 300] to produce scaffolds for bone tissue engineering to affect the mechanical properties and biocompatibility of the final composite [301]. Combinations of these polymers have become more common in research because synthetic polymer scaffolds have poor cell affinity owing to their low hydrophilicity and lack of cell recognition sites [302]. A strategy to make blood vessels with high surface area to volume ratios via electrospinning techniques has drawn the attention of many scientists. Zhang et al. presented a new vascular patch of polyelectrolyte multilayers via a layer-by-layer self-assembly method (Fig. 5.17) [303]. Heparin and chitosan were deposited onto the polyurethane-coated decellularized scaffold (PU/DCS). The in vitro and in vivo investigations of these polyelectrolyte multilayer vascular patches showed the developed biocompatibilities, including reduced hemolysis rate, prolonged in vitro coagulation time, and improved resistance to platelet adhesion. Metallic and ceramic NPs can increase the biological and mechanical properties of polymeric scaffolds for bone tissue engineering. Nanohydroxyapatite (nHAp) and nano-copper-zinc alloy were added to a chitosan/gelatin (Ch/G) scaffold to study their effects on morphological, physical, and biocompatibility properties. Scaffolds were made via freeze-drying method using different prefreezing temperatures. Mouse embryonic fibroblast cells loaded in the

FIG. 5.17 Schematic representation of the formation of a multistructured vascular patch by a layer-by-layer self-assembly of heparin and chitosan [303]. Reprinted with permission from Zhang J, Wang D, Jiang X, He L, Fu L, Zhao Y, Wang Y, Mo H, Shen J. Multistructured vascular patches constructed via layer-by-layer self-assembly of heparin and chitosan for vascular tissue engineering applications. Chem Eng J 2019;370:1057–67.

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Ch/G/nHAp/nCuZn nanocomposite scaffold showed suitable behavior based on cell growth, cell adhesion, alkaline phosphatase (ALP) activity as a marker of osteogenic difference, and histological in vitro cross-sections. In vivo subcutaneous implants exhibited granulation tissue creation and new tissue infiltration into the scaffold [304]. To improve the mechanical function of biopolymer, composites were prepared using inorganic metal oxide nanoparticles as fillers to make nanobiocomposite and provide bioactivity to an inert material [305, 306]. Furthermore, nanofillers furnish enhanced physicochemical properties of nanobiocomposites because of their high surface area and interactions with polymer chains at the molecular level [307]. Among the nanofillers, ceramic nano-TiO2 is biocompatible, nontoxic, flexible, and corrosion resistant and has high tensile strength [308–310]. High purity TiO2 NPs were synthesized by hydrothermal method. A biomimetic nanocomposite scaffold containing chitosan-SA blended with different concentrations of hydrothermally synthesized TiO2 NPs was obtained by the solvent casting process. Biomimetically produced chitosan-SA scaffold with TiO2 NPs (1 wt%) was observed to exhibit superior biocompatibility for bone tissue engineering applications [311]. Some of research reports on chitosan-based materials for tissue engineering purposes are given in Table 5.7.

5.2.2.2 Cellulose-based (nano)materials in tissue engineering Cellulose, due to its high crystallinity, high wet tensile strength, good water holding capacity, low cytotoxicity, and excellent stability, has been investigated as a potential biomaterial for scaffolds. Several researchers have investigated the use of chemically modified cellulose scaffolds, which promote better cell adhesion for tissue engineering [333, 334]. In addition, cellulose materials are highly attractive in tissue engineering owing to their customizability and control over the features at all levels. Zhang et al. fabricated 3D-scaffolded collagen/bacterial cellulose/bone morphogenetic protein 2 (BMP-2) by the template method in combination with the reverse phase suspension technique. The microspheres were full of pores and had a rough surface. Furthermore, the microspheres exhibited good biocompatibility and the 3D porous microspheres with multiple structures and components efficiently promoted the proliferation, adhesion, and osteogenic differentiation of mice MC3T3-E1 cells [335]. Carbon nanomaterials, for example, carbon nanotubes (CNT), could be perfect construction blocks to be combined into the bacterial cellulose matrix to improve its electrical conductivity [336]. The fabrication of BC/CNT nanocomposites by means of dipping technique using immersion of the BC in multiwalled carbon nanotube (MWCNT) solution has been developed by Yoon et al. [337]. Injectable hydrogels including chitosan, aldehyde-modified pectin (ADpectin), and aldehyde-modified cellulose nanocrystals (AD-CNCs) were fabricated with good internal structures, which is important for tissue engineering.

TABLE 5.7 Applications of chitosan-based materials in tissue engineering.

Entry

Chitosan-based materials

Organ

In vivo/ in vitro

Improvement

References

1

Chitosan/nHAP/polyethylene glycol

Bone

In vitro

Good mechanical strength supportive of bone tissue ingrowths

[300]

2

Chitosan/polycaprolactone blend fibrous mat

Skin

In vitro

Swelling property, thermal stability, surface roughness, and tensile strength

[312]

3

Glycosaminoglycans/chitosan complex membranes

Blood vessel

In vitro

Removes the shortcomings of existing small diameter vascular grafts by eliminating incomplete endothelialization and smooth muscle cell hyperplasia

[313]

Collagen/chitosan hydrogel

Corneal

Good permeability to albumin and glucose, regeneration of corneal epithelium, nerves, and stroma

[314]

Improved bone regeneration and healing of defects

[315]

4

In vivo

In vitro In vivo

5

Hemicellulose xylan/chitosan

Bone

In vitro In vivo

6

Chitosan/disodiumglycerophosphate

Intervertebral disc

In vitro

Thermosensitive hydrogels; shows excellent bioactivities and biocompatibilities for adiposederived stem cells induced NP-like cells

[316]

7

Chitosan/polycaprolactone blend

Corneal

In vitro

A suitable alternative for cadaveric cornea transplantation; limited biodegradability and cell support after long-term coculture from artificial substrate

[317]

8

Chitosan-derived sandwiched tubular scaffold

Blood vessel

In vitro

Regulation of pore diameter, very high burst strength, high suture retention strength

[318] Continued

TABLE 5.7 Applications of chitosan-based materials in tissue engineering—cont’d

Entry

Chitosan-based materials

Organ

9

Chitosan hydrogel/poly (butylene succinate-coterephthalate) copolyester (PBST) electrospun fibers

Intervertebral disc

Chitosan/gelatin/bioactive glass nanocomposite hydrogels

Bone

11

Chitosan/vitamin C/lactic acid composite membrane

Skin

12

Chitosan/PVA/graphene oxide/ hydroxyapatite/gold films

13

14

10

15

In vivo/ in vitro

Improvement

References

Mechanical property meets the requirement of the normal IVD; both in vivo and in vitro experiments suggest the hydrogel as promising candidate for IVD replacement therapies

[319]

In vivo and in vitro evaluation demonstrated good candidate as temporary injectable matrix to promote bone regeneration

[320]

In vitro

Provides optimum environment for skin cell attachment, spreading, and growth

[321]

Bone

In vitro

Quality obtained texture

[322]

Chitosan/PVA/graphene oxide composite nanofibers

Cartilage

In vitro

Increased mechanical properties of nanofibers; chitosan/PVA/GO showed most appropriate environment for the growth of ATDC5 cells compared with chitosan/PVA

[323]

Glycol chitosan-based hydrogel

Intervertebral disc

In vitro

Thermosensitive injectable hydrogels with tunable thermosensitivity and enhanced stability

[324]

Provide proliferation and growth along with potential support for angiogenesis during wound healing; show sustained ampicillin and bovine serum albumin release

[325]

Gelatin/carboxymethyl chitosanbased scaffolds

In vitro In vivo

In vivo In vitro

Skin

In vivo In vitro

16

Chitosan scaffold with PVA and amine coupling

Corneal

17

Thiolated chitosan nanoparticles

Corneal

In vitro

Addresses the issues of present amniotic membrane for corneal epithelium; better mechanical strength

[326]

In vitro

Potential antifibrotic and antiangiogenic therapeutics for corneal injuries

[327]

In vivo 18

Chitosan/gelatin/bioactive glass nanoparticle composites

Bone

In vitro

Promising temporary injectable matrix for bone tissue engineering; improved elastic modulus

[328]

19

Clay/chitosan/hydroxyapatite/ zinc oxide

Bone

In vitro

Enhanced biological and mechanical properties for the application in bone tissue engineering

[329]

20

Henna leaves extract-loaded chitosan-based nanofibrous mats

Skin

In vitro

Incorporation of extract showed synergistic antibacterial activity against bacterial cells; in vivo experiment supported cell viability and proliferation of human foreskin fibroblast cells on the prepared scaffolds

[330]

21

Chitosan/cellulose nanofibers

Intervertebral disc

In vitro

Combating mechanical disc failure shows promising results as nanofibril reinforced and noncellularized bioactive biomaterial to promote intervertebral disc regeneration

[331]

22

Chitosan/g-pluronic hydrogel (nanocurcumin-formulated)

Skin

In vitro

Enhances burn wound repair; has great potential to apply for wound healing

[332]

In vivo

In vivo

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Pectin and chitosan-based hydrogels, which mimic the ECM, are broadly used to maintain the balance between biofunctional and physical properties [338]. These hydrogels show low mechanical strength, which limits their applications in cartilage repair. Therefore, cellulose nanocrystals were utilized as nanofillers to reinforce the hydrogels based on the natural polysaccharide. The results indicated that lower equilibrium swelling ratios, more compact network structure, and good resistance to composite hydrogels degradation were observed by enhancing the cellulose nanocrystals content. The properties of cellulose acetate butyrate (CAB) nanofibers were improved by producing the composite nanofibers using CAB and hydrophilic PEG by Pushpamalar and coworkers. The tensile test results displayed that CAB/PEG composite had 2-fold higher tensile strength than pure CAB nanofibers. The hydrophobic properties of the composite nanofibers were also reduced. As the hydrophilicity increases, the swelling capacity of the composite nanofiber grows by 2-fold with more rapid biodegradation. The biocompatibility of nanofibers was investigated with normal human dermal fibroblasts. Furthermore, CAB/PEG nanofibers have better cell attachment compared with pure CAB nanofibers [339]. Combining metal and metal oxide nanoparticles with cellulose in tissue engineering helps improve the desired properties. A group of researchers has developed a novel design of injectable hydrogels, including collagen, aldehyde-modified nanocrystalline cellulose, and chitosan loaded with Au nanoparticles (collagen/ADH-CNCs/CS-Au) (Fig. 5.18). The results showed that the different molar ratios of collagen/CNCs and the presence of CS-Au content have important effects on the equilibrium swelling, microscopic morphology, mechanical properties, and in vitro degradation of the hydrogels.

FIG. 5.18 Schematic representation of cross-linked hydrogels formation [340]. Reprinted with permission from Nezhad-Mokhtari P, Akrami-Hasan-Kohal M, Ghorbani M. An injectable chitosan-based hydrogel scaffold containing gold nanoparticles for tissue engineering applications. Int J Biol Macromol 2020;154:198–205.

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The cytotoxicity study for the NIH 3 T3 cell line showed the efficiency and nontoxicity of the developed hydrogels in the destruction of the cells [340]. In another work, a green method was used to synthesize a composite hydrogel of regenerated silk fibroin stabilized with carboxymethylcellulose-Na and loaded with Ag NPs as one of the most active antimicrobial agents to facilitate tissue regeneration [341]. Furthermore, researchers prepared a nanocomposite of silver nanoparticles decorated on carboxylated cellulose nanowhiskers, which served the dual functions of furnishing antimicrobial activity and mechanical strength. Scaffolds including chitosan and carboxymethyl cellulose with varying nanocomposite percentages were formulated using freeze-drying technique. This study confirmed the excellent properties of manufactured scaffolds, which make them self-sustained and potential antimicrobial scaffolds to overcome bone-associated infections such as osteomyelitis [342]. In a recent study, polyaniline (PANI) was prepared in situ within bacterial cellulose/silver nanoparticle hydrogels synthesized by green hydrothermal reduction process in 0.01 and 0.25 M concentrations of HCl solution and PEG. PEG was applied as a soft template to guide and control the final morphology of PANI in ternary aerogels [343]. Table 5.8 briefly states the examples of utilization of cellulose-based materials in tissue engineering.

TABLE 5.8 Examples of cellulose-based materials used in tissue engineering purposes.

Entry

Cellulosebased materials

Organ

In vivo/ in vitro In vitro

1

Bacterial cellulose membrane conjugated with plantderived osteopontin

Bone

2

Polylacticacid/ polybutylene succinate/ cellulose nanofibrils

Vessel

Improvement

References

Improve the ability to promote cellular adhesion and bone differentiation

[344]

Improve the fiber morphology, indentation modulus, tensile strength, elastic modulus, and scaffolds biocompatibility

[345]

Continued

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TABLE 5.8 Examples of cellulose-based materials used in tissue engineering purposes—cont’d

Entry

Cellulosebased materials

Organ

In vivo/ in vitro In vitro

Improvement

References

Increase of alkaline phosphatase activity in bone cells

[346]

3

Bacterial cellulose/ hydroxyapatite nanocomposite

Bone

4

Microporous bacterial cellulose

Bone

Has great potential to apply for bone regeneration

[347]

5

Alginate/ cellulose nanocrystal hybrid bioink

Liver

The bioink combined superb properties counting prominent shear thinning, extrudability, and shape fidelity

[348]

6

Cellulose nanowhiskers

Vessel

Significant improvement in directional rigidity and strength

[349]

7

Sulfated sodium cellulose sulfate/gelatine

Cartilage

In vitro

Enhanced chondrogenesis compared to scaffolds made from pure gelatin

[350]

8

Bacterial cellulose

Cartilage

In vitro

Include good potential as a scaffold for tissue engineering of cartilage

[351]

In vivo

5.2.2.3 Alginate-based (nano)materials in tissue engineering Alginate has been widely studied over the past several decades as a vehicle to deliver proteins or cell populations, which can direct the reengineering or regeneration of various organs and tissues in the body. Alginate gels have exploited the wide range of gelling approaches, cell adhesion, physical properties, and degradation behavior of these materials. There are limits to the size of the generative agent, which can be released from alginate hydrogels with diffusion due

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to the pore size of 5 nm. Most proteins readily diffuse out from alginate gels, even in the absence of gel degradation, although degradation can speed release [41]. In addition, alginate-based materials have been broadly used in tissue engineering because they possess several features similar to the extracellular matrix of human tissues [352]. Among the appropriate scaffolds applied for tissue engineering, hydrogels can be considered the best since they have significant properties and overcome the limitations of scaffolds. Hydrogels including hydrophilic polymers with a 3D structure have significant potentials for restoring and absorbing water or biological fluids without any degradation or change in their chemical structure [353]. Yuan et al. formed a hydrogel by a double cross-linking process using gelatin and SA in which the amino group in gelatin and aldehyde group in alginate react to produce the first cross-linking agents. In addition, UV light can shape the second network of the hydrogel to improve and control the mechanical characteristics [354]. To address the requirement for biodegradable, electroactive conduits accelerating nerve regeneration, Homaeigohar et al. developed a hydrogel nanocomposite of alginate reinforced using citric acid functionalized graphite nanofilaments. Green, simple functionalization improves the distribution of nanofillers and their biocompatibility, as confirmed using mesenchymal stem cells in vitro. The uniformly distributed nanofilaments increase the mechanical stability of the hydrogel nanocomposite compared with the neat one up to three times. Moreover, the nanofilaments enable electrical contact and intercellular signaling, thereby stimulating their biological activity. In vitro investigations proved the biocompatibility of the hydrogel nanocomposite, which evidently proliferate and spread on PC12 cells. In vivo studies also supported the applicability of the hydrogel nanocomposite for implantation within the body, and the samples presented no adverse reaction or inflammatory responses after 14 days [355]. The studies have shown that tricalcium silicate bone cements possess good bioactivity and a suitable degradation rate. However, they also exhibit some drawbacks such as poor washout resistance, injectability, and formability, which seriously hinder their medical applications. Xu et al. reported the development of a novel type of bone cements-tricalcium silicate/sodium alginate (C3S/SA) composites via the interaction of SA molecules with Ca ions, in which an interpenetrating double network of calcium hydrate silicate (CSH) and alginate hydrogel was formed to improve the washout resistance, injectability, formability, and compressive strength of C3S. The results indicated that the washout resistance, injectability, and formability of C3S could indeed be importantly enhanced by the introduction of SA. Moreover, the compressive strength of the C3S/SA composite cement with an optimum composition could reach 54 MPa, which was considerably higher than that of C3S (i.e., 35.3 MPa). Moreover, the C3S/SA composite cements retained the bioactivity of C3S, such as the activity to induce apatite fabrication in simulated body fluid and promote cell proliferation [356].

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The macroporous three-dimensional spongy scaffolds composed of alginate, gelatin, and poly (vinyl alcohol) were prepared by cryogelation technique, and silver hydroxyapatite (HAP) was reinforced into the 3D matrix. The appropriateness of scaffolds for bone tissue engineering uses was determined by evaluating their antibacterial and cytotoxic nature against gram-negative and gram-positive bacteria and MC3T3-E1 preosteoblast cells, respectively. They do not show any cytotoxicity against osteoblast cell lines [357]. Moreover, alginate/HAP composite scaffolds were used as bone grafts with antibacterial properties owing to the presence of Ag NPs [358]. Silk fibroin/nHAp hydrogels modified by in situ manufactured Ag and Au NPs are very good for bone tissue engineering because of their antimicrobial activity and no toxicity against osteoblastic cells [359]. Table 5.9 shows the other examples of the utilization of alginate-based compounds in tissue engineering.

5.2.2.4 Pectin-based (nano)materials in tissue engineering Few studies report the application of pectin for tissue regeneration, probably taking into account the nonadhesiveness of this polysaccharide for cells. However, pectin hydrogels were found to have an outstanding potential for bone tissue engineering, as they promote the nucleation of a mineral phase if immersed in adequate physiological solutions [49], with the formation of biomimetic constructs better mimicking the natural architecture of the bone. Unmodified and chemically modified pectin gels, microspheres, and coatings were studied for the 2D and 3D culture of bone cells, showing interesting properties for metabolic activity, cell viability, and differentiation [368]. New cross-linked pectin nanofibers with improved cell adhesion have also been reported. The nanofibers are made via first oxidizing pectin with periodate to produce aldehyde groups, followed by cross-linking the nanofibers with adipic acid dihydrazide to covalently connect pectin macromolecular chains with adipic acid dihydrazone linkers. Moreover, the cross-linked pectin nanofibers display excellent mechanical strength and much improved body degradability. The combination of excellent cell adhesion capability, body degradability, and mechanical strength suggests that the cross-linked pectin nanofibers are promising candidates for in vivo applications such as wound healing and tissue engineering [369]. Peripheral vascular and coronary artery illnesses are the leading cause of mortality and morbidity worldwide and often require surgical intervention to replace damaged blood vessels, including the use of vascular patches in endarterectomy processes. In a work, porous or dense scaffolds composed of chitosan (Ch) complexed with pectin (P) or alginate (A) were manufactured and characterized considering their application as tissue engineered vascular patches. Scaffolds made with alginate showed higher culture medium uptake capacity than compounds fabricated with pectin. In the presence of lysozyme, degradation analysis of the patches presented longer term stability for Ch-P-based

TABLE 5.9 Examples of alginate-based materials used in tissue engineering.

Entry

Alginate-based materials

Organ

In vivo/ in vitro

Improvement

References

1

Poly(vinyl alcohol)/gelatin/alginate/ collagen

Skin

In vitro

Good cell viability and proliferation, high swelling, increased elongation at break

[360]

2

Oxidized alginate/hyaluronate hydrogels

Cartilage

In vitro In vivo

Useful in cartilage regeneration

[361]

3

RGD-grafted oxidized SA-N-succinyl chitosan hydrogel

Bone

In vitro

Good degradability, improved cell adhesion and proliferation, promoted endothelial differentiation, and osteogenic differentiation of bone-marrowderived mesenchymal stem cells

[362]

4

Co-encapsulation of anti-BMP2 monoclonal antibody and mesenchymal stem cells in alginate microspheres

Bone

In vitro In vivo

The advantages of system contain its simplicity and ease with which it can be modified to encapsulate hBMMSCs in an injectable and biodegradable alginate hydrogel, yielding a three-dimensional, cell delivery scaffold for bone tissue engineering

[363]

5

Alginate/hydroxyapatite composite

Bone

In vitro

Improve the mechanical and cell-attachment properties of the scaffolds

[364]

6

Calcium phosphate-alginatechitosan microencapsulated MC3T3E1

Bone

In vivo

Alginate-chitosan microcapsule is better than alginate one for seeding cells in calcium phosphate cement

[365]

7

Porous hydroxyapatite/chitosanalginate composite

Bone

In vivo

No cytotoxic effects, good biocompatibility, and strong positive effect on bone formation

[366]

8

Alginate combined calcium phosphate cements

Bone

In vivo

Promising biomaterials to improve the properties in osteogenic differentiation

[367]

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scaffolds. Pectin including matrices offered higher elastic ability and modulus to withstand larger deformations. Furthermore, these compounds showed better efficiency when tested for hemocompatibility, with lower levels of platelet adhesion and activation. Human smooth muscle cells (HSMCs) were adhered, spread, and proliferated better on matrices formed with pectin, probably as a consequence of cell response to higher stiffness of this compound [370]. In a recent study, pectin hydrogel nanofiber scaffolds were fabricated by a multistep approach, including periodate oxidation, electrospinning, and adipic acid dihydrazide cross-linking. The analysis showed that the prepared pectin nanofiber mats had a nano-sized fibrous structure with a 300–400 nm diameter. Physicochemical properties tests showed that the hydrophobicity and stiffness of the fiber mat could be manipulated through adjusting the oxidation and crosslinking levels of the pectin hydrogels. Live/dead staining presented high viability of the mesenchymal stem cells (MSCs) cultured on the pectin hydrogel fiber scaffold for 14 days. Furthermore, the potential application of pectin hydrogel nanofiber scaffolds of various stiffness in stem cell difference toward vascular cells was evaluated by gene expression analysis. Real-time RT-PCR results showed that stiffer scaffolds simplified the differentiation of MSCs toward vascular smooth muscle cells, while softer fiber mats promoted MSC differentiation into endothelial cells [371]. The fabrication of porous tubular scaffolds is of good interest in tissue engineering field, given the presence of some tubular structures in the human body. In a work, a methodology was reported for the production of tubular-shaped scaffolds based on the casting of polymeric solutions by controlled cross-linking mediated using a semipermeable cast. The production of hydrogel tubular scaffolds from chitosan-pectin polymeric mixtures was achieved to verify the feasibility of the method. The structures are highly porous, presenting interconnected pores with an average diameter of about 360 μm. The seeding of human smooth muscle cells on the material was effectively achieved using collagen gel to facilitate cell migration and retention inside the scaffold structure [372]. In another study, new porous 3D scaffolds from silk fibroin and functionalized citrus pectin were developed for skin tissue engineering applications. Cross-linking was performed by Schiff’s reaction in the presence of borax as a cross-linking coordinating agent and CaCl2. After freeze-drying and methanol treatment, plasma treatment (10 W, 3 min) was used to eliminate the surface skin layer formed on scaffolds. 3D matrices had high porosity and interconnectivity with pore sizes of 120 mm, which provided an appropriate microenvironment for the cells. The mechanical properties of 3D matrices satisfied the scaffolds stability under compressive stress and supported adhesion, proliferation, and penetration of fibroblast cells. Scaffolds presented low weight loss (21.3% in 40 days) and high water uptake capability in phosphate buffered saline (800% in 24 h) [373]. Furthermore, Ba´rtolo et al. reported the synthesis and photo cross-linking of cell instructive pectin hydrogels by cell degradable peptide cross-linkers and integrin-specific adhesive ligands. Protease-degradable hydrogels generated

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by photoinitiated thiol-norbornene click chemistry are rapidly shaped in the presence of dermal fibroblasts, display tunable properties, and are capable of modulating the behavior of embedded cells, including the hydrogel contraction, cell spreading, and secretion of matrix metalloproteases. Keratinocytes seeded on top of fibroblast-loaded hydrogels are able to adhere and make a compact and dense layer of the epidermis, mimicking the architecture of the native skin. Thiol-ene photocrosslinkable pectin hydrogels support the in vitro generation of full-thickness skin and are thus a highly promising plan for skin tissue engineering purposes, including in vitro testing models and wound healing [374]. One of the most common methods to reinforce hydrogels is to produce composites of hydrogel precursors and micro/nano-sized fillers. However, composites are generally complicated and are sometimes ineffective. In a study, the mechanical properties of a pectin-based hydrogel have been considerably increased by the chemical modification of pectin chains and combination with a polypeptide. Functionalized polysaccharide and polypeptide were blended with different ratios. A covalently cross-linked network between aldehyde functionalized pectin and amine bearing fibroin was observed. Moreover, cell culture investigations showed that a blend with the oxidized pectin to fibroin ratio of 50:50 (P50 F50) prevailed over other compositions with respect to cell viability and function [375]. In a study, a tough pectin-Fe3+/poly (acrylamide-co-stearyl methacrylate) (P(AAm-co-SMA)) double physical cross-linking (DPC) network hydrogel was fabricated by a three-step method. The first HPAAm network was made by hydrophobic associations between the PSMA segment in P(AAm-co-SMA) and trivalent ions (Fe3+) cross-linked pectin network as the second network. Because of the reversibility of dual physical cross-linking structures, the pectin-Fe3+/HPAAm hydrogel displays excellent toughness. Moreover, the pectin-Fe3+/HPAAm DPC hydrogels have tunable mechanical properties via adjusting the ratio of pectin and HPAAm networks. To explore their potential application in tissue engineering, ATDC5 chondrocytes were seeded on the prepared DPC hydrogels. The findings suggest that the pectin-Fe3+/HPAAm DPC hydrogels can support the adhesion and proliferation of ATDC5. Moreover, the ATDC5 cells can penetrate into the hydrogel [376]. Thermosensitive hydrogels based on chitosan/pectin and chitosan/pectin/Au NPs were successfully prepared using various Au NP levels. By tilting method, gelation temperature was decreased when the amount of Au NPs increased and pectin concentrations reduced. All samples were extremely cytocompatible with many cell types such as epithelial colorectal adenocarcinoma, normal kidney epithelial, HPV-16-positive human cervical tumor, kidney epithelial, and murine macrophage cells. Cell viability assays using the MTT method upon mouse preosteoblastic cells (MC3T3-E1 cells) indicated that the prepared composites had the potential to foster the growth and proliferation of bone cells, making them possible stimulators for the bone tissues reconstruction [377]. Some of research reports on pectin-based materials for tissue engineering purposes are given in Table 5.10.

TABLE 5.10 Applications of pectin-based materials in tissue engineering. Entry

Pectin-based materials

Organ

In vivo/ in vitro

1

Thiol-ene photocrosslinkable pectin hydrogels

Skin

2

Hyaluronic acid/RGDfunctionalized pectin hydrogel

3

Improvement

References

In vitro

Formation of full-thickness skin and a highly promising platform for purposes

[374]

Cartilage

In vitro In vivo

Best host tissue-mimetic microenvironment for enhancing chondrogenesis and maintaining chondrocyte phenotype

[378]

Pectin and high molar weight chitosan

–

–

Improved elastic moduli

[379]

4

Calcium phosphate/pectin cement

Bone

In vitro In vivo

Significantly promoted osteogenic differentiation in vitro and bone regeneration in vivo

[380]

5

Pectin/chitosan

–

–

Promote anchorage, adhesion and support human stem cell growth

[381]

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5.2.2.5 Gelatin-based (nano)materials in tissue engineering Different properties of gelatin such as biodegradability, biocompatibility, and absorbability have attracted significant interest in the use of gelatin for tissue engineering applications. However, gelatin is not stable at normal body temperature in vivo mainly because of its relatively low melting temperature. Therefore, cross-linking is required to stabilize its macromolecular structure, enhance its mechanical properties, and prevent its rapid degradation and swelling upon long-term exposure to the host tissue. To date, numerous techniques based on enzymatic physical and chemical processes have been applied for the crosslinking of gelatin. Using these techniques, it is possible to derive gelatin in the forms of foams, gels, and porous structures with precisely modulated physiochemical properties. In a recent study, a dual nonwoven ultrafine fibrous scaffold composed of polyurethane (PU)/Nylon 6 (N6) hybrid polymers mixed with natural gelatin (Gel) was prepared by dual syringe electrospinning method. Pronounced dual composite fine fibers of (PU-Gel)/(N6-Gel) (161  79 nm) and PU/N6 (148  43 nm) with an interconnected porosity were obtained. The dual N6/Pu fibrous scaffold showed higher tensile strength and modulus than a dual PU-Gel/N6-Gel scaffold, whereas the dual composite fibrous scaffold containing gel induced the largest elongation at breaking load. Biomimetic mineralization characteristics observed at different time intervals showed the formation of a bone apatite like layer on the dual composite fibrous scaffold, indicating good bioactivity. The dual (PU-Gel)/(N6-Gel) nanofiber composite fibrous scaffolds had better wettability compared with the other scaffolds and supported high osteoblast cell proliferation. This suggests that the fabricated dual composite fibrous scaffolds containing gelatin may have the potential to be used in bone tissue engineering [382]. Corneal disease is considered the second leading cause of vision loss, and keratoplasty is known as an efficient treatment for it. However, the tissue engineered corneal substitutes are promising tools in experimental in vivo repair of the cornea. Selecting appropriate cell sources and scaffolds are two important concerns in corneal tissue engineering. Gelatin-based biomaterials have been attractive candidates for corneal tissue engineering since they are mechanically stable, are transparent, and support cell adhesion and proliferation. For instance, gelatin in the form of porous films has been used as an appropriate carrier for fibroblast, corneal endothelial, and fibroblast precursor cells for transplantation applications [383]. In a study, researchers investigated the physical and biocompatibility properties of the bioengineered cornea fabricated from gelatin (Gel) and type-I collagen (COL). Two gelatin-based hydrogels cross-linked with EDC/NHS were prepared, and their physicochemical properties were studied. The equilibrium water content and enzymatic degradation of these materials can be easily controlled by adding COL. The findings suggested that the incorporation of COL-I increases optical properties, hydrophilicity, stiffness, and Young’s modulus. This biocompatible hydrogel may be a promising artificial corneal substitute [383].

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In another study, the development of gelatin/ascorbic acid (AA) cryogels was reported for keratocyte carriers in vivo and in vitro. The cryogel samples were prepared by the blending of AA (0–300 mg) with gelatin and carbodiimide cross-linking via cryogelation method. The hydrophilic AA content in the carriers was found to significantly affect the cross-linking degree and pore dimension of cryogels, thereby dictating their biological and mechanical stability and AA release profile. The cryogel carriers with low-to-moderate AA loadings were well tolerated by rabbit keratocyte cultures and anterior segment eye tissues, demonstrating good ocular biocompatibility. Although higher incorporated AA levels contributed to enhanced metabolic activity and biosynthetic capacity of keratocytes grown on cryogel matrices, the presence of excessive amounts of AA molecules could lead to toxic effects and limit cell proliferation and matrix formation. The cytoprotective activity against oxidative stress was shown to be strongly dependent on AA release, which further determined cell culture performance and tissue reconstruction efficiency. With the optimum AA content in carrier materials, intrastromally implanted cell/cryogel constructs showed better capability to enhance tissue matrix regeneration and transparency maintenance, as well as mitigate corneal damage in an alkali burn-induced animal model. Thus, the understanding of antioxidant molecule mediated, structure property function interrelationships in gelatin/AA cryogels is critical for the design of carriers for potential use in corneal stromal tissue engineering [384]. In addition, every year, millions of patients suffer from major liver failure and diseases. Recent developments in the tissue engineering field and stem cellbased therapies have exhibited a great promise in the regeneration of damaged liver tissues. Collagen types I and IV are the main constituents of liver ECM [385]. Thus, gelatin-based biomaterials have attracted important attention for the development of biomimetic scaffolds to support hepatic cell functions. For example, gelatin-coated substrates have been extensively used to direct the hepatic differentiation of stem cells on 2D surfaces. Studies have shown that gelatin-coated substrates can generate fully functional hepatocytes from human embryonic stem cells (ESCs), as well as inducing pluripotent stem cells (iPSCs) in the presence of growth factors such as acidic fibroblast growth factor (aFGF) and hepatocyte growth factor (HGF) [386, 387]. There have also been other reports focusing on various gelatin-based composite scaffolds and microspheres such as silk fibroin/gelatin and chitosan/gelatin to enhance hepatic cell functions (i.e., albumin secretion, viability) [388–390]. In a study, it was established that silk-based scaffolds containing gelatin significantly enhanced the spread and proliferation of human hepatic cells [389]. Furthermore, increasing the percentage of gelatin within the composite scaffold promoted cellular adhesion with minimal inflammation in vivo. In general, gelatin-based biomaterials exhibited valuable properties for liver tissue engineering by promoting specific functions. Articular cartilage is an avascular tissue, which contains only one cell type (chondrocyte) and has a very limited capacity of self-repair. Chondrocytes are

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responsible for the fabrication and maintenance of their extracellular matrix, which is composed of a hydrated collagen network, a highly charged proteoglycan gel, and other glycoproteins and proteins [391]. The biomimetic scaffolds of PLLA-gelatin were successfully fabricated by the co-electrospinning technique [392]. The scaffold matrix showed good proliferation and differentiation of primary human chondrocytes. In a different study, the addition of hyaluronic acid blends to a gelatin synthetic polymer matrix improved the biocompatibility of chondrocytes, extracellular matrix fabrication, cell proliferation, and structural and mechanical properties [393]. Brochhausen et al. demonstrated that the exogenous stimulation of human articular chondrocytes (HACs) with a low dose of prostaglandin E2 (PGE2) growth on the 3D gelatin-based scaffold induced the HACs phenotypic differentiation and collagen type II expression. This study exhibited the potential of 3D scaffolds for guided tissue engineering of cartilage [394]. Soluble starch-coated Ag NPs and bioactive glass (BG) particles were incorporated into gelatin (Gt) to fabricate Gt/Ag-NPs/BG nanocomposite membranes. Employing Box-Behnken design, second-order models have been successfully obtained to evaluate the statistical significance of interaction and individual effects of applied voltage and flow rate on fiber diameter, tip to collector distance (TCD). Under optimum conditions (applied voltage of 26 kV, TCD of 180 mm, and flow rate of 0.5 mL/h), nanocomposite membranes with similar fiber size of bone tissue extracellular matrix can be fabricated with the predicted value of 557 nm by the proposed model. The optimized nanofiber membrane was prepared with average fiber diameter of 472  94 nm. The characterization of this nanofiber suggests that the synthesized nanocomposite is a potential candidate for bone tissue engineering purposes [395]. Furthermore, chitosan gelatin/zinc oxide nanocomposite hydrogel scaffolds (CS-GEL/nZnO) were synthesized via in situ fabrication of ZnO NPs to reach a scaffold with both drug delivery and inherent antibacterial properties. The swelling, cytocompatibility, antibacterial, biodegradation, and cell attachment of the scaffolds were evaluated. The results showed that the obtained scaffolds had high porosity with a pore size of 50–400 μm, and ZnO NPs were well distributed on the CS-GEL matrix without any agglomeration. In addition, the nanocomposite scaffolds showed enhanced swelling, biodegradation, and also antibacterial properties. Moreover, the drug delivery studies showed that ZnO NPs could control naproxen release. Cytocompatibility of the samples was carried out using normal human dermal fibroblast cells (HFF2). In comparison to the previous reports in which ZnO NPs were simply added to the scaffold matrix, the in situ fabrication of ZnO NPs led to lower cytotoxicity and higher antibacterial effects as a result of good distribution of ZnO NPs in this procedure. According to the obtained results, the CS-GEL/nZnO is strongly recommended for biomedical applications, especially skin tissue engineering [396]. Some of research reports on gelatin-based materials for tissue engineering purposes are given in Table 5.11.

TABLE 5.11 Applications of gelatin-based materials in tissue engineering.

Entry

Gelatin-based materials

Organ

In vivo/ in vitro

1

Methacrylated gelatin hydrogels

Corneal

2

Alginate/gelatin scaffolds incorporated with silibinin-loaded chitosan NPs

3

Improvement

References

In vivo

High transparency, adequate mechanical strength, biocompatibility, and well integration with the host tissue

[397]

Bone

In vitro

Potential for prolonged and sustained release of silibinin to promote bone fabrication

[398]

Functional nanofiber mat of PVA/gelatin containing NPs of biphasic Ca3(PO4)2

Bone

In vivo

Increased bone fabrication was observed for the 50% BCP-loaded electrospun PVA/GE blends within 2 and 4 weeks

[399]

4

Aligned and random polycaprolactone (PCL)/gelatin fibrous scaffolds

Bone

In vitro

Blending PCL with gelatin increased the mechanical properties of the scaffolds

[400]

5

Bovine gelatin electrospun scaffolds

Bone

In vivo

Mechanically enhanced scaffold

[401]

6

Incorporation of vitamin D3 and nHAp into electrospun PCL/gelatin scaffolds

Bone

–

Indicated superior properties of nHAp and vitamin D3 incorporated in PCL/gel scaffold for use in bone tissue engineering

[402]

7

Poly ε-caprolactone-gelatin/MWCNT electrospun scaffolds

Cartilage

–

Presented more bioactivity and slower degradation rate and not have any cytotoxicity

[403]

8

Gelatin/polycaprolactone-polyethylene glycol

Cartilage

In vitro

Showed the potential to express collagen II and aggrecan genes

[404]

9

Bone morphogenetic protein-2-loaded polycaprolactone-gelatin-biphasic Ca3(PO4)2 fibrous scaffolds

Bone

In vivo

Improved cell proliferation and cell adhesion behavior and sustained release behavior for 31 days

[405]

Bioactive NP-gelatin composite scaffold

Bone

Excellent biodegradability, bioactivity, and cytocompatibility

[406]

10

In vitro In vivo

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5.2.2.6 Lignin-based (nano)materials in tissue engineering Among the great number of compounds reported for tissue engineering, only very few have been developed from lignin derivatives. An alginate-lignin composite aerogel has been fabricated by Quraishi et al. They combined solutions of lignin and alginate and used CO2-induced gelation and foaming to fabricate aerogels with micrometer-sized interconnecting pores. Aerogels exhibited low stiffness in the range of fibrous tissue, but no cytotoxic effects on mouse fibroblast like L929 cells in vitro [407]. Glycinated Kraft lignin produced after the Mannich reaction was cross-linked to hyaluronan, and the hydrogels obtained were found good for tissue engineering because of their stability, viscoelastic behavior, swelling capacity, and mechanical properties, as well as their cytotoxicity effect [408]. Moreover, Morganti et al. investigated the potential of lignin and chitin for application as natural scaffold compounds imitating the extracellular matrix. They synthesized composites including nanoscaled lignin and chitin nanofibrils of high surface area to weight ratios [409]. In another study, Farhat and coworkers prepared a variety of different polysaccharide-based composites by reactive extrusion process. Hemicellulose, lignin, or starch were cross-linked with citric acid, and the corresponding hydrogels were characterized by degradability, swelling, and mechanical strength. Degradation rates were analyzed at physiological conditions for 15 days. Degradation could be decreased using additional catalysts during polymer extrusion. Swelling is dependent on pH and the amount of citric acid applied as a cross-linker. Dynamic mechanical analysis showed that hydrogel degradation induced an important reduction in the compressive modulus [410, 411]. Recently, lignin-carbohydrate linkage/cellulose nanofiber-based tubular porous carriers synthesized during various ball milling times have been reported to stimulate the coronary stent of the heart to some extent and provide a suitable 3D environment for the growth of coronary artery endothelial cells. Tubular carriers have a relatively small specific surface area and pore size compared with the spherical carrier. The carriers have effective stability at different pH values and can adapt to a variety of weak acid and alkali environments [412]. Wang and coworkers reported reinforced chitosan microfibers synthesized by adding different amounts of lignin during the spinning process. They showed that the addition of 3%–5% lignin increased the stiffness and tensile strength of chitosan. They predict suitable biocompatibility, but this not been proven by experimental data [413]. Electrospinning of synthetic and natural polymers opens a new applied approach to tissue engineering through producing fibers. In another study, aligned electrospun PVA-poly(glycerol sebacate) (PGS) fibers with different percentages of lignin were prepared for nerve tissue engineering. The effect of the various amounts of lignin on the diameter and morphology of the fibers was investigated. The results showed smooth fibers with a uniform diameter and the increased amount of lignin decreased the fiber

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diameter from 530 to 370 nm. Finally, the results suggest PVA-PGS/5% lignin as a promising material for nerve tissue engineering [414]. Spiridon and Tanase reported PLA-lignin composites. In their study, the addition of up to 7% lignin microparticles led to a reduction in tensile strength. However, adding 7%–15% lignin improved the tensile strength. Moreover, the biocompatibility of the composites was investigated on SaOS-2 cells with no observed adverse effects [415]. In a work, LNPs were used as cross-linking junctions to produce hydrogels and PAM/LNP nanocomposite hydrogel with high mechanical properties. First, hydroxyl free radicals were produced from H2O2 reduction using AA. The hydroxyl free radicals had a stronger interaction with LNP and produced phenoxy free radicals. Free radical polymerization was then initiated from the nanolignin surface, followed by propagation. PAM chains cross-linked by N, N0 -methylenebisacrylamide (MBAAm), connecting neighboring LNP, were then formed by the disproportionation termination reactions of the propagating chains (Fig. 5.19). The hydrogel showed high compressive and tensile strengths and excellent recoverability. The fracture strength of the PAM/LNP hydrogel under compressive stress is on the order of megapascals, which is many orders of magnitude higher than those of pure PAM hydrogels. The synergistic effect of nanocomposite network structure and the strong H-bonding between polymer chains endow the hydrogel with a superb mechanism of distributing the applied load. Considering good mechanical properties, noncytotoxicity, and simple synthesis techniques, this high-performance hydrogel material has potential applications in the tissue engineering field [416]. Lignin-based copolymers comprised of lignin-poly(ε-caprolactone-colactide) were prepared via solvent-free ring-opening polymerization and subsequently spun into blend nanofibers. The copolymers were blended with either PLLA or PCL during electrospinning. The spun mats were evaluated in terms of their antioxidant activity, biocompatibility, and mechanical properties. PCL blends were mechanically developed. However, the stability of the PLLAblends was slightly reduced. Biocompatibility and antioxidant property were improved. PLLA blends presented increased viability and proliferation of NIH3T3 fibroblasts, making them attractive candidates for tissue engineering purposes [417]. In addition, Erakovic and colleagues synthesized a bioactive coating for titanium implants. The coatings consisting of HAP and organosolv lignin in different ratios were deposited onto the implants electrophoretically and were sintered afterward. The coatings displayed good biocompatibility, and when doped with Ag during deposition, even a good antibacterial effect against S. aureus [418].

5.2.3 Wound dressing/healing Wound healing is the result of a complex process of tissue repair consisting of several intracellular and intercellular pathways [419]. There are two important groups of wounds, “acute” including thermal, mechanical, surgical, and

FIG. 5.19 (A) Schematic representation of the design of the PAM/LNP hydrogel. (B) The reaction of forming lignin NP free radical (1) and PAM/LNP hydrogel (2). (C–F) Photographs of the PAM/LNP hydrogel: (D) compressing, (E) bending, and (F) knotting [416]. Reprinted with permission from Chen Y, Zheng K, Niu L, Zhang Y, Liu Y, Wang C, Chu F. Highly mechanical properties nanocomposite hydrogels with biorenewable lignin nanoparticles. Int J Biol Macromol 2019;128:414–20.

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Hemostasis

Inflammatory

Blood clot

Scab

Fibroblast Macrophage

BLOOD VESSEL

BLOOD VESSEL

Remodeling

Proliferative Freshly healed epidermis Fibroblasts proliferating Freshly healed dermis Subcutaneous fat BLOOD VESSEL

BLOOD VESSEL

FIG. 5.20 The four stages of wound healing [422]. Reprinted with permission from Negut I, Grumezescu V, Grumezescu AM. Treatment strategies for infected wounds. Molecules 2018; 23(9):2392.

chemical and “chronic” injuries, for example, diabetic wounds and bedsores [420]. Wound healing is a normal biological process in any tissue, which includes four steps: (a) homeostasis; (b) inflammation, which typically lasts up to 6 days [421], (c) proliferation, which usually covers the following 2 weeks; and (d) restoration, which continues for up to 2 years (Fig. 5.20) [422, 423]. The inflammatory phase starts with a vascular reply, which confirms hemostasis through the formation of blood clots. Distress molecules released using injured cells then act as chemoattractants for leukocytes, which show two major functions: recognition and annihilation of infectious agents, as well as cytokine release stimulating cells involved in the proliferative phase [419]. The moment when granulation tissue starts to cover the surface of the wound marks the transition to the proliferative phase. The main factors in this stage are signified by activation of fibroblasts, which fabricate collagen and other extracellular matrices, as well as neoangiogenesis [422]. The last phase of remodeling restores the morphology and function of the tissue [419]. Old-style wound dressings including herbal products such as crude extract of plants, or animal products such as fat or skin, have been developed during many years to shape the modern wound dressings [424–426]. Today, modern

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science uses the energetic sources of naturally available materials to treat a various range of illnesses. Traditionally, biomaterials derived from natural sources have been utilized as vital sources of medicine for different wounds, and there has been excessive interest in their use in wound healing. Nowadays, the application of naturally available materials, for example, biomaterials, for biomedical and clinical applications is significantly increasing because of their versatile qualities, including biocompatibility, optimal mechanical property, biodegradability, and nonimmunogenicity [427]. Biopolymer-based wounddressing compounds are widely used in clinical trials and are showing positive results.

5.2.3.1 Chitin and chitosan-based (nano)materials in wound dressing/healing Chitin hydrogels have been extensively used as wound dressings because of their biocompatibility and ability to provide a moist environment for wound healing. However, a bacterial infection often delays the healing process. A novel thermosensitive and pH-sensitive hydroxypropyl chitin/tannic acid/ferric ion (HPCH/TA/Fe) hydrogel composite was prepared via a simple assembly (Fig. 5.21). The precooled hydrogel precursor solution can be injected onto the irregular wound area and gel rapidly at physiological temperature. The TA acted not only as a cross-linker to enhance the mechanical properties of the hydrogel but also as an antibacterial agent, which could be sustainably released in response to the acidic medium. The composite exhibited an excellent

HPCH

TA

TA release

Dead bacteria

Live bacteria

FIG. 5.21 Preparation process and schematic structure of HPCH/TA/Fe hydrogel [428].

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broad spectrum of antibacterial activity up to 7 days with negligible cytotoxicity. Moreover, the hydrogel can inhibit bacterial infection and accelerate the wound-healing process without scars in the mouse experiment. These results confirm the potential use of this composite for infected wound healing [428]. Chitosan has been shown to be an efficient biomaterial to promote wound healing. Most of the studies have reported that chitosan is a nontoxic, slowly biodegradable and biocompatible material, which combines a unique set of useful properties for wound healing. Chitosan-based wound dressings possess a set of special properties, including biodegradable, hemostatic, and antibacterial properties, which make them useful for wound healing. The antibacterial property of chitosan was already observed at low concentrations against S. aureus or E. coli and may be used in various formulation types such as films, gels, or NPs. As a consequence, it is widely used in medical and veterinary fields as a woundhealing promoter [429–434]. N-Acetyl glucosamine in chitosan and chitin is the main constituent of dermal tissue, which is vital for the repair of scar tissues [435]. A water-soluble chitosan derivative, N-succinyl-chitosan, was prepared using hydrochloric acid, alkaline chitosan, and succinic anhydride. The capacity of this chitosan derivative to accelerate the wound-healing progress was then evaluated. Animal wound-healing trial showed that N-succinyl-chitosan considerably reduced the time of healing compared with chitosan [436]. Chitosan cannot be twisted by an electrospinning technique directly because of its polycationic nature in solution. Several investigations were carried out to modify chitosan with other polymers to overcome this challenge. Chitosan and poly (ethylene oxide) have been produced into a CS/polyethylene oxide nanofibrous-type extracellular matrix, which releases a dual growth factor for wound healing in such a way as the wound healing happens by a natural process. The design and release of the dual growth factor happen at the wound site (Fig. 5.22) [437].

FIG. 5.22 Preparation of chitosan-based composite loaded with two growth factors for increasing the wound healing by electrospun fibers by a simple technique [437].

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Recently, biocompatible nanocomposite films based on polyethylene glycol and chitosan polymers including zeolitic imidazolate framework-8 (ZIF-8) nanoparticles and cephalexin antibiotic drug have been fabricated to improve wound dressing compounds capable of controlled drug release [438]. The variety of wound dressings already present in different forms including sponges, gels, granules, and sprays prove that chitosan is a good material for woundhealing applications (Table 5.12) [37].

TABLE 5.12 Chitosan-based materials on the market [37]. Product

Material

Dressing type

Producer

Axiostat

100% chitosan

Sponge

Axiobio

Chitoderm plus

Strong superabsorber coated with chitosan

Super absorber

Trusetal

ChitoSAM 100

100% chitosan

Nonwoven chitosan dressing spun directly from chitosan

Sam Medical

Celox

Chito-R activated chitosan granules

Gauze, granules

MedTrade

ChitoClear

ChitoClear positively charged chitosan

Gel or liquid spray

Primex

Opticell

Primarily composed of chitosan (cytoform chitosanbased gelling technology)

Gelling fiber

Medline

ChitoGauze PRO

Chitosan-based dressings

Chitosan-coated gauze

Tricol Biomedical

ChitoFlex PRO

Chitosan-based dressings

Hemostatic dressing active on both sides

Tricol Biomedical

ChitoDot

Chitosan-based dressings

Double-sided hemostatic dressing

Tricol Biomedical

HemCon Patch PRO

Chitosan-based dressings

Noninvasive hemostatic patch

Tricol Biomedical

HemCon Bandage PRO

Chitosan-based dressings

Hemostatic bandage

Tricol Biomedical

HemCon Strip PRO

Chitosan-based dressings

Hemostatic bandage

Tricol Biomedical

KytoCel

Chitosan fibers

Gelling fiber

Aspen Medical Continued

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TABLE 5.12 Chitosan-based materials on the market—cont’d Product

Material

Dressing type

Producer

HemoPore

Chitosan lactate

Hemostatic bioresorbable nasal dressing

Stryker

ExcelArrest XT

MC (modified chitosan)

Hemostatic patch

Hemostasis

PosiSep

NOCC (N-Ocarboxymethyl chitosan)

Hemostatic sponge

Hemostasis

XSTAT

Wood pulp sponges coated with chitosan

Hemostatic device containing superabsorbent sponges of chitosan

RevMedX

Alchite (University of Bolton patent)

Alginate and chitosan

Composite fiber

University of Bolton patent

LQD

CHITOSAN-FH02 a higher positive charge and the highest degree of deacetylation of any chitosan product

Spray

Medoderm GmbH Brancaster Pharma

ChitoHeal

N-acetyl-D-glucosamine (chitosan)

Gel

ChitoTech

ChitoClot Gauze

100% medical-grade chitosan

Gauze

BenQ Materials BioMedical

ChitoClot Bandage

100% chitosan-based, nonwoven with adhesive back sheet

Nonwoven dressing

BenQ Materials BioMedical

ChitoClot Pad

100% medical-grade chitosan

Sponge

BenQ Materials BioMedical

ChitoRhino

Distilled water, xylitol, chitosan, natural sea salt, citric acid, grapefruit seed extract

Spray

Ideoto LLC

ChitoRhino

Distilled water, xylitol, allnatural sea salt, chitosan, methylcellulose, Aloe vera, citric acid, grapefruit seed extract

Gel

Ideoto LLC

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In addition, when Ag NPs are linked with chitosan and chitin, they accelerate the wound-healing process with superb antimicrobial properties. An antiinfectious wound dressing was developed in the form of chitin nanofiber sheet composites with the effective loading of size controlled spherical Ag NPs ( .05) with respect to commercial chitosan (Fluka, BioChemika) (56.16%). All chitosan films displayed similar glass transition temperatures (P > .05) with respect to cellophane control. According to FTIR spectroscopic analysis of chitosan films, the fungistatic activity could be associated with the formation of hydrogen bonds between the amino groups of chitosan and the hydroxyl groups of polymer or sorbitol. Even in plasticized or no plasticized films, chitosan displays fungistatic activity, which makes possible the development of active packaging based on mixtures of chitosan with excellent thermal stability. Factors such as kind of chitosan, storage temperature, and the modification of barrier and mechanical properties may enhance the antimicrobial effect of the films by the addition of antimicrobial or plasticizers agents [216]. Heterocyclic compounds [217] have been used for many synthetic and medical chemistry applications because of their exceptional bioactivities, including antifungal [218], antibacterial [219], antitumor [220], antiinflammatory [221], and antiviral [222] activities. To be precise, some nitrogen-comprising heterocycles, which display excellent biological properties such as triazoles, thiadiazoles, and thiazoles, are used considerably in current commercial agrochemicals. In another study, five new urea-functionalized chitosan derivatives were fabricated via reactions of chloroacetyl chitosan (CTCS) with urea groups bearing nitrogen-containing heterocycles. The synthetic strategy of the chitosan derivatives is presented in Scheme 6.5. The antifungal performance of the derivatives against four species of phytopathogen (Phomopsis asparagus, Botrytis cinerea, Fusarium oxysporum f. sp. Niveum, and Fusarium oxysporum f. sp. cucumebrium Owen) was estimated. Additionally, superoxide and hydroxyl radical scavenging assays tested the antioxidant activity of chitosan derivatives. The results suggested that these derivatives could be ideal compounds for antioxidant and antifungal applications [223]. In another example, the antifungal action of chitosans with 94.2% Ndeacetylation and different molecular weights A (MW ¼ 92.1 and 357.3 kDa for A and B, respectively) was studied in different concentrations against fungi, including Penicillium italicum, Penicillium digitatum, Botrytis cinerea, and

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SCHEME 6.5 Synthesis routes for chitosan derivatives [223].

Botrydiplodia lecanidion. The effectiveness of these chitosans were examined to control the postharvest quality of Tankan fruit. Chitosan, depending on concentration and type, shows 25.0%–90.5% growth inhibition on test organisms after 5 days of cultivation at 24°C. Chitosan treatment significantly reduced (P < .05) the percentage of decay of Tankan fruit during storage at 24°C. After 42 days of storage at 13°C, chitosan-coated Tankan fruits were firmer, showed

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less decay and weight loss, and presented higher titratable acidity, AA, and total soluble solids than the control fruit. The weight loss of Tankan fruits decreased as the concentration of chitosan was increased. Moreover, chitosan A, regardless of concentrations tested, was more effective in retaining the firmness, total solid content, water ratio, titratable acidity, and AA content of Tankan fruits than chitosan B. As a result, chitosans A and B showed numerous ranges of antifungal performance toward the test organisms at the concentrations tested. Chitosan treatment significantly reduced the decay of Tankan fruit with or without the inoculation of test fungi [224].

6.2.4.2 Cellulose-based (nano)materials CMC displays appropriate film-forming potential and affords transparent films with excellent oxygen and lipid barriers [225–227]. A study investigated the influence of ginger and cinnamon oils on some physical, biological, and physicochemical features of chitosan-CMC films emulsified with oleic acid. Cinnamon oil awards better antifungal activity to the films in vitro against Aspergillus niger in comparison with ginger. Unlike ginger-based compounds, increasing the concentration of cinnamon oil decreased the crystallinity of the film. The SEM analysis was carried out to evaluate the microstructure of the active films. It presented a distinct morphology depending on the composition of essential oils (EOs). As predictable, the water vapor permeability of the active films was decreased by both EOs; but cinnamon presented a higher decreasing effect. The resulting water contact angles were improved by 65%–93% for cinnamon films and 36%–59% for ginger films, depending on the concentration of EO. Regarding mechanical properties, the highest concentrations of EOs led to improvements of 111% and 328% of the elongation with ginger and cinnamon, respectively. The different behavior of both EOs regarding mechanical, physical, thermal, and water vapor permeability properties could be related to the differences in their chemical compositions. The cinnamaldehyde present in cinnamon EO can afford many kinds of interactions with the network made by oleic acid, CMC, and chitosan. According to the results, EOs, especially cinnamon oil, have potential to be used for plasticizing chitosan-CMC films while improving moisture permeability and maintaining antifungal ability. This biomaterial could be employed for food preservation purposes [228]. The improvement of functional materials with antifungal ability is of supreme importance assuming the intricate problem of multidrug-resistant pathogenic fungi. Another study prepared nanocomposites consisting of cross-linked poly([2(methacryloyloxy)ethyl]trimethylammonium chloride) (PMETAC) and bacterial nanocellulose (BNC) and tested that toward the polymorphic fungus C. albicans. The three-dimensional network of BNC enabled the in situ polymerization of the nontoxic and bioactive quaternary ammonium monomer, which originated transparent nanocomposites containing 10 and 40 wt% of cross-linked PMETAC. The fungal inactivation reached a 4.4  0.14-log CFU reduction

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for the nanocomposite containing only 10 wt% of cross-linked PMETAC. Hence, these noncytotoxic and bioactive materials can constitute potentially effective systems for the treatment of C. albicans infections [229]. As another example, the coating of ZnO-cellulose composites has potential technological applications on the paper surface. The SEM results displayed that ZnO NPs were simply and uniformly dispersed in the CNC. The ZnO-cellulose composite nanofluids were synthesized by dispersing the composites in isopropanol as a base fluid. To determine the protective potential of these coatings, the mechanical and chemical properties of the coated papers were measured after dry heat and UV accelerated aging. In addition, excellent color stability of the paper coated with nanocomposites was detected via colorimetric measurements. The paper coated with ZnO-cellulose composites was found to possess antifungal and antibacterial activities against five common fungi (Mucor, Aspergillus niger, Rhizopus nigricans, Aspergillus versicolor, Saccharomycetes) observed in the archive or museum and two bacteria (S. aureus and E. coli) in common life [230]. In another study, the synthesis of Ag NP/CNF composite aerogels was studied using supercritical CO2 (scCO2) drying. CNF (cellulose nanofiber) hydrogel-ethanol solutions were mixed with Ag NP dispersions in ethylene glycol by ball milling. ScCO2 drying and conventional vacuum drying were then assessed for Ag NP/CNF composite aerogel formation. After scCO2 drying of the CNF hydrogel solution, a sponge-like CNF aerogel was formed with Ag NPs dispersed in the CNF matrix. In contrast, sheet-like structures and Ag NP agglomerates were found by conventional drying. The antibacterial and antifungal activities of the Ag NP/CNF aerogels obtained were assessed. The composites presented excellent fungal (for A. niger) and bacterial (for E. coli) inhibition properties. In addition, the effects of the method and the presence of Ag NP on the properties of the CNF aerogels such as porosity, surface area, and antifungal and antibacterial abilities were investigated [231].

6.2.4.3 Pectin-based (nano)materials Pectin can act as the primary barrier against pathogens. Among the extracellular pectinolytic enzymes, pectin methylesterase (PME) demethylesterifies pectin is secreted into the cell wall in a highly methylesterified form. In a study, An et al. reported the isolation and characterization of the pepper (Capsicum annuum L.) gene CaPMEI1, which encodes a PME inhibitor protein (PMEI), in pepper leaves infected by Xanthomonas campestris pv. vesicatoria (Xcv). CaPMEI1 transcripts are localized in the xylem of vascular bundles in leaf tissues and pathogens, and abiotic stresses can induce deferential expression of this gene. PuriWed recombinant CaPMEI1 protein not only inhibits PME but also displays antifungal performance against some plant pathogenic fungi. Virus-induced gene silencing of CaPMEI1 in pepper confers enhanced susceptibility to Xcv, accompanied by suppressed expression of some defense-related genes.

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Transgenic Arabidopsis CaPMEI1-overexpression lines exhibit enhanced resistance to Pseudomonas syringae pv. tomato, methyl viologen and mannitol, but not to the biotrophic pathogen Hyaloperonospora parasitica. These results indicate that CaPMEI1, an antifungal protein, may be involved in basal disease resistance, as well as drought and oxidative stress tolerance in plants [232]. Tomato is a fruit broadly used because of its nutritional value and flavor though it is susceptible to fungi contamination. Oregano essential oil (OEO) is a fungicide whose constituents are volatile. Thus, their incorporation within edible coatings can protect them and maintain their efficacy. A study assessed the influence of OEO in pectin coatings on the antioxidant content, inhibition of Alternaria alternata growth, and sensorial acceptability of tomatoes. The results illustrated that pectin-OEO coatings displayed antifungal activity and enhanced the antioxidant ability without negative effects on the sensorial acceptability of tomatoes [233].

6.2.4.4 Alginate-based (nano)materials Calcium alginate fibers have been widely applied in wound management in recent years since they have advantages over traditional cotton gauzes, including high absorbency, softness, and the ease of fabricating diverse products [234]. Several fungi and bacteria such as E. coli, S. aureus, P. aeruginosa, and C. albicans cause wound infections since most wounds provide a favorable environment for both bacteria and fungi [235–237]. Nevertheless, calcium alginate fibers do not efficiently control bacteria reproduction. Some researchers have modified alginate fibers to kill bacteria and fungi. However, their modifications may alter the property of fibers [238]. In a study, the cytotoxicity and antifungal properties of alginate fibers were examined to broaden their application in tissue engineering. Copper, calcium, and zinc alginate fibers were separately synthesized by replacing Na+ with Cu2 + , Ca2+, or Zn2+. The antifungal activities of the fibers were investigated after coming into contact with C. albicans. Afterward, the fungal inhibitory rates were measured using the plate count technique following the shake-flask test. Furthermore, an inhibition zone test and observation by SEM were carried out. The inhibitory rate of the copper, calcium, and zinc alginate fibers were 68.6%, 49.1%, and 92.2%, respectively. The results of the shake-flask tests and inhibition zone show that zinc alginate fibers have the best antifungal performance and that copper alginate fibers have obvious inhibitory action. However, the calcium alginate fibers have weak inhibitory effects. The SEM similarly shows that the fungal surfaces appear most irregular after the interaction between zinc alginate fibers and C. albicans. Additionally, the relative growth rates of calcium or zinc alginate fibers in human embryonic kidney and fibroblast cells were more than 100%. No significant results were gained (P > .05). The calcium alginate fibers in human fibroblast cells were not much different from the negative control group (P > .05). Nevertheless, zinc alginate fibers had a significant change

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(P < .05). Thus, the good antifungal property of zinc alginate fibers demonstrates their potential application in skin tissue engineering compared with copper or calcium alginate fibers [239]. For more than 50 years, amphotericin B (AmB) has been widely applied to treat systemic fungal infections [240]. Many recent efforts have studied the potential of polymeric prodrugs of AmB as a therapeutic strategy vis-a-vis liposomal AmB. Thus, AmB has been conjugated to various biopolymers. Such conjugates displayed much decrease in the toxicity of the AmB and in many cases potent antifungal performance. For example, SA was oxidized using periodate, and AmB was conjugated via imine and amine linkages to the oxidized alginate. Scheme 6.6 shows the formation of the conjugate. The molecular weight of the alginate is drastically reduced by oxidation. The conjugates were highly water soluble to the amount of 1000 mg/mL, making them useful for therapeutic purposes. SA-AmB conjugates derived from 20% and 50% oxidized alginate were nontoxic to HEK 293T and RAW 264.7 cell lines at 100 μg/mL and were also nonhemolytic to human blood at 100 μg/mL. The in vitro release of AmB into phosphate buffer from the imine conjugates was negligible with less than 0.2% of the drug released in 2 days. Capping of residual aldehyde using glycine or 2-ethanolamine resulted in increased release of the drug in vitro. Injectable gels of gelatin cross-linked with oxidized alginate incorporating the SA-AmB conjugates and AmB were also fabricated. The in vitro release from the gel discs displayed that AmB was released by 15%–20% in 48 h. The SA-AmB conjugates displayed strong antifungal performance when faced C. parapsilosis, C. neoformans, and C. albicans. The injectable gels seem to have potential for prolonged release of AmB when implanted [241]. Another study introduced a double-step strategy to prepare silver NPs (AAgNPs) from aldehyde-modified SA. The size of the A-Ag NPs prepared was 6–40 nm with a high dispersibility in water. Moreover, compared to bared Ag NPs (n-Ag NPs), the AAg NPs presented improved broad spectrum ant microorganism performance. The A-Ag NPs chiefly used their antifungal activity by changing cell membrane permeability and affecting the soluble protein synthesis, destruction of DNA structure, and inhibition of DNA replication. Temporarily, the A-Ag NPs presented no inhibition of rice and N. benthamiana seed germination. Considering their high biocompatibility and the highly efficient ant microorganism activity, A-Ag NPs can be potentially used in plant protection. Some studies have shown that alginate-coated Ag NPs could be prepared in one-step by oxidizing silver ions via alginate. However, as displayed in Fig. 6.28, a novel double-step approach to organize alginate-coated Ag NPs was presented. In this strategy, SA was first oxidized to obtain aldehyde groups, which were then applied to reduce silver ions into Ag NPs. After the synthesis, alginate molecules were tightly coated onto the Ag NP surface via the interaction between silver atoms and carboxyl groups. Therefore, the size of the Ag NPs could be well controlled by the additional amount of the oxidized alginate during the reaction [242].

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SCHEME 6.6 Synthesis of SA-AmB conjugates [241].

In addition, the antifungal ability of alginate-CuO bionanocomposite was evaluated against A. niger using colony forming units (CFU) and disc diffusion techniques. Following the Taguchi technique, nine experiments were considered to fabricate alginate-CuO nanocomposite with the highest antifungal performance. The nanocomposite prepared under the conditions of experiment

Ag+

Ag

CHO CHO

Ag COOH COOH

Heating 6 min

Damage cell

Antifungal

Nucleus

Ag(NH)2OH + ASA

Glycoprotein

Protein or enzyme

Destroy cell membrane FIG. 6.28 Fabrication of A-Ag NPs and their antiplant fungi activity [242]. (Reproduced with permission from Xiang S, Ma X, Shi H, Ma T, Tian C, Chen Y, Chen H, Chen X, Luo K, Cai L, Wang D, Xue Y, Huang J, Sun X. Green synthesis of an alginate-coated silver nanoparticle shows high antifungal activity by enhancing its cell membrane penetrating ability. ACS Appl Bio Mater 2019;2(9):4087–96.)

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(1 mg/mL alginate and 4 mg/mL CuO NPs with stirring time of 90 min) displayed the greatest inhibition rate on fungal growth (83.17%). Under the optimum conditions for the fabrication of alginate-CuO nanocomposite with the highest antifungal activity, the second level of CuO NPs (14.14%), alginate (8.16%), and stirring time (5.63%) displayed the best improvement in performance on inhibiting the fungal growth. Due to the favorable properties of the alginate-CuO nanocomposite, its antifungal feature can be used in different biomedical applications. Diffusion and endocytosis of the NPs into the fungi and ROS (superoxide anions, hydroxyl radicals, and H2O2) can interrupt the functions of all intercellular organelles such as endoplasmic reticulum, lysosome, mitochondria, and ribosome. Furthermore, NPs smaller than 50 nm can penetrate into the nucleus by transferring via the pores of the nucleic membrane and larger particles through damaging the nuclear membrane. By attaching to DNA, they then interrupt processes such as transcription, replication, and translation and lastly undergo apoptosis. However, further studies are needed to acquire a deeper knowledge of CP NPs and their composites against fungi. The mechanisms displayed in Fig. 6.29 are based on the results of previous studies on some microorganisms [243].

Interrupt electron transport e−

Lysosome −

e

Nucleus Ribosome

ROS Mitochondrion

Endoplasmic reticulum

Protein damaged

Leakage FIG. 6.29 Schematic representation for antifungal activity of alginate-CuO nanocomposite [243]. (Reproduced with permission from Safaei M, Taran M, Imani MM. Preparation, structural characterization, thermal properties and antifungal activity of alginate-CuO bionanocomposite. Mater Sci Eng C 2019;101:323–9.)

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6.2.4.5 Gelatin-based (nano)materials Gelatin films without any nanoparticles have no antifungal activity [244]. Mint essential oil (MEO) consists of volatile components, viz., quinones, organic acids, and flavonoids. It has antispamodic, antiinflammatory, and analgesic features and has potential antimicrobial ability. Plus, MEO can enhance the physical and chemical efficacy of the edible films. It also can prevent the fungi growth and avoid internal and external food contamination owing to its barrier property. The following study was carried out to produce gelatin-based edible films with varied concentrations of mint oil and characterization of their effectiveness against R. stolonifera and B. cinerea [245]. In another study, MEO was added into gelatin films, and the antifungal performance of the product was estimated. Five concentrations of MEO (0%, 0.06%, 0.13%, 0.25%, 0.38%, 0.50% (g/g gelatin)) were incorporated into gelatin solutions. The films were synthesized by casting and characterized for their mechanical resistance, barrier properties, morphology, and thermal and antifungal abilities. The addition of oil into the solution slightly enhanced the water vapor barrier, increased opacity and thickness, decreased transparency, and modified the mechanical and thermal properties of the films. With addition of oil above 0.38%, the films were effective against the growth of R. stolonifer and B. cinerea, showing an inhibitory activity. Thus, gelatin-based edible films incorporated with MEO displayed an effective tool to inhibit microbial growth on the surface of the film [245]. Furthermore, fish skin gelatin films incorporated with different concentrations of cinnamon essential oil (CEO) were synthesized and characterized. The results presented that the TS, EAB, and water content (WC) of the gelatin-based films decreased with the increasing concentrations of CEO, but WVP increased. The addition of CEO enhanced the light barrier efficacy of the film. The gelatinCEO films displayed good inhibitory abilities when faced E. coli, S. aureus, R. oryzae, A. niger, and Paecilomyces varioti, and their antifungal ability appeared to be better than their antibacterial performance. The in vitro release studies indicated an initial burst effect of CEO release, which subsequently slowed down at 40°C, but was not obvious at 4°C. The obtained results recommended that the addition of CEO as a natural antimicrobial agent into gelatin film can afford a suitable active food packaging [246]. Gelatin represents superior biodegradation and biocompatibility properties since it is derived from animal resources. As mentioned, Ag is the most efficient and safe metal with antimicrobial ability, especially antifungal activity [247]. In a study, the 3D scaffoldtype biocomposites of gelatin/Ag NPs were organized through the formation of Ag NPs in gelatin solution using solution plasma method and their antifungal performance was assessed. The mixture of 3% gelatin solution and AgNO3 (1–10 mM) was subject to discharge at high voltage (1600 V) under the controlled conditions to form the suspension of Ag NPs in the gelatin matrix. The freeze-drying process of lyophilization was used to fabricate the 3D scaffold type biocomposite of gelatin/Ag NPs from the suspension. Water solubility

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was improved by cross-linking using UV irradiation (γ ¼ 254 nm for 15 min). The biocomposite was characterized using UV-vis spectroscopy, FE-SEM, EDS, and TEM. The outcomes displayed that the prepared biocomposite had spherical shape with approximately 11–12 nm diameter. The antifungal activity analysis indicated that the biocomposite with Ag NPs could significantly inhibit the growth of C. albicans and those of hyphae and spores of A. parasiticus. MIC of the biocomposite for C. albicans and A. parasiticus was determined as 80 mg/mL and 240 mg/mL of Ag NPs, respectively. The growth inhibition of 92.8% was detected in the biocomposite with 10 mM Ag against C. albicans [247]. In another study, the gelatin-based nanocomposite films (GNCFs) containing 0%, 1%, 3%, and 5% zinc oxide NPs (N-ZnO) and/or 0%, 3%, 5%, and 10% chitin nanofibers (N-chitin) were synthesized. The results displayed that the addition of N-ZnO improved WVP, thermal, mechanical, and antifungal features of the gelatin-based films. Additionally, increasing the N-ZnO concentration enhanced the antifungal and physicochemical properties of the nanocomposite films. However, applying N-chitin in gelatin films could not improve the barrier abilities of the films against water vapor, possibly owing to the hydrophilic nature of N-chitin. Furthermore, the TS of the GNCFs containing N-chitin enhanced by an increase in NPs concentration up to 5%. The addition of N-chitin in the gelatin film raised both antifungal activity and thermal stability. The simultaneous incorporation of chitin and ZnO NPs in the GNCFs had an interactive effect on improving the antimicrobial and physicochemical properties of GNCFs. For example, DSC analysis showed that the melting point and ***ΔHm of GNCF containing both NPs increased compared with net gelatin film. Moreover, TGA analysis showed that employing both NPs in gelatin films caused better thermal stability of polymer against decomposition at higher temperatures in comparison to the gelatin film containing each of them. According to outcomes, films comprising both NPs presented more efficacy toward fungal growth inhibition than other film formulations. Therefore, gelatin nanocomposite films containing N-ZnO and N-chitin can be applied to increase the storage life of packaged foods [244].

6.2.4.6 Lignin-based (nano)materials The results of antifungal and antibacterial studies proved the ability of Kraft lignins against different foodborne and human pathogenic microorganisms. Moreover, both Kraft and organosolv lignins offered an efficient protection factor (SPF values of 10–20), representing their efficacy as natural additives for the sun lotion market. Also, lignin samples offered high antioxidant performance in comparison to butylated hydroxytoluene, a common commercial antioxidant. Consequently, the development of innovative applications of lignins as a commodity for the pharmaceutical, chemical, or cosmetic industries could expand their possible uses in the market, giving new added values to lignin. Moreover,

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the remarkable antimicrobial capacity of lignins, especially in the case of Kraft lignins, against A. niger and diverse foodborne and human pathogenic microorganisms opens new perspectives for the pharmaceutical and food industries [248]. The fabrication of dynamic networks from lignin with multifunctional and multipurpose practical applications is highly required, but still challenging. In a study, the combination of a grafting from reversible addition fragmentation chain transfer (RAFT) polymerization and dynamic chemistry was applied to prepare lignin-based dynamic networks. Vanillin, a chemical derived from lignin, was employed as a building block to determine the structural reorganization of lignin via RAFT polymerization together with fatty acid derivatives as the comonomer. It was proved that the physicochemical features of the grafted lignin were adjustable depending on the polymerization reaction conditions. Respecting the aldehyde groups present in vanillin, a dynamic network was organized by diamines as cross-linkers. The mechanical properties were also tunable via controlling the structure of the cross-linkers. The cross-linked lignin-based dynamic networks showed different appealing abilities, including UV adsorption ability and recyclability. Moreover, it could be applied as an antifungal, self-healing, and conductive adhesive. The shear strength after first time self-healing could reach 2.9 MPa, which was 83.1% of the pristine adhesion. This damage and repair procedure could be carried out at least four times under relatively low temperature (80°C) and pressure (1.0 MPa). More significantly, antifungal performance was detected for the self-healing adhesive, which might extend its applications. Additionally, with incorporation of carbon nanotubes, the generated conductive adhesive was weldable without compromising its conductivity. This study proved that the lignin has potential to organize high value added materials applicable in biorefinery and material areas [249]. Another study reported the green preparation of lignin-capped silver NPs (LCSN) and their antibacterial, antioxidant, antiplatelet, and antifungal abilities. LCSN was prepared in water using lignin as both reducing and capping agent. The results showed that the spherical Ag NPs were well dispersed on lignin with an average particle size of 10–15 nm. The antifungal and antibacterial performances of LCSN were tested against E. coli, S. aureus, and A. niger human pathogens, and the percentage of the zones of inhibition were 12%, 10%, and 80%, respectively [250].

6.2.5 Antiviral applications Recent intelligence reports and actions highlight the rising risk of hazardous biological materials employed for nefarious purposes. Community health responses effective in natural outbreaks of infectious disease may not be sufficient to deal with the severe consequences of a deliberate release of such agents. The main aspect of countermeasures against viral biothreat agents is the

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antiviral treatment options available for use in postexposure prophylaxis [251]. Most viral illnesses, with the exception of those caused by human immunodeficiency virus, are self-limited diseases, which do not need specific antiviral cure. With the exception of the antisense molecule fomivirsen, all antiherpes drugs prevent viral replication by serving as competitive substrates for viral DNA polymerase [252]. Believed to be a bridge between the nonliving and the living organisms, viruses have either RNA or DNA, seldom both. Their genome is surrounded by a protein coat called the capsid. Certain viruses have an envelope, often derived from the host cell membrane during lysis and release. Multiple characteristics, including the type of nucleic acid, presence or absence of envelope, and single or double strands, are taken into account in the classification of viruses [170].

6.2.5.1 Chitin and chitosan-based (nano)materials Chitin has the ability to induce interferon synthesis, which is an important factor in antiviral resistance [253]. A novel technique for the regioselective synthesis of sulfated analogs of chitosan and chitin is described in relation to studies on structure biological activity. Completely protected, soluble derivatives of chitosan were found to be valuable intermediates for the preparation of a class of sulfated polysaccharides, 3-sulfate (3S, 4) and 2,3-disulfate (23S, 3). Scheme 6.7 outlines the synthetic process for 3 and 4, 3S. These compounds were tested for their activities in (i) inhibiting HIV-1 replication in vitro and (ii) inhibiting blood coagulation. The outcomes show that the selective sulfation at O-2 and/or O-3 affords potent antiretroviral agents, which display a much higher inhibitory effect on the infection of AIDS virus in vitro than that by

T D A

SCHEME 6.7 (i) (A) ethylene glycol, phthalic anhydride, DMF, 130 °C, (B) pyridine-4-dimethylaminopyridine, TrCl, 90°C, (C) NH2NH2H2O, 100°C (93% from chitosan); (ii) acetic anhydride, DMF-MeOH (87%); (iii) (A) pyridine, SO3-pyridine, 80°C, (B) dichloroacetic acid, 20°C, (C) aq. 1 M NaOH pH 8–9, dialysis and gel filtration by Sephadex G-25 (62% for 3% and 80% for 4) [254].

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the known 6-O-sulfated derivative (6-sulfate, 6S). Furthermore, the 23S product completely inhibited the infection of AIDS virus to T lymphocytes at concentrations as low as 0.28 μg/mL without significant cytotoxicity. The regioselective introduction of sulfate group(s) at O-2 and/or O-3 had little effect on generating anticoagulant activity, whereas 6-O-sulfated chitin strongly inhibited blood coagulation. These results suggest that the specific interaction of these types of chitin sulfates with gp 120 of the AIDS virus depends significantly on the sites of sulfation rather than the total degree of substitution on sugar residues [254]. Chitin nanofiber sheets (CNFSs) are nanoscale fiber-like surfaces with nontoxic structures, biodegradable biomaterials, and large surface to mass ratios. CNFSs were immersed in suspensions of Ag NPs (5.17  1.9 nm in diameter) for 0.5 h at room temperature to synthesize CNFS/Ag NPs. CNFS/Ag NPs were tested for antimicrobial activities against E. coli, P. aeruginosa, and H1N1 influenza A virus, which are the three pathogens representing the most widespread infectious viruses and bacteria. The CNFSs alone have only weak antimicrobial activity, but CNFS/Ag NPs display much stronger antimicrobial properties against E. coli, P. aeruginosa, and influenza A virus, with the Ag NPs immobilized onto CNFSs [255]. The properties of chitosan such as the degree of N-deacetylation, positive charge, mean polymerization degree, and nature of chemical modifications must be taken into account in the analysis of its antiviral activity. The extent of suppression of viral infection directly depends on the concentration of chitosan. Moreover, antiviral ability depends on the molecular structure of chitosan and its molecular weight. The ability of chitosan to induce interferon synthesis can be an additional important factor of antiviral resistance. It is also important to note that chitosan inhibits the reproduction of Chlamydia trachomatis (which, like viruses, is an obligate intracellular parasite) in HeLa cells, mainly by suppressing its adsorption on cells. Interferon is known to suppress virus replication by impairing the translation ability of the genomic RNAs or early viral mRNAs [253]. One of the most determining characteristics of chitosan is its molecular weight, which affects its processability and function as a biological substance. However, the data about the effect of this parameter on the formation of electrosprayed chitosan microcapsules is scarce. In an example, the influence of chitosan molecular weight on its electrospray ability was studied and associated with its influence on the surface tension, viscosity, and electrical conductivity of solutions. Discriminant function analysis shows that the morphology of the electrosprayed chitosan materials could be properly foreseen using these three parameters for almost 85% of the samples. The suitability of using electrosprayed chitosan capsules as carriers for bioactive agents was also considered by loading them with a model active compound, ()-epigallocatechin gallate (EGCG). This encapsulation, with an assessed efficacy of about 80% in terms of preserved antioxidant performance, displayed the potential to prolong the antiviral ability of EGCG against murine norovirus via gradual bioactive release combined with its protection against

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degradation in simulated physiological conditions. Microencapsulated EGCG presented prolonged antiviral performance against murine norovirus as related to the free compound, proposing that EGCG was gradually released from the chitosan capsules and that the encapsulation matrix had a protective effect on the active compound against degradation in simulated physiological conditions [256]. In another study, an antiinfective material was defined by Webster as “an agent capable of acting against infection, by inhibiting the spread of an infectious agent or killing the infectious agent outright” [257]. Some of the emerging and drug-resistant infectious diseases with research priority are human immunodeficiency virus (HIV) or AIDS, hepatitis C and B viruses, respiratory infections such as influenza and respiratory syncytial virus (RSV), and dengue fever [258]. Chitin is broadly found in crustaceans, invertebrates, fungi, and insects [259]. The sulfated derivatives of chitin and chitosan possess activities, including anti-HIV-1, antioxidant, antimicrobial, etc. [260]. N-Carboxymethylchitosan N,O-sulfate is known to inhibit the transmission of HIV-1 in human CD4+ cells. This inhibition is due to the blockade of the interactions between the glycoprotein receptors present on the viral coat and the target proteins present on the lymphocytes, thereby inhibiting the HIV-1 reverse transcriptase [261]. The sulfation at the 2 and 3 positions led to the complete inhibition of HIV-1 infection to T-lymphocytes at 0.02 μM concentrations without any cytotoxicity. These outcomes display that the biological activity of the sulfated chitins can be controlled by changing the sulfate group position. Chitosan is converted to chitooligosaccharides to recover its water solubility and thus its biological activity [257]. As another example, new sulfonated derivatives of poly(allylamine hydrochloride) (NSPAHs) and N-sulfonated chitosan (NSCH) have been prepared, and their performances against influenza A and B viruses have been tested and compared with those of a series of carrageenans, marine polysaccharides of well-documented antiinfluenza activity. NSPAHs were proved to be safe and very soluble in water, in contrast to gel forming and thus generally poorly soluble carrageenans. The ex vivo and in vitro studies, using susceptible cells (Madin-Darby canine kidney epithelial cells and fully differentiated human airway epithelial cultures) confirmed the antiviral efficiency of NSPAHs. The efficacy of NSPAHs was dependent on the molecular weight of the chain and the degree of substitution of amino groups with sulfonate groups. Mechanistic studies displayed that the NSPAHs and carrageenans prevent the assembly of influenza A and B viruses in the cell. The N-sulfonated derivatives of high– molecular weight poly(allylamine) with a high degree of substitution of the sulfonic groups represent strong inhibitory effects on replication of influenza A virus ex vivo and in vitro, mostly at later steps of the infection. The mechanism of action is similar for NSPAHs and carrageenans and may be related to the inhibition of virus release from infected cells. Additionally, even though NSPAHs display similar efficacy as carrageenans, these newly developed antiinfluenza compounds present far better physicochemical properties such as lack of gelling properties and high solubility [262].

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6.2.5.2 Pectin-based (nano)materials The isolated pectin (denoted as PDTS) from Inga spp. fruit pulp was assessed using HEp-2 cells against the herpes simplex virus type 1 (HSV-1) and the poliovirus (PV). PDTS was characterized by gel permeation chromatography and 1H NMR. The antiviral activity was checked by plaque reduction assay, polymerase chain reaction (PCR), and immunofluorescence assay (IF), and the cytotoxicity was studied by the MTT technique. The cytotoxic concentration (CC50) of PDTS was 870 μg mL1, and the inhibitory concentrations (IC50) were 58 and 179 μg mL1 for PV and HSV-1, respectively. Better inhibitory performance was detected when the cells were simultaneously treated with PDTS and infected, suggesting that PDTS inhibited the initial viral replication stages and revealing its antiviral potential [263]. 6.2.5.3 Gelatin-based (nano)materials Different synthetic and natural polyanionic polymers with various chemical structures are known to exhibit potent antiviral activity in vitro toward a variety of enveloped viruses and may be considered as promising therapeutic agents. A water soluble conjugate of 2,5-dihydroxybenzoic acid (2,5-DHBA) with gelatin was prepared via laccase-catalyzed oxidation of 2,5-DHBA in the presence of gelatin, and its antiviral activity against bovine herpesvirus type 1 (BoHV-1) and pseudorabies virus (PRV), two members of the Alphaherpesvirinae subfamily, was investigated. The conjugate produced no direct cytotoxic effect on cells and did not inhibit cell growth at concentrations up to 1000 μg/mL. It showed potent antiviral activity against BoHV-1 (IC50 of 0.5–0.7 μg/mL) and PRV (IC50 of 1.5–15 μg/mL for different virus strains). When present during virus adsorption, the conjugate strongly inhibited the attachment of PRV and BoHV-1 to cells. The 2,5-DHBA-gelatin conjugate had no direct virucidal effect on the viruses and did not influence their penetration into cells, cell-tocell spread, production of infectious virus particles in cells, and expression of E and B PRV glycoproteins. The results showed that the 2,5-DHBA-gelatin conjugate strongly inhibited the adsorption of alpha herpesviruses to cells and can be a promising synthetic polymer for the development of antiviral formulations against alpha herpesvirus infections [264]. 6.2.5.4 Lignin-based (nano)materials Lentinula edodes mycelia solid culture extract (MSCE) contains several bioactive molecules, including some polyphenolic compounds, which exert immunomodulatory, antitumor, and hepatoprotective effects. In a study, the antihepatitis C virus (HCV) activity of MSCE and low–molecular weight lignin (LM-lignin), which is the active component responsible for the hepatoprotective effect of MSCE, was examined. Both LM-lignin and MSCE inhibited the entry of two HCV pseudovirus (HCVpv) types into Huh7.5.1 cells. LM-lignin inhibited

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HCVpv entry at a lower concentration than MSCE and inhibited the entry of HCV particles in cell culture (HCVcc). MSCE also inhibited HCV subgenome replication. LM-lignin had no effect on HCV replication, suggesting that MSCE contains additional active substances. The hepatoprotective effect of LM-lignin suggests that lignin derivatives, which can be produced in abundance from existing plant resources, may be effective in the treatment of HCV-related diseases [265]. Table 6.1 briefly presents some of the reports on the biological applications of biopolymer-based (nano)materials.

6.3

Conclusion

Oxidants are active molecules in the human body and environment, which can react with other molecules present in the body such as DNA, protein, and lipids, and result in deep damages. Furthermore, the presence of harmful microorganisms such as some kinds of bacteria, fungi, viruses, and biofilms in the host cell can cause various illnesses. Therefore, it is important for human beings to follow a safe lifestyle to decrease the illnesses and diseases caused by these factors. Biopolymers play significant roles in human life. They are safe to the human body, environmentally benign, and cost-effective. Biopolymers and their derivatives alone or in combination with other materials, especially when complexed with transition metals such as Ag, Au, TiO2, ZnO, and CuO, represent biological properties such as antioxidant, antibacterial, antifungal, antibiofilm, and antiviral properties, as indicated in this chapter. Transition metals in the form of ions or nanoparticles are well known for their high biological properties and biopolymers have high potential to combine with them. The presence of nanoparticles strengthens the biological properties of biopolymers. Biological features give special importance to biopolymers and make them suitable for use in various parts of the textile industry, food packaging, paper industry, pharmaceutical industry, etc. Recent advances in the production of these biocomposites are expected to be useful in the future and lead to improvements in the health field. They help reduce costs and provide better services because they are affordable. However, due to the importance of using nanoparticle-based biopolymers in the food and pharmaceutical fields, there is a need for further research on the toxicity of these substances. Despite the fact that the presence of biopolymers increases the biocompatibility of the metal complexes, the compatibility of these materials with human body tissues should further be investigated and evaluated, especially in nano-scale due to their high penetration. Furthermore, their life cycle analysis for different applications should be evaluated. Therefore, future studies should clearly address the long-term toxicity and biological properties such as protein adsorption, cell adhesion, tissue compatibility, and overall in vivo effect of such composite systems. A study should be carried out on these materials to ensure that no harm is done to the human body, animals, and nature.

TABLE 6.1 Biological applications of biopolymer-based (nano)materials.

Entry

Biopolymerbased (nano) material

1

Chitosan (CS)

2

Biological activity

Microorganism

Application

References

Antioxidant, antifungal

Phomopsis asparagus, Fusarium oxysporum f. sp. niveum, Fusarium oxysporum f. sp. cucume brium Owen, and Botrytis cinerea

–

[34]

Chitin and chitosan

Antioxidant

–

Food and pharmaceutical industries

[33]

3

Chitosan

Antioxidant

–

Food industry

[266]

4

Chitosan/sea urchin spine powder (SUSP)

Antioxidant

–

Food industry

[267]

5

Chitosan-ZnO NPs

Antioxidant

–

Improve the health status, immune function, and antioxidant capacity of the cultured beluga juvenile

[268]

6

Au NPs/chitosan (CH)/ellagic acid (EA)

Antioxidant

–

Cosmetic

[269]

7

Hordeinquercetinchitosan electrospun nanofiber film

Antioxidant

–

Food packaging

[270]

8

Chitosan

Antibacterial

E. coli, Salmonella typhimurium, S. aureus, and B. cereus

–

[271]

9

Chitosan/Ag/ ZnO nanocomposite

Antibacterial

B. licheniformis and B. cereus, V. parahaemolyticus and P. vulgaris

–

[272]

10

Chitosan/Ag/ ZnO nanocomposite

Antibiofilm

C. albicans

–

[272]

11

Chitosan-based films

Antibacterial

S. aureus, Listeria innocua, E. coli

Food packaging

[273]

12

Chitosan-silver (CS-Ag)

Antibacterial

Klebsiella pneumonia, S. epidermidis, S. aureus, and E. coli

Biomedical and industrial applications

[274]

13

Chitosan-silver (CS-Ag)

Antibiofilm

Staphylococcus epidermidis, Klebsiella pneumonia, S. aureus, and E. coli

Industrial applications

[274]

14

Chrysin-loaded chitosan nanoparticles

Antibiofilm

S. aureus

Anti-biofilm coatings

[275]

15

CMC/curcumin/ ZnO composite

Antioxidant

–

Packaged foods

[276]

16

CMC/curcumin/ ZnO composite

Antibacterial

L. monocytogenes and E. coli

Packaged foods

[276]

17

Graphene oxide/ cellulose nanofiber

Antibacterial

E. coli and Klebsiella

–

[277]

Continued

TABLE 6.1 Biological applications of biopolymer-based (nano)materials—cont’d

Entry

Biopolymerbased (nano) material

Biological activity

Microorganism

Application

References

18

Crystalline jute cellulose (SCJC)/ Ag NPs

Antibacterial

S. aureus, E. coli, Shigella dysenteriae, and Shigella boydii

Wound dressing, health products, antimicrobial filters, hygienic materials, coating for medical equipment, and textile products

[278]

19

CDP/CMC/TP compositea

Antibacterial

S. aureus, Bacillus subtilis, and E. coli

Functional packaging materials (food systems)

[279]

20

Carrageenan/ chitin nanofibril (CNF) nanocomposite

Antibacterial

Listeria monocytogenes

–

[280]

21

CMC/chitin nanowhiskers/ ZnO-Ag NPs

Antibacterial

E. coli and L. monocytogenes

Food packaging

[281]

22

Pectin-GeO2 nanocomposite

Antibacterial

E. coli

Potential material for environmentally friendly electronic material

[282]

23

Pectin/Ag NPs

Antibacterial

Dickeya spp. and Pectobacterium spp.

–

[283]

24

Pectin-cadmium sulfide nanocomposite (Pc/CSNC)

Antibacterial

E. coli

–

[284]

25

Pectin-capped copper sulfide NPs

Antibacterial

Bacillus subtilis, E. coli, P. aeruginosa, and S. aureus

–

[285]

26

Pectin-based silver nanocomposite

Antibacterial

S. aureus and E. coli

Platform for the controlled release of hydrophilic drugs, in transdermal applications

[286]

27

Pectin/Ag NPs

Antibacterial

E. coli and Listeria monocytogenes

Food safety and prolong the shelflife of packaged foods

[172]

28

Pc/TWMb

Antibacterial

S. aureus

Adsorbent for the remediation of metals and dye pollutants

[287]

29

AgNPs-doped HAp/Alg

Antibacterial

E. coli and S. aureus

Biomedical applications

[288]

30

TiO2/SA

Antibacterial

Salmonella typhimurium

Hygienic and food packaging

[289]

31

Chitosan on calcium alginate fibers

Antibacterial

Staphylococcus epidermidis, E. coli, and various aureus strains, namely MSSA (Methicillin Sensitive S. aureus), CAMRSA (Community Associated Methicillin Resistant S. aureus) and HAMRSA (Healthcare Associated Methicillin Resistant S. aureus)

Against the infections and more particularly nosocomial diseases

[290]

32

CA-AgNPsc

Antibacterial

S. aureus and E. coli

Wound dressing

[290]

33

SA

Antioxidant

–

Food packaging

[291]

34

Protein hydrolysate incorporated alginate

Antioxidant

–

Food simulants

[292]

Continued

TABLE 6.1 Biological applications of biopolymer-based (nano)materials—cont’d

Entry

Biopolymerbased (nano) material

Biological activity

Microorganism

Application

References

35

SA

Antioxidant

–

Quality during the shelf life of vegetables and fruits

[293]

36

SA

Antifungal

Candida krusei, Candida parapsilosis, Candida tropicalis, and C. albicans

Antifungal drugs

[294]

37

Alginate oligosaccharides

Antifungal

C. albicans, Candida tropicalis, Candida parapsilosis, and Candida krusei

Antifungal drugs

[294]

38

Gelatin containing an ethanolic extract of Propolis

Antifungal

P. expansum, P. digitatum, P. italicum, A. alternata, A. carbonarius, and B. cinerea

–

[295]

39

Gelatin/agar/ VLEd

Antioxidant

–

Food packaging

[296]

40

Gelatin-AgNPs

Antimicrobial

–

Pharmaceutical and biomedical applications

[297]

a

Tea polyphenol (TP) into corn distarch phosphate (CDP)/CMC films. Pectin thorium(IV) tungstomolybdate. Silver nanoparticles (AgNPs)-doped collagen-alginate (CA-AgNPs). d Vine leaves ethanolic extract (VLE). b c

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Chapter 7

Catalytic applications of biopolymer-based metal nanoparticles Mahmoud Nasrollahzadeh, Nayyereh Sadat Soheili Bidgoli, Zahra Nezafat, and Nasrin Shafiei Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

7.1

Introduction

Efficient research on nanotechnology has received great interest in this century because of its interdisciplinary applications in the fields of catalysis, biomedicine, fuel cells, magnetic data storage and energy technology [1]. Nanoparticles, with sizes in the range of 10.0–100.0 nm in diameter, have special features including high surface area and quantum property and show great potentials for different applications. Among all nanoparticles, metallic nanoparticles (MNPs) are particularly attractive due to their unique properties and various applications [2]. In recent decades, noble metal nanoparticles (NPs) such as silver (Ag), gold (Au), palladium (Pd), and platinum (Pt) have been widely used as catalysis, fuel cells, chemical sensors, biological materials, and data storage [3–7]. To prevent NPs from aggregation, using matrix materials is an efficient technique to stabilize NPs and improve their fundamental properties. Compared with the typical matrices such as active carbon and silica, biopolymers are attracting increasing attention because of their low environmental pollution, biocompatibility, and good stability [8–11]. In homogeneous catalysis, the catalysts are finely dispersed at the molecular level in the reaction environment to assure high catalytic activity [12]. Homogeneous catalysts cannot be removed from the reaction media or recovered and produce toxic wastes. One of the effective ways to overcome the drawbacks of homogeneous systems is the use of heterogeneous catalysis due to their exceptional properties including high stability, insolubility in solvents, ease of handling, simplicity of removal from the reaction mixture, recyclability, reusability, and the wide availability of support [13]. Heterogeneous nanosized catalysts are reported to own catalytic activities similar to the homogenous ones [14]. In addition to the excellent catalytic Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00007-X Copyright © 2021 Elsevier Inc. All rights reserved.

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activities of nanoparticles, their separation method is cost effective with respect to time and energy [2]. Meanwhile, most catalytic nanoparticles can be recovered from the reaction medium by centrifugation or magnet-assisted recovery for reuse at the industrial scale. As mentioned earlier, nanoparticles tend to aggregate due to their high energy level, which reduces their catalytic activity [12, 14]. Therefore, novel approaches have been considered for the retrieval of the metal nanoparticle catalysts [15]. Owing to their very safe and stable biodegradation and biocompatibility, biopolymers are considered the best supports in the synthesis of catalytic nanoparticles [16]. In the past years, different biopolymers such as polysaccharides, proteins, and nucleic acids, obtained from animals, plants, and microbes, have been employed for packaging materials, drug delivery, regenerative medicine, and catalytic applications [17, 18]. As important biopolymers, natural polysaccharides, in particular, have some excellent properties due to their chemical and structural properties [19, 20]. Carbohydrates are the most applied polymeric carbon derivatives, which have gained lot of attention in the synthesis of heterogenized homogeneous catalysts [21]. Given their very safe and stable biodegradation and biocompatibility, polysaccharides are considered the greatest promising hosts in the synthesis of polysaccharide-based metallic nanoparticles (PMNPs) with guest MNPs [22, 23]. Among all the nanocatalysts, PMNPs are particularly attractive owing to their high surface area to volume ratios and high surface energy, which makes their catalytic sites available [24]. Since catalytic reactions require transition metals, polysaccharides could act as appropriate functional supports for dispersing the noble MNPs as hosts and control the size and shape of the catalysts [1]. Cellulose, starch, alginate, gum, chitin, and chitosan are classified as polysaccharides. Polysaccharides are organic polymers in which the repeating unit consists of monosaccharides. Monosaccharide (general formula Cn(H2O)n) is a polyhydroxycarbonyl compound categorized as tetrose, pentose, hexose, etc., according to the number of carbon atoms in the molecule [25]. Proteins are another type of biopolymer used as supports for catalytic applications. Proteins have different types, but the most important are collagen and gelatin, which are used for catalytic applications. Lignin, which is a polyphenol used as a suitable support and stabilizing agent for the manufacture of various catalysts, is one of the most important biopolymers [26, 27]. Biopolymer-based metal NPs, in general, are widely used today in a variety of reactions such as reduction, degradation, coupling, synthesis of organic compounds, oxidation etc. and will be discussed in the following sections.

7.2 Catalytic applications of polysaccharide-based metal nanoparticles Polysaccharides are one of the important types of biopolymers due to their individual properties and structural and chemical variety [28, 29]. They can vary in

Catalytic applications of biopolymer-based metal nanoparticles Chapter

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stereochemistry, chain sizes, charge, and monosaccharide sequences, providing the highest capability for the improvement of progressive functionalized materials and biomedicine [30]. Due to their incredibly stable and nontoxic biodegradation, polysaccharides are designed as the greatest hosts in the structures of polysaccharide-based metallic nanoparticles (PMNPs) with metallic ions or MNPs as guests [16, 31]. Polysaccharides are also used as excellent stabilizing and reducing agents to control the physical properties of PMNPs through the synthesis process [32]. In addition to biocompatibility features, there are several properties of polysaccharides, for example, their availability, stability, protection, economy, and hydrophilicity, which make them suitable drug carriers [33]. Biodegradable and renewable biopolymers with supported NPs can be utilized to prepare novel, efficient, and environmentally friendly compounds with appropriate thermomechanical features, as promising alternatives for conventional materials. Polysaccharide-based NPs became progressively significant materials several years ago. Recently, a high number of polysaccharides have been considered for the preparation of nanoparticles and impregnation of metal nanoparticles on them for catalytic applications. In the next section, the structural properties of some of the most famous biodegradable polysaccharidebased metal nanoparticles are outlined [34].

7.2.1

Cellulose

Cellulose, a biogenic raw material with enthralling structure and properties, is one of the most important and richest sources of renewable organic polymers, the yearly production of which is around 1.5
1012 ton [35]. It is composed of linearly chained glucose molecules and is a semicrystalline biopolymer (Fig. 7.1) of high molar weight and has a flat strip-like composition. Cellulose is the most accessible biopolymer with many advantages such as renewability, biodegradability, and sustainability. Cellulose is the most abundant polymer on earth [36]. Cellulose-based NPs have several applications including water purification, sensing organic pollutants, energy conversion, and absorption of oil spills from water and are widely used in catalytic reactions such as degradation of organic hazardous compounds. One of the cellulose derivatives is nanocellulose, which is a functional nanostructure with attractive properties. The word “nanocelluloses” typically refers to nanostructures obtained by top-down methods from vegetal or bacterial cellulose biopolymers. Nanocellulose has

FIG. 7.1 Semicrystalline structure of cellulose.

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III Further sustainability applications of biopolymer-based MNPs

many advantages such as great biological properties, interesting physical characteristics, superior surface chemistry, biodegradability, nontoxicity, biocompatibility, and availability. Some of the most common forms of cellulose including natural fibers (e.g., wood) are cellular hierarchical biocomposite wood, cotton, and paper. These materials have been mostly investigated as important components in the design of pharmaceuticals, aerogels, composites, chiral materials, supercapacitors, and catalysts [37–39]. Cellulose is one of the significant and suitable catalyst supports owing to its appropriate properties. Compared with other carbon sources, cellulose is a low cost, sensible, biodegradable, and abundant biopolymer and one of the renewable and ecofriendly sources of carbon [40–44]. The hydroxyl groups on the cellulose backbone function as necessary binding sites for different surface modifications. To obtain advantageous, unique structures, a series of surface modifications have been performed on cellulose to improve its stability and catalytic performance using grafting functional moieties [45–48]. There are some examples in which cellulose-based metal NPs have been used for various catalytic applications. Cellulose-based metal NPs have been applied as heterogeneous catalysts in many reactions such as oxidation, reduction, degradation, and coupling reactions and synthesis of various organic compounds such as hydroxymethylfurfural, which is an important organic compound. Cellulose-based metal NPs are mostly used in the coupling and degradation reactions. For example, in 2014, Ashraf and colleagues developed a method to coat silver and gold NPs on the surface of cellulose fibers [49]. To do this, they found out that Ag and Au NPs can be decorated on cellulose fibers by boiling cellulose in an alkaline solution of silver and gold salts. Fig. 7.2 shows the synthetic method for cellulose metal NPs. The thiol-modified cellulose gold NP composite participates as an active catalyst in the reduction of 4-nitrophenol (4-NP) to 4aminophenol (4-AP). Nanofibrillated cellulose (NFC), a type of nanocellulose used as a carrier for nanoparticles, has gained considerable attention in recent years owing to its unique properties such as high surface area, thermal stability, functionalized surface, and environmental aids [50, 51]. For example, in 2013, Xiong et al. developed an efficient and ecofriendly approach for the synthesis of Fe3O4/ Ag@nanofibrillated cellulose (NFC) nanocomposites (Fig. 7.3) [52]. In this study, NFC has two functions including (1) reducing Ag+ and (2) biodegradable support for the magnetic Ag NPs. One of the benefits of this study is that no toxic solvents or reducing agents have been used. In this work, 1-butyl-3methylimidazolium chloride ([Bmim]Cl), a room temperature ionic liquid (IL), was used as a recyclable solvent for cellulose. Fe3O4/Ag@NFC aerogel shows high catalytic performance in the reduction of 4-NP and has high antibacterial properties in both aerogel and film forms. The catalyst can be easily separated from the reaction by a magnet and recycled several times without significant loss of catalytic activity. In another example, Zhang et al. used NFC as a multipurpose carrier of Ru and Cu NPs (RuCu@NFC) to improve their activities in the catalytic

Catalytic applications of biopolymer-based metal nanoparticles Chapter

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427

f

m

m

FIG. 7.2 Flowchart presentation of the experimental processes for the synthesis of cellulose-MNP composites [49].

FIG. 7.3 Schematic representation of the formation of Fe3O4/Ag@NFC nanocomposites [52].

transfer hydrogenation (CTH) of 5-hydroxymethylfurfural (HMF) into 2,5-bis (hydroxymethyl)furan (BHMF) [53]. The experimental results showed that the Ru and Cu NPs were well distributed on the surface of NFC. In addition, the study of CTH of HMF into BHMF showed a 97.0% HMF conversion via a suitable BHMF selectivity of up to 91.5% over RuCu@NFC using isopropanol as the H-donor. In another study, Tajik et al. extracted cellulose from the wood of the Sesbania sesban plant and immobilized iron Schiff on it (FeSAC) to prepare a novel biodegradable heterogeneous catalyst using 2-hydroxy-1naphthaldehyde as a ligand (Scheme 7.1) [54]. FeSAC was utilized in oxidizing alcohols under green, solvent-free conditions using H2O2 as a safe oxidant. The reaction showed excellent yields and high selectivities. Finally, the used

SCHEME 7.1 Synthesis of FeSAC procedure [54].

Catalytic applications of biopolymer-based metal nanoparticles Chapter

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free

SCHEME 7.2 Solvent-free oxidation of alcohols over FeSAC using H2O2 and synthesis of αFe2O3 by calcination of this biocatalyst at 650°C for 3 h [54].

catalyst was calcinated to α-Fe2O3 using solid-state degradation at 650°C within 3 h (Scheme 7.2). Metal NPs are directly deposited on cellulose, but the bond between metal NPs and cellulose is unstable. Therefore, NPs simply fall off from cellulose after several reactions. To solve this problem, researchers focused on functionalized celluloses. Several studies have been reported on the functionalization of cellulose with various compounds such as diphenylphosphinate and ethylenediamine [55, 56]. For example, Wei et al. successfully developed a method for the synthesis of Pd NPs supported on 2-aminopyridine-functionalized cellulose (Cell-AMP-Pd) (Scheme 7.3) [57]. The heterogeneous catalyst can be used in the Suzuki cross-coupling reaction of aryl halides with arylboronic acids in high yield (Scheme 7.4). The synthesized catalyst can be recycled and easily separated from the reaction mixture without loss of Pd NPs.

SCHEME 7.3 Synthesis of Cell-AMP-Pd [57].

SCHEME 7.4 Suzuki cross-coupling reactions using Cell-AMP-Pd as an efficient catalyst [57].

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III Further sustainability applications of biopolymer-based MNPs

Different microstructured fiber-based materials such as cellulose paper have many advantages as support materials for catalysts including NPs. These advantages include economy, availability, flexibility, high surface area, threedimensional structure, simplicity of metal recovery, and solvent compatibility, among others [58–60]. In a study, Zheng and co-workers used filter cellulose paper for the immobilization of Pd NPs [61]. They used oleylamine to stabilize Pd NPs on cellulose filter paper. The synthesized Pd NP-loaded paper substrates were studied in several reactions such as oxidative homocoupling of arylboronic acids, Suzuki cross-coupling reaction, and nitro to amine reductions (Scheme 7.5) as effective catalysts, which could be simply recycled and reused. In addition, Zareyee and co-workers developed an efficient and simple method for the synthesis of 2-aminopyrimidine nanocellulose-supported palladium NPs (CNC-AMPD-Pd) (Scheme 7.6) [62]. The prepared CNC-AMPD-Pd was used as a heterogonous catalyst in Pechmann condensation of different substituted phenols and ethyl acetoacetate to obtain coumarin derivatives (Scheme 7.7).

(A)

(B)

(C) SCHEME 7.5 Catalytic application of Pd NP-loaded paper substrates in oxidative homocoupling of arylboronic acids (A), Suzuki cross-coupling reaction (B), and reduction of 4-NP to 4-AP (C) [61].

n

n

SCHEME 7.6 Synthesis of CNC-AMPD-Pd [62].

n

n

Catalytic applications of biopolymer-based metal nanoparticles Chapter

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431

SCHEME 7.7 Preparation of coumarin derivatives using CNC-AMPD-Pd as catalyst [62].

SCHEME 7.8 Reduction of different nitroaromatics using PCNC in the presence of NaBH4 as the reducing agent [64].

In the field of nanotechnology and catalytic systems, the use of bimetallic nanomaterials has attracted researchers’ interest. In particular, in reduction reactions, the use of bimetallic systems such as Pd-Ni, Pd-Cu, and Pd-Ag improves the reduction rate [63]. For example, Keshipour and Adak developed a method for the synthesis of an efficient bimetallic catalytic system using Pd and Co NPs deposited on cellulose (PCNC) [64]. The synthesized bimetallic catalyst can be used in the reduction of nitroaromatics using NaBH4 (Scheme 7.8). Table 7.1 shows some other examples of cellulose-based MNP catalysts and their applications in various reactions.

7.2.2

Starch

Starch is a renewable, organic, biodegradable, and biocompatible polymer fabricated using several plants to reserve carbohydrates. Starch is a biopolymer present in the roots of several plants, crop seeds, stalks, and staple crops. Commonly, the major sources of natural starch are rice, wheat, cassava, maize, potatoes, and so on. It is the second most abundant biomass present on earth. A starch granule has a 3D architecture with crystallinity in the range of 15%–45% and consists of D-glucose units with two different bio-macromolecules, namely amylose and amylopectin [178]. Amylose units are lightly branched carbohydrates while amylopectin units are highly multiple branched polymers with a large molecular weight responsible for their crystallinity [179]. There are semicrystalline and amorphous growth rings (120–500 nm) arranged alternately encircling hilum, which are the initiation points of the granule. Starch crystallite, starch nanocrystal, microcrystalline starch, and hydrolyzed starch all stand

TABLE 7.1 Application of cellulose-based MNP catalysts in various reactions. Entry

Catalyst

Application

Size (nm) and morphology

Ya or C (%)

References

1

Pd NPs@pectin/carboxymethyl cellulose/Fe3O4

Synthesis biaryls and reduction of 4-NP

49–85/spherical

Y ¼ 45–99

[65]

2

Pt NPs on bacterial cellulose membranes

Electrocatalytic oxidation of hydrogen

3–4/spherical

–

[66]

3

Au NPs/cellulose

Aerobic oxidation of glucose

2

–

[67]

4

Mesoporous triazine-based carbon (MTC)-supported Pd NPs

Heck cross-coupling reaction

10.85

Y ¼ 95–98

[68]

5

Cellulose matrix-embedded copper-decorated magnetic bionanocomposite

Synthesis of dihydropyridines and polyhydroquinolines

30/spherical

Y ¼ 80–93 Y ¼ 80–98

[69]

6

Ethylenediamine celluloseimmobilized Pd NPs

Electrocatalytic oxidation of hydrazine

4.7–6.9

–

[70]

7

Au@cellulose nanocrystalsgraphene

A3-coupling reactions

3

Y ¼ 95

[71]

8

Palladium nanocatalyst on chitosan/cellulose composite

Suzuki coupling reaction

26–30/spherical

Y ¼ 55– 100

[72]

9

Cu NPs supported over nanocellulose

C-N coupling reactions

7/spherical

Y ¼ 82–95

[73]

10

Au NPs@cellulose aerogel

Epoxidation of styrene

81–89/rod-like

Y ¼ 96

[74]

11

Pd@cationic cellulose nanofibrils

Suzuki coupling reaction

3–9

Y ¼ 68–99

[75]

12

Ag NPs supported on cellulose

Degradation of hazardous dyes

4/spherical

–

[76]

13

Cellulose-supported Pd NPs

Chemoselective hydrogenation of nitroarenes

2–3/spherical

Y ¼ 84–99

[77]

14

Ag NP@bacterial cellulose

Decolorization of organic dyes

8.1/spherical

Y ¼ 99

[78]

15

Au@poly(4-vinylpyridine)-grafted cellulose nanocrystals

Reduction of 4-NP

2.9

–

[79]

16

Ag@cellulose paper

Reduction of 4-NP

4.3/spherical

C ¼ 97.8

[80]

17

Ag NPs/nanofibrillated cellulose

Reduction of 4-NP

30/spherical

–

[81]

19

Au NP/cellulose hydrogels

Reduction of 4-NP

3/spherical

–

[82]

20

Pd NPs@carboxymethyl cellulose/agar polysaccharides

Synthesis of biphenyl compounds

37–55/spherical

Y ¼ 43–98

[83]

21

Pd NPs@cellulose nanofiber

Suzuki and Heck cross-coupling reactions

2.5/spherical

Y ¼ 98–99 Y ¼ 62–99

[84]

22

Cu NPs@nanocrystalline cellulose

Reduction of methylene blue (MB)

2.71  1.12/ spherical

–

[85]

23

Magnetic cellulose/Ag

Synthesis of chromene-linked nicotinonitriles

27.56/spherical

Y ¼ 80–91

[86]

24

Cellulose microfiber-supported TiO2@Ag nanocomposite

Photodegradation of 4-chlorophenol

10/quasi-spherical

–

[87]

25

Ni-doped spherical mesoporous carbon

Hydrogenation of p-nitrophenol

23.6/cubic

C ¼ 99.7

[88]

26

WSC-g-PAA/PVAb-Cu nanocomposite

Reductive degradation of chloramphenicol

20–50/cubic

–

[89] Continued

TABLE 7.1 Application of cellulose-based MNP catalysts in various reactions—cont’d

Entry

Catalyst

Application

27

Pd NPs supported on TiO2 cellulose

Carbon-carbon cross coupling reactions

28

Pt nanoparticles@bacterial cellulose derived carbon nanofibers

29

Size (nm) and morphology

Y or C (%)

References

39–45/ nonspherical

Y ¼ 36–90

[45]

Hydrogen evolution reaction

2

–

[90]

Ru/3D-interconnected hierarchical porous N-doped carbon

Hydrogenation of toluene and quinoline

2.6

C ¼ 92 C ¼ 97

[91]

30

Cellulose-supported copper(0)

Synthesis of N-glycosyl-1,2,3-triazoles

5–10

Y ¼ 90–93

[92]

31

Cellulose-supported chiral Rh NPs

Asymmetric 1,4-additions to enones and α,βunsaturated esters

2–5

Y ¼ 83–95 Y ¼ 81–96

[93]

32

Pd NPs@amine-functionalized silica-cellulose substrates

C-C and CdS coupling reactions

3.5/quasispherical

Y ¼ 75–92 Y ¼ 80–88

[94]

33

Cellulose-supported Pd(0) nanoparticles

Suzuki and Heck coupling reactions

10–30/spherical

Y ¼ 82–94 Y ¼ 87–89

[95]

34

Ru NPs@cellulose nanocrystals

Toluene hydrogenation

3.3  1

Y ¼ 100

[96]

35

Ir NPs@cellulose acetate

Hydrogenation reactions

2.1  0.5/ spherical

–

[97]

36

Au NPs/Amidoxime surfacefunctionalized bacterial cellulose

Reduction of 4-NP

10.6  2.9/ spherical

–

[98]

37

Ag NPs@bacterial cellulose

Oxygen reduction reaction

10–20/spherical

–

[99]

38

Pd NPs@cellulose acetate

Suzuki-Miyaura reaction

2.7  0.4

Y ¼ 31–99

[100]

39

γ-Fe2O3@cellulose-OSO3H

Synthesis of diverse pyrano[2,3-c]pyrazole derivatives

25–55

Y ¼ 86–99

[101]

40

Ag PTNPc-immobilized cellulose filter paper

Reduction of 4-NP

4.6/spherical

–

[102]

41

Fe3O4@nano-cellulose/TiCl

Synthesis of 4H-pyrimido[2,1-b] benzothiazoles

–

Y ¼ 69– 98.5

[103]

42

CeO2 using MCCd

Ozonation of phenol

7–10

–

[104]

e

43

TiO2/NCC-EDA

Photocatalytic reduction of CO2/H2O to methyl formate

20/near-spherical

–

[105]

44

Fe3O4@nanocellulose/Cu(II)

Synthesis of 4H-pyrimido[2,1-b] benzothiazole derivatives

Below 70

Y ¼ 71–97

[106]

45

Ag@CAFf

Reduction of nitrophenols

 25 (3)

–

[107]

Reduction of 2-nitrobenzoicacid

2–5

–

[108]

Reduction of 4-NP

2–4

–

[109]

g

46

m-WSC/FP-Cu

47

h

Pd NPs@CHI

i

48

CMC-Co-BCN

Reduction of 2,6-dinitrophenol and MB

>100

–

[110]

49

Cellulose-supported Ag-Ag2S NPs

Oxidative decarboxylation of phenylacetic acids

16/spherical

Y ¼ 60–82

[111]

50

Ag NPs@MOF-199 s/CCFsj

Reduction of 4-NP

6–20

C ¼ 94

[112]

51

Fe3O4@SiO2@cellulose@poly glycidyl methacrylate@EDAe

Reduction of 4-NP

12–23

–

[113] Continued

TABLE 7.1 Application of cellulose-based MNP catalysts in various reactions—cont’d

Entry

Catalyst

Application

Size (nm) and morphology

Y or C (%)

References

52

Ag NPs@CMC-Agar-Pectin

Reduction of nitroarenes

44–57/spherical

Y ¼ 89–99

[114]

53

CuO@cellulose sponge

Reduction of toxic organic dyes

51  3/spherical

–

[115]

54

Lignocellulose-supported Pd-In

Nitrate reduction

5–10/near spherical

–

[116]

55

CdxZnxS@CMC hydrogel

Hydrogen production

3

–

[117]

k

56

HKUST-1 /Fe3O4/cellulose microfibrils

Degradation of MB

10/spherical

–

[118]

57

CdS/Pt-CMC

Hydrogen production

3

–

[119]

58

CuS/cellulose-based aerogel

Photodegradation of MB

Hexagonal

–

[120]

e

l

59

[(EDA -g-DAC )@Fe3O4]

Degradation of AB74 dye

55/spherical

Y ¼ 66

[121]

60

Nano-Fe3O4@celloluse-SO3H

Synthesis of functionalized pyrimido[4,5-b] quinolines and indeno-fused pyrido[2,3-d] pyrimidines

8.91

Y ¼ 70–95

[122]

61

Cellulose/TiO2

Photodegradation of MB

40 nm/3D

–

[123]

Reduction of 4-NP

4.30  0.97/ spherical

–

[124]

Synthesis of 4H-pyrimido[2,1-b] benzothiazole derivatives

Below 50

Y ¼ 68–97

[125]

m

62

AuNPs/TOBCNs

63

Nano-TiCl2/cellulose

64

Cu2O/cellulose-based aerogel

Photodegradation of MB

20–140/ octahedral

–

[126]

65

Ag2S-ZnS loaded on cellulose

Photodegradation of rhodamine B (RhB)

0.4

–

[127]

66

Fe3O4@nanocellulose-OPO3H

Synthesis of dihydro-2-oxopyrrole derivatives

60/quasi-spherical

Y ¼ 72–91

[128]

67

Nano-Fe3O4/TiCl2/cellulose

Synthesis of 2,3-dihydroquinazolin-4(1H)ones

Below 50

Y ¼ 79–96

[129]

68

Cu-Co/cellulose

Alcohol synthesis

Below 20

–

[130]

69

Cellulose nanofibril-Pd NPs

Discoloration of anionic and cationic dyes

Ni(II) > Zn(II) > Cd(II) [229]. In another study, the adsorption capability of magnetically separable pectin-Fe3O4 nanocomposite has been investigated in the effective removal of Cu(II) (48.99 mg/g) from wastewater [230]. In addition, hybrid pectin/titanium oxide nanobeads have been reported as bionanosorbents for the removal of ionic heavy multimetals with adsorption capacities of 0.83, 0.68, 1.37, and 0.51 mmol/g for Pb(II), Cd(II), Cu(II), and Zn(II), respectively [231]. Moreover, pectin-CuS nanocomposite has been utilized in the adsorption and photocatalytic degradation of MB under solar light at 30°C [232]. In another study, a novel agar/pectin composite (APC)-functionalized with Pd NPs (34–54 nm) was prepared and applied in the o-nitroaniline reduction to 1,2-benzenediamine by aqueous NaBH4 at ambient temperature [233]. It was found that PdNPs@APC natural biopolymer composites can be effectively utilized as stabilizers for diverse noble metal NPs. Most recently, a novel ethylenediamin-modified pectin (EP) with different degrees of amidation (DA) was fabricated via a facile precipitation route and applied in the Pb(II) adsorption from an aqueous solution (Fig. 8.7) [234]. It was observed that EP48 (with the highest DA) exhibited high elimination efficiency of Pb(II) (94%) at a low concentration of 40–80 mg/L. The adsorption mechanisms showed that Pb(II) ions were bio-adsorbed via an ion exchange of carboxylic groups and coordination chelation with amino and acylamino groups. Other documented studies about the use of pectin-based (nano)composites in the removal of organic/inorganic contaminants are summarized in Table 8.6.

8.3.7

Lignin-based bio(nano)sorbents

Lignin is a significant constituent of the lignocellulosic biomass biopolymers along with cellulose. Among diverse types of natural biopolymers, lignin has a complex and irregular structure, abundance, and varying physicochemical properties and not surprisingly, it can convert into various types of cheaper and environmentally benign biosorbents for water/wastewater purification. In spite of being cheap, eco-friendly, and the most abundant natural biopolymer, lignin macromolecules have been limited due to their low response rates and low adsorption capabilities for the removal of heavy metals. In a recent study,

FIG. 8.7 Synthesis, application, and adsorption mechanisms of EPs [234]. (Reproduced with permission from Liang RH, Li Y, Huang L, Wang XD, Hu XX, Liu CM, Chen MS, Chen J. Pb2+ adsorption by ethylenediamine-modified pectins and their adsorption mechanisms. Carbohydr Polym 2020;234:115911.)

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TABLE 8.6 Other examples of pectin-based nanocomposites in elimination of organic/inorganic pollutants. Pectin-based nanocomposites

Pollutants

Highlights

Reference

FN-PA, FN-PAG, and FN-PAAa

MB

High degradation and adsorption force (FN-PAA > FNPAG > FN-PA)

[225]

FFNPs-CPAc

Amaranth (AM)

Degradation percent: 98.2

[226]

Modified Fe3O4 NPs with the extracted pectin of Azolla filiculoides

Methyl orange

Maximum uptake capacity at 5°C: 0.533

[235]

(PPA3)b-Cu and (PPA3/ Fe3O4)-Cu nanocomposite Hydrogels

2-Nitrophenol

High reduction

[236]

Pectin-stabilized magnetic graphene oxide Prussian blue nanocomposites

Cesium

Adsorption capacity (mg/g): 1.230

[237]

Pectin-stabilized nano zerovalent iron

Cr(VI)

Removal from water

[238]

Magnetite/silica/ pectin NPs

Fluoroquinolones (ciprofloxacin and moxifloxacin)

Removal percent: 89

[239]

Living and dead Azolla-FNPsd

MB

Highest possibility of the total degradation

[240]

a

Stabilized Fe3O4 NPs using the extracted pectin from apple waste (FN-PA) and its cross-linked forms by glutaraldehyde (PAG) and adipic acid (PAA). Cross-linked pectin-polyvinyl alcohol-co-acrylamide hydrogel (PPA). c 0 Fe and Fe3O4 NPs synthesized and stabilized by the cross-linked pectin with adipic acid (CPA) d Fe NPs were connected to the cell wall’s pectin of the dead or living Azolla. b

lignin microspheres have been fabricated via inverse suspension copolymerization technique for the Pb(II) removal from an aqueous solution [45]. It was shown that the surface area of these microspheres was 5.3 times that of lignin and included many amine functional groups. The microspheres also exhibited a fast response rate and an excellent adsorption capacity for Pb(II) (33.9 mg/g), which is 280% and 137% greater than the corresponding values for poplar and alkaline lignin, respectively. Recently, lignin and its derivatives have shown an excellent performance for efficient removal of pollutants such as metal ions and dyes from water/wastewater [241–246].

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Crude lignin, in general, has poor efficiencies for the heavy metal elimination (10 mg/g) from contaminated water [247, 248]. It has been suggested by researchers that lignin modification can affect the elimination of heavy metals form aqueous media. Thermal or chemical modification of lignin mostly involves fragmentation, functionalization of hydroxyl groups, and formation of new chemically active sites. Thus, dithiocarbamate-functionalized lignin has been prepared as an effective and natural biosorbent for the removal of multimetallic ions, including Cu(II) (98.95%) and Pb(II) (98.6%) ions, using optimal cross-linked biopolymer dosage (50 mg/L) [249]. In another study, a highly porous lignosulfonate sphere was prepared by epichlorohydrin cross-linking and sodium alginate via gelation solidification method and used to adsorb lead ions (27.1 mg/g) from water/wastewater [250]. Nowadays, the adsorption properties and performance of lignin-based bio (nano)sorbents can be further improved by combination of lignin and nanostructures such as nanocomposites and nanohydrogels [251–253]. The use of lignin and/or lignocellulose fibers for the fabrication of lignin-based bio(nano)sorbents could be improved by incorporating metal/metal oxide NPs, silicate NPs, nanocellulose, carbon nanotubes, graphene, or graphene oxide, leading to the enhanced adsorption efficiency and mechanical strength of lignin [254–259]. Other documented studies on the use of lignin-based bio(nano)sorbents in wastewater treatment are summarized in Table 8.7.

8.3.8 Protein-based (nano)composites The application of protein-based bio(nano)composites in water treatment is not wide, but limited to the removal of oil spills from contaminated water. Generally, spent oils are toxic and oil contamination in coastal waters causes severe environmental/ecological, and economic impacts. Oil spills in waterbodies are a main environmental concern all over the world. In this context, sustainable collagen-based magnetic nanocomposites have been fabricated via a facile process using protein biowastes from the leather industries [273]. The developed bionanocomposite exhibited good properties in terms of selective oil adsorption, and magnetic tracking ability in treating oily wastewaters. Gelatin biopolymer, in general, possess many chemical groups (particularly unbonded carboxylic groups), which have strong affinity to metal ions. Therefore, hydroxyapatite, gelatin, or modified gelatin have been widely applied for the removal of heavy metals from aqueous solutions. (Nano)composites are prepared by multimaterials to enhance the adsorption capacities, bioactivity, recyclability, efficiency, and specific surface area. Among the protein biopolymers, gelatin and modified gelatin-based bionanocomposites can be extensively applied in the adsorption of various pollutants, defluoridation, or phosphate retention from aqueous media [274–278].

Environmental applications of biopolymer Chapter

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TABLE 8.7 Lignin-based (nano)composites used for water treatment. Lignin-based (nano)composites

Contaminants

Reference

Pd NPs@Fe3O4-lignin

Cr(VI)

[37]

Lignin-based magnesium hydroxide nanocomposite

Ni(II), Pb(II), and Cd(II)

[260]

Bentonite/sodium lignosulfonate/acrylamide/ maleic anhydride hydrogel

Pb(II)

[261]

Lignin-grafted polyacrylic hydrogel

Pb(II)

[262]

Alkaline lignin-dopamine/Fe3O4 NPs

Cr(III)

[263]

Cellulose-lignin composite hydrogel

Pb(II)

[264]

Manganese peroxidase/lignin peroxidase/laccase/ polyacrylamide/pectin hydrogel

Bisphenol A

[265]

Poly(ethyleneimine)-graft-alkali lignin loaded with nanoscale lanthanum hydroxide

Phosphate

[266]

Lignin sulfonate-g-poly(acrylic acid-r-acrylamide) copolymer adsorbent

Malachite green

[267]

Lignosulfonate-g-acrylic acid hydrogel

MB

[268]

Acylated hemicelluloses/acrylic acid/sodium lignosulfonate hydrogel

MB

[269]

Kraft lignin-N-isopropyl acrylamide hydrogel

MB

[270]

Magnetic-lignin-based carbon NPs

Methyl orange

[271]

Surface-modified spherical lignin particles

Cr(VI)

[272]

In one study, novel nano-hydroxyapatite (n-HAp)-embedded gelatin prepared via in situ precipitation process was utilized for the efficient removal of toxic metals from contaminated water [279]. Three isotherm models, Freundlich, Langmuir, and Dubinin-Radushkevich, were utilized to study the adsorption isotherm. It was found that the sustainable bionanocomposite was able to efficiently adsorp Cr(VI). Similarly, magnetic-reinforced n-HAp/gelatin biocomposite was applied in the efficient Cr(VI) removal from wastewater [280]. The enhanced Cr(VI) biosorption capacities of Fe3O4@n-HAp/gelatin prepared via both hydrothermal and in situ approaches were 22.55 and 29.06 mg/g, respectively. Table 8.8 illustrates the potential of gelatin-based (nano)composites in the removal of heavy metals and dyes from water/ wastewater.

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TABLE 8.8 Gelatin-based photocatalysts/catalysts in the removal of organic/ inorganic contaminants. Gelatin-based photocatalysts/ catalysts

Contaminants

Highlights

Reference

Gelatin-zirconium dioxide nanocomposite

MB

Degradation of 82% of MB within 5 h of solar irradiation

[281]

Gelatin-zirconium (IV) tungstophosphate nanocomposite

Methyl violet

84.61% degradation under solar illumination

[282]

CTAB-Silica gelatin composite

Cr(VI)

Adsorption capacity (mg/g): 16.60

[283]

Chitosan/gelatin filled with graphene

Orange II

Removal efficiency of 84.3%

[284]

Magnetic nanocomposite beads of gel-CNT-MNPs

Direct red 80 (DR) and MB

Removal of 96.1% of DR and 76.3% of MB

[285]

Dumbbell MnO2/ gelatin composite

Pb(II) and Cd(II) ions

Adsorption capacity (mg/g): 318.7 (lead) and 105.1 (cadmium)

[286]

Tannin-immobilized gelatin/PVA nanofiber

Uranium (VI)

Adsorption capacity (mg/g): 170

[287]

8.4 Other environmental applications 8.4.1 Biohydrogen production Besides water treatment discussed thus far in the chapter, natural biopolymers can also serve as substrates for biological hydrogen production. Biohydrogen is regarded a renewable, clean, and sustainable energy carrier with high energy potentials (122 kJ/g) [288, 289]. Thus, biohydrogen can be efficiently applied as the main source of fuel in the future. Considering the imminent energy crisis scenario, the development of an alternative energy source, which provides economic, social, and environmental benefits, is of great significance [288, 289]. Nowadays, the use of lignocellulosic biopolymers as the main substrate for biohydrogen production is a relevant area of environmental research due to their renewability, nonpolluting nature, and availability [290]. For example, there are some reports on the biohydrogen production from lignocellulosic biomass/ waste [290, 291]. Nevertheless, lignocellulosic biohydrogen conversion

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FIG. 8.8 Schematic representation of the dark fermentation integrated with microbial electrolysis cells process for higher hydrogen yield [292]. (Reproduced with permission from Chandrasekhar K, Lee YJ, Lee DW. Biohydrogen production: strategies to improve process efficiency through microbial routes. Int J Mol Sci 2015;16(4):8266–93.)

through dark fermentation has several disadvantages (e.g., low biohydrogen yield), which prevent researchers from exploiting these biomass substrates to the fullest extent. To overcome this, many solutions such as the combination of photofermentation, microbial electrochemical, and anaerobic digestion systems can be used for achieving industrialized biohydrogen production, making the process more competent and applicable. For this, the microbial electrolysis cell bioprocess is feasible to produce hydrogen in connection with simultaneous water treatment for a diversity of soluble organic substances in the presence of an external voltage (Fig. 8.8) [292–294]. A two stage bioprocess, i.e., microbial electrolysis cells integrated with dark fermentation, can be a viable option to obtain additional H2 production. In stage 1, a complex organic substrate is applied for H2 generation by dark fermentation and in stage 2, an acid-rich effluent is applied as a substrate in microbial electrolysis cells for further hydrogen production [292–294]. Indeed, lignocellulose structures need pretreatment owing to their recalcitrant structure. During dilute acid pretreatment, lignocellulosic biomass is exhibited to be an appropriate substrate for the fermentative production of hydrogen [295]. In one of the studies, efficient biohydrogen production was carried out using L-arabinose (component of hemicellulosic biopolymers) as a viable substrate [296]. Biohydrogen production from sugarcane bagasse as a cellulosic substrate has been significantly enhanced by using Clostridium thermocellum

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supplemented with CaCO3 [297]. These stimulatory effects are often attributed to the buffering capacities of carbonate and generally provide a new strategy to improve biohydrogen fabrication from lignocellulose. In another study, solar hydrogen production from timber waste, namely lignin and cellulose, by enzymatic and artificial photosynthesis technology has been reported [298]. There are also notable examples of other natural biopolymer-based catalysts, which are beneficial in this process, alginate polysaccharides being the most obvious one. Alginate, which has an excellent photocatalytic activity in biohydrogen production from methanol and water mixtures, can be applied in the fabrication of active titania photocatalysts such as Au-TiO2 and TiO2 [299]. A facile and reliable method to fabricate titania samples was reported. Au-TiO2 sample fabricated via biopolymer templating technique was almost eight times more active in biohydrogen production using a solar simulator compared with the analogous sample fabricated via the conventional depositionprecipitation technique. Moreover, the preparation of graphitic carbon sheets decorated with Mo2C NPs (Mo2C/GCSs) was reported by the biopolymerderived, solid-state reaction of sodium alginate and (NH4)6Mo7O244H2O at 900°C under Ar [300]. The novel Mo2C/GCSs hybrid catalysts exhibited substantial long-term durability (3000 cycles) in hydrogen production. In another example, cobalt grown in situ on a macroscopic alginate hydrogel as a recyclable catalyst was reported for biohydrogen production from the hydrolysis of borohydrides (e.g., NaBH4) [301]. As a result, biopolymers are useful in the fabrication of catalysts for hydrogen production.

8.4.2 Electrochemical applications The mechanical, thermal, and electrochemical stabilities of solid polymer electrolytes applied in electrochemical devices, e.g., batteries; fuel cells, etc. are of supreme importance. Due to the better environmental acceptability of electrolytes, which make use of natural biopolymers, there is a need for easily processable, nontoxic, cost-effective, and high-performance proton-conducting membranes. Owing to their different chemical structures, economy, richness, and biodegradability, natural biopolymer-based electrolytes have achieved considerable attention in recent years as an eco-friendly, green compounds. Polysaccharides are demonstrated to be the prominent class of natural biopolymers applied to improve electrochemical devices [302–307]. Most of the solid biopolymer electrolytes are based on hydroxyethylcellulose [308], chitosan [309–311], starch [312], pectin [313], etc., in which the ionic conductivities have been reported in the order of 104 S/cm at ambient temperature. Chitosan and its derivatives can constitute biopolymer hosts for electrolytes since they are able to dissolve ionic salts [314, 315]. Indeed, when a chitosan membrane is swollen in an aqueous medium, its amino groups can be protonated, thereby leading to protonic conductivity [315, 316]. In this respect, important electrical properties of chitosan-based electrolytes have been reported via

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complexation by ammonium and/or lithium salts [317–320]. Based on chitosan and ammonium salts, e.g., NH4NO3 and NH4CF3SO3 [321, 322], a variety of conductivities (105–104 S/cm) have been described for proton-conducting, biopolymer-based electrolytes. The corresponding value for chitosan and kappa (κ)-carrageenan comprising ammonium-nitrate-based films is 106– 104 S/cm [323, 324]. Moreover, LiMn2O4 chitosan doped with carbon has been reported as a biopolymer-in-salt-based electrolyte, which can show the best ionic conductivity (3.9
103 S/cm) at ambient temperature [325]. Natural biopolymer electrolytes based on the cellulose derivatives from Kenaf Bast fiber have been studied [326]. Additionally, electrochemical studies have been reported on a cellulose acetate-LiBOB polymer gel electrolyte [327]. In another study, a natural biopolymer-based electrolyte was prepared via combining various NH4Br compositions as ionic dopants since ammonium salts with carboxymethyl cellulose (CMC) are considered good donors to the host biopolymer, which has been used to develop rechargeable proton batteries [328]. Another system based on a blend of CMC and CMΥ-carrageenan was developed for designing dye sensitized solar cells [329]. In this context, there are numerous reports on the biopolymer-based electrolytes such as tamarind seed polysaccharide with NH4SCN as the dopant [330], I-carrageenan membranes doped with NH4Br [331], CMΥ-carrageenan doped with 1-butyl-3methylimidazolium chloride ionic liquid [332], and pectin doped with NH4Cl or NH4Br [333]. The incorporation of salts to polymers is a significant method to afford ions as charge carriers. Magnesium batteries by utilizing natural biopolymers as electrolyte membranes have hardly been reported. The incorporation of Mg (ClO4)2 [334], Mg(NO3)2 [335], and Mg(C2H3O2)2 [336] can enhance the ionic conductivity of I-carrageenan and potato starch to 2.18
103, 6.1
104, and (2.44  0.37)
108 S/cm at room temperature, respectively. Most recently, the incorporation of Mg(ClO4)2 into cellulose-acetate-based electrolytes increased their room temperature conductivity to 4.05
104 S/cm [337]. In two of the studies, natural lignin matrixes have been applied as environmentally friendly, gel biopolymer-based electrolytes in lithium ion batteries [338], and lignosulfonate graphene hydrogels have been used as supercapacitor electrodes [339]. Furthermore, CMC/chitosan, dual-blend-based natural biopolymer electrolytes [340], and bionanocomposite membranes made of sulfonated chitosan/sulfonated graphene oxide [341] are other examples of the application of biopolymers in electrochemical applications.

8.5

Conclusion and future perspective

Application of natural biopolymers in the fabrication of bio(nano)composites, bio(nano)sorbents, and biopolymer membranes for the removal of an array of organic pollutants (e.g., dyes, pigments, and oil spills) and inorganic pollutants (e.g., heavy metals and radioactive ions) has been reviewed. Using natural

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biopolymer-based resources derived from various living organisms, animals, plants, or agricultural by-products, including polysaccharides, lignin, gelatin, and their derivatives, is undoubtedly the future wave. Among the biopolymers, alginates and chitosan polysaccharides are the best for coagulation/ flocculation of heavy metals. Generally, natural polysaccharides have attracted much attention in wastewater treatment. In addition, natural biopolymer-based electrolytes used for electrochemical applications such as rechargeable batteries and/or fuel cells have been commercialized. Various methods used to treat contaminated water and combinations of advanced nanotechnology-oriented methods with the traditional techniques provide interesting benefits. Metal/metal oxide NPs play a major role in nanotechnology and nanoscience. Thus, it is very critical to find innovative and effectively advanced water nanotechnologies with the capacity to efficiently remove toxic and unsafe pollutants, thereby ensuring the excellent quality of safe drinking water. The application of nanomaterials in water/wastewater treatment has proven to have better selectivity, sustainability, and stability and more effective adsorption abilities than NPs. Indeed, nano-engineered materials, e.g., nanocomposites, nanomembranes, nanoadsorbents, and photocatalysts, are promising candidates for such treatment objectives and could be industrially fabricated after comprehensive optimization and assessment studied. Eventually, biopolymer-based nanocomposites lead to an important improvement in the adsorbent and membrane performances in terms of environmental friendliness, sustainability, cost-effectiveness, permeation, or self-cleaning properties, from the standpoints of both environmental cleanup and resource conservation. In this chapter, the chemistry, properties, and environmental applications of natural biopolymer-based nanocomposites, namely chitosan, cellulose, gum, starch, pectin, alginate, lignin, collagen, and gelatin bio(nano)composites/bio (nano)sorbents have been described. These biopolymers have been considered alternative and effective supports in the literature for the fabrication of biopolymer-based metal/metal oxide NPs such as biopolymer-supported Pd, Ag, Cu, Au, TiO2, ZnO, Fe3O4 NPs. In water treatment, these bionanocomposites have been successfully applied in the adsorption of organic dyes, nitroarenes, radioactive ions, and heavy metal ions and their antimicrobial potential has also been studied. Although biopolymer-based bionanocomposites have major applications in many industrial fields, several economic and technical obstacles restrict their extensive commercialization. Indeed, the problems and difficulties associated with poor adhesion of fiber and matrix, achievement of nanoscale range, orientation of fiber, and/or achievement of actual renewable biopolymers need widespread research. As it is clear from this chapter, nanotechnologies have the potential to make industrial water treatment more effective by the successful removal of numerous pollutants using different biopolymer nanosystems. However, this field still needs further development. Water treatment industries are also promoting

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sustainable developments of simplified and cost-effective systems to find different methods to treat wastewater. Therefore, the large-scale applications of natural biopolymer-based bionanocomposites and their effective applications in the near future are feasible. Although there are notable advances in the use of natural biopolymer-based metal/metal oxide NPs for environmental applications, specific considerations should be paid to the following subjects in future studies: ✓ Scalable preparation of biopolymer-based bionanocomposites at a relatively lower cost. ✓ Until now, biopolymers such as cellulose, chitosan, gum, starch, pectin, alginate, and lignin have been utilized to make adsorbents. However, further studies regarding the application of biopolymers such as collagen, gelatin, silk fibroin, etc. to make bio(nano)sorbents are necessary. ✓ Application of diverse biowastes as renewable alternative feedstocks for the fabrication of biopolymers and their application in wastewater treatment. ✓ Exploitation of natural supports, e.g., clays, zeolites, etc. as low-cost, nontoxic, and available sources for the fabrication of nanocatalysts and environmental applications. ✓ Improvement of existing approaches for easier fabrication of these biopolymers from biorenewable raw resources. ✓ Improvement of biopolymer-based magnetic NPs for water/wastewater treatment. ✓ Manipulation of animal residues such as bone, bristles, and eggshell for the synthesis of biopolymer-based bionanocomposites and their environmental applications.

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[305] Singh R, Jadhav NA, Majumder S, Bhattacharya B, Singh PK. Novel biopolymer gel electrolyte for dye-sensitized solar cell application. Carbohydr Polym 2013;91(2):682–5. [306] Singh R, Baghel J, Shukla S, Bhattacharya B, Rhee HW, Singh PK. Detailed electrical measurements on sago starch biopolymer solid electrolyte. Phase Transit 2014;87(12): 1237–45. [307] Shuhaimi NEA, Alias NA, Kufian MZ, Majid SR, Arof AK. Characteristics of methyl cellulose-NH4NO3-PEG electrolyte and application in fuel cells. J Solid State Electrochem 2010;14(12):2153–9. [308] Machado GDO, Ferreira HCA, Pawlicka A. Influence of plasticizer contents on the properties of HEC-based solid polymeric electrolytes. Electrochim Acta 2005;50(19):3827–31. [309] Idris NH, Majid SR, Khiar ASA, Hassan MF, Arof AK. Conductivity studies on chitosan/PEO blends with LiTFSI salt. Ionics 2005;11:375–7. [310] Pawlicka A, Danczuk M, Wieczorek W, Zygadlo-Monikowska E. Influence of plasticizer type on the properties of polymer electrolytes based on chitosan. J Phys Chem A 2008; 112(38):8888–95. [311] Shuhaimi NEA, Alias NA, Majid SR, Arof AK. Electrical double layer capacitor with proton conducting k-carrageenan-chitosan-electrolytes. Funct Mater Lett 2008;1(3):195–201. [312] Mattos RI, Tambelli C, Donoso JP, Pawlicka A. NMR study of starch based polymer gel electrolytes: humidity effects. Electrochim Acta 2007;53(4):1461–8. [313] Leones R, Botelho MBS, Sentanin F, Cesarino I, Pawlicka A, Camargo ASS, Silva MM. Pectin-based polymer electrolytes with Ir(III) complexes. Mol Cryst Liq Cryst 2014;604 (1):117–25. [314] Morris GA, K€ok SM, Harding SE, Adams GG. Polysaccharide drug delivery systems based on pectin and chitosan. Biotechnol Genet Eng Rev 2010;27(1):257–84. [315] Singh AV, Nath LK, Singh A. Pharmaceutical, food and non-food applications of modified starches: a critical review. Electron J Environ Agric Food Chem 2010;9(7):1214–21. [316] Sousa AM, Sereno AM, Hilliou L, Gonc¸alves MP. Biodegradable agar extracted from Gracilaria vermiculophylla: film properties and application to edible coating. In: Materials science forum, vol. 636–637. Trans Tech Publications Ltd.; 2010. p. 739–44. [317] Buraidah MH, Teo LP, Majid SR, Arof AK. Characteristics of TiO2/solid electrolyte junction solar cells with I-/I3-redox couple. Opt Mater 2010;32(6):723–8. [318] Mohamed NS, Subban RHY, Arof AK. Polymer batteries fabricated from lithium complexed acetylated chitosan. J Power Sources 1995;56(2):153–6. [319] Buraidah MH, Teo LP, Yusuf SNF, Noor MM, Kufian MZ, Careem MA, Majid SR, Taha RM, Arof AK. TiO2/chitosan-NH4I(+I2)-BMII-based dye-sensitized solar cells with anthocyanin dyes extracted from black rice and red cabbage. Int J Photoenergy 2011;, 273683. [320] Buraidah MH, Arof AK. Characterization of chitosan/PVA blended electrolyte doped with NH4I. J Non Cryst Solids 2011;357(16–17):3261–6. [321] Majid SR, Arof AK. Proton-conducting polymer electrolyte films based on chitosan acetate complexed with NH4NO3 salt. Phys B Condens Matter 2005;355(1–4):78–82. [322] Hamdan KZ, Khiar ASA. Conductivity and dielectric studies of methylcellulose/chitosanNH4CF3SO3 polymer electrolyte. In: Abdullah MMAB, Jamaludin L, Abdullah A, Razak RA, Hussin K, editors. Key Engineering Materials, vol. 594–595. Trans Tech Publications Ltd.; 2014. p. 818–22. [323] Nijenhuis K. Thermoreversible networks: viscoelastic properties and structure of gels. vol. 130. Berlin: Springer; 1997. p. 194–202. [324] Campo VI, Kawano DF, da Silva Jr DB, Carvalho I. Carrageenan: biological properties, chemical modifications and structural analysis-a review. Carbohydr Polym 2009;77(2): 167–80.

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[325] Kamarulzaman N, Osman Z, Muhamad MR, Ibrahim ZA, Arof AK, Mohamed NS. Performance characteristics of LiMn2O4/polymer/carbon electrochemical cells. J Power Sources 2001;97:722–5. [326] Rani MSA, Rudhziah S, Ahmad A, Mohamed NS. Biopolymer electrolyte based on derivatives of cellulose from kenaf bast fiber. Polymers 2014;6(9):2371–85. [327] Abidin SZZ, Ali AMM, Hassan OH, Yahya MZA. Electrochemical studies on cellulose acetate-LiBOB polymer gel electrolytes. Int J Electrochem Sci 2013;8:7320–6. [328] Samsudin AS, Lai HM, Isa MIN. Biopolymer materials based carboxymethyl cellulose as a proton conducting biopolymer electrolyte for application in rechargeable proton battery. Electrochim Acta 2014;129:1–13. [329] Rudhziah S, Ahmad A, Ahmad I, Mohamed NS. Biopolymer electrolytes based on blend of kappa-carrageenan and cellulose derivatives for potential application in dye sensitized solar cell. Electrochim Acta 2015;175:162–8. [330] Premalatha M, Mathavan T, Selvasekarapandian S, Monisha S, Pandi DV, Selvalakshmi S. Investigations on proton conducting biopolymer membranes based on tamarind seed polysaccharide incorporated with ammonium thiocyanate. J Non Cryst Solids 2016;453:131–40. [331] Karthikeyan S, Selvasekarapandian S, Premalatha M, Monisha S, Boopathi G, Aristatil G, Arun A, Madeswaran S. Proton-conducting I-Carrageenan-based biopolymer electrolyte for fuel cell application. Ionics 2017;23(10):2775–80. [332] Shamsudin IJ, Ahmad A, Hassan NH, Kaddami H. Biopolymer electrolytes based on carboxymethyl Υ-carrageenan and imidazolium ionic liquid. Ionics 2016;22(6):841–51. [333] Vijaya N, Selvasekarapandian S, Sornalatha M, Sujithra KS, Monisha S. Proton-conducting biopolymer electrolytes based on pectin doped with NH4X (X ¼ Cl, Br). Ionics 2017;23 (10):2799–808. [334] Priya SS, Karthika M, Selvasekarapandian S, Manjuladevi R, Monisha S. Study of biopolymer I-carrageenan with magnesium perchlorate. Ionics 2018;24(12):3861–75. [335] Priya SS, Karthika M, Selvasekarapandian S, Manjuladevi R. Preparation and characterization of polymer electrolyte based on biopolymer I-carrageenan with magnesium nitrate. Solid State Ion 2018;327:136–49. [336] Shukur MF, Ithnin R, Kadir MFZ. Ionic conductivity and dielectric properties of potato starch-magnesium acetate biopolymer electrolytes: the effect of glycerol and 1-butyl-3methylimidazolium chloride. Ionics 2016;22(7):1113–23. [337] Mahalakshmi M, Selvanayagam S, Selvasekarapandian S, Moniha V, Manjuladevi R, Sangeetha P. Characterization of biopolymer electrolytes based on cellulose acetate with magnesium perchlorate (Mg(ClO4)2) for energy storage devices. J Sci Adv Mater Dev 2019;4 (2):276–84. [338] Gong SD, Huang Y, Cao HJ, Lin YH, Li Y, Tang SH, Wang MS, Li X. A green and environment-friendly gel polymer electrolyte with higher performances based on the natural matrix of lignin. J Power Sources 2016;307:624–33. [339] Xiong C, Zhong W, Zou Y, Luo J, Yang W. Electroactive biopolymer/graphene hydrogels prepared for high-performance supercapacitor electrodes. Electrochim Acta 2016;211: 941–9. [340] Hafiza MN, Bashirah AN, Bakar NY, Isa MI. Electrical properties of carboxyl methylcellulose/chitosan dual-blend green polymer doped with ammonium bromide. Int J Polym Anal Charact 2014;19(2):151–8. [341] Shirdast A, Sharif A, Abdollahi M. Effect of the incorporation of sulfonated chitosan/ sulfonated graphene oxide on the proton conductivity of chitosan membranes. J Power Sources 2016;306:541–51.

Chapter 9

Biopolymer-based metal nanoparticles for biosensing Zahra Nezafata, Mahmoud Nasrollahzadeha, Talat Baranb, and Nasrin Shafieia a

Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran, bDepartment of Chemistry, Faculty of Science and Letters, Aksaray University, Aksaray, Turkey

9.1

Introduction

Biosensors, known as a sort of analytical device, have great importance in the detection of biological and chemical elements in different fields, such as food, clinical, environmental, and so on [1]. Biosensors were initially reported in 1962. They are commonly defined as sensors containing biological recognition elements, frequently called bioreceptors or transducers [2, 3]. For the past few years, biosensors have been efficiently used in biological and chemical processes, which have wide applications in the fields of environment, bioprocessing, homeland security, drug, food, and agricultural industries [4, 5]. Biosensors have two fundamental principles, which make them different from conventional chemical sensors: (1) the sensing elements are biological structures, viz. cells, enzymes, or nucleic acids and (2) the sensors are used to measure biological procedures or physical changes [6]. Classical biosensors generally consist of three important components as follows: (1) bioreceptors or bioelements, which are composed of nucleic acids, antibodies, cells, etc. (2) transducers and (3) electronic units. Fig. 9.1 shows the three important components of a biosensor [7]. Fig. 9.2 displays a typical biosensor [7]. As previously indicated, a classical biosensor is composed of three central parts: the electronic system, which includes the signal amplifier, processor and display unit, the transducer, which changes the reaction of the sample analyte and bioreceptor into an electrical signal, and a bioreceptor composed of a biological substance, which aims and/or binds to a particular compound. The transducer used in the biosensor depends on the reaction, which occurs between the sample and the bioreceptor [7]. A biosensor fundamentally uses a biorecognition element (such as enzymes, aptamers, nucleic acids, and whole cells), which interacts with the analyte to Biopolymer-Based Metal Nanoparticle Chemistry for Sustainable Applications https://doi.org/10.1016/B978-0-323-89970-3.00009-3 Copyright © 2021 Elsevier Inc. All rights reserved.

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FIG. 9.1 Schematic representation of the essential components of a biosensor [7].

FIG. 9.2 Representation of a classical biosensor [7].

produce a biological signal. This signal is changed into an electronic sign by the transducer element [2]. The effective interaction between the biorecognition unit and the analyte is the key to the efficient development of a biosensor. This needs effective immobilization or attachment of the biorecognition element to the sensor interface. Additionally, the biosensor material needs to have good biocompatibility to maintain the activity of the bioreceptor. Biorecognition elements are sensitive to external factors, such as pH, ionic strength, and temperature. Therefore the immobilization matrix should be capable of shielding the bioreceptor from external conditions, which are detrimental to its activity. The immobilization matrix has to allow easy diffusion of the analyte to the bioreceptor without presenting a barrier. At the same time, it needs to prevent the leaching of the bioreceptor out of the matrix. Biopolymers are a class of compounds, which satisfy many of the aforementioned prerequisites and hence find wide applications in the development of biosensors [8].

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Recently, with the development of nanotechnology, noble metal nanoparticles (NPs) have been widely used for the design of new biosensors/biosensing platforms due to their unique spectral and optical properties [9, 10]. Therefore, different noble metal NPs such as Ag, Au, Pt, and Pd have been used in the development of many types of biosensors in different areas, such as disease diagnosis, cancer, and other clinical and electrochemical applications [11]. Among noble metal NPs, in particular, Au NPs are one of the most preferred by researchers for biosensor applications due to their optical, electrical, and biocompatibility properties [12]. Different biosensors with good analytical performances, such as enzyme sensors, DNA sensors, and immunosensors have been designed using Au NPs [13–15]. One of the most important parameters for the synthesis of noble metal NPs is the selection of the support/stabilizer. An ideal stabilizer should be biodegradable, biocompatible, and have reactive functional groups for immobilization of metal NPs for various biosensor applications. Among the stabilizers used, biopolymers fabricated by living organisms are the most important support materials. Biopolymers can be classified into three main groups according to their monomer units: (1) polynucleotides, which consist of nucleotide monomers, (2) polypeptides, which consist of amino acids, and (3) polysaccharides, which are carbohydrates such as chitosan, cellulose, and pectin. Among these, polysaccharides have very suitable polymeric matrices for immobilizing different noble metal NPs and constructing biosensors. This is because polysaccharides exhibit large surface areas, strong adsorption capacity, high thermal and mechanical stability, and susceptibility to various chemical reactions. Therefore, polysaccharide-based metal NPs have been extensively used in the preparation of different biosensors [16]. Generally, biopolymers, such as chitosan, alginate, cellulose, pectin, gelatin, and acacia gum, have been widely used in the development of biosensors. As reported in several studies, the preparation of metal NPs is vital for biosensors/biosensing applications and biopolymers have been shown to be one of the ideal supports compared to other macromolecules for the fabrication of metal NPs.

9.2

Types of biosensors

Biosensors can be categorized according to the mode of physicochemical transduction or the type of biorecognition element. Based on the transducer, biosensors can be categorized into electrochemical, piezoelectric, thermal, and optical biosensors [17].

9.2.1

Electrochemical biosensors

Electrochemical biosensors can also be classified into amperometric biosensors (which measure the current generated during oxidation or reduction of electroactive products or reactants), potentiometric biosensors (which measure the potential of the biosensor electrodes with respect to a reference electrode),

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FIG. 9.3 Representation of an electrochemical biosensor [18].

and conductometric biosensors (which measure the alterations in conductance due to the biochemical reaction) [18]. Fig. 9.3 shows an electrochemical biosensor [18]. Electrochemical biosensors are the most widely considered biosensors, as they afford the advantages of low detection limit, specificity, ease of construction, and operation. Considering the recent developments in electronic instrumentation, these biosensors can be miniaturized as lab-on-chip devices for in vivo monitoring or as handheld devices for on-site monitoring [18].

9.2.2 Optical biosensors Optical biosensors are based on the measurement of light absorbed or emitted due to a biochemical reaction. Optical biosensors are prepared by different optical methods, such as absorption, fluorescence, luminescence, and surface plasmon resonance (SPR) [19]. Among these, the colorimetric biosensors are widely utilized because of the ease of detection of the visible color change displayed by these biosensors. Plasmonic properties of noble metal films are used for SPR-based biosensors. The advent of fiber optics technology has given a boost to the improvement of different optical biosensors [19]. These biosensors offer a fast, very sensitive, real-time, and high-frequency monitoring without any time-consuming sample concentration and/or sample pretreatment steps. However, optical biosensors have excessive potential applications in the areas of environmental monitoring, food safety, drug development, biomedical research, and diagnosis. The application of optical biosensors in the fields of controlling the environmental pollution and early warning is still in the initial stages [20–26]. Fig. 9.4 shows an optical biosensor [19].

9.2.3 Thermal biosensors Thermal biosensors are based on the measurement of the thermal changes happening on biochemical recognition. Most biochemical reactions include a change in enthalpy, and the heat changes can be measured by sensitive thermistors [8]. In other words, thermometric biosensors use the essential property of

FIG. 9.4 Representation of an optical biosensor [19].

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biological reactions such as absorption or evolution of heat [27]. Thermal biosensors have attracted less attention. Disadvantages such as difficult thermosetting, very weak sensitivity, or nonspecific heating effects result in poor reputation. Actually, this trend is amazing since thermal biosensors have influenced the entire biosensor research over and over [28]. Thermal biosensors have various advantages [28], such as. – Thermistors have very good long-term stability since there is no chemical contact between the transducer and the sample. – Thermistors are cheap bulk products. – Measurements are not disturbed by variable optical or ionic sample characteristics. – In some cases, thermal biosensors work without difficulty and interferenceprone, multienzyme systems such as disaccharide analysis. – Thermal biosensors have found various applications.

9.2.4 Piezoelectric biosensors Piezoelectric biosensors measure the mass changes occurring due to biomolecular interactions. Piezoelectric crystals are employed to measure the mass change, which affects the change in the oscillation frequency of the piezo crystal [8]. The piezoelectric biosensors recording hybridization have excellent properties including a rapidly established equilibrium of interaction and capturing of the single-stranded chain from the solution, good sensitivity, and low interference. The excellent analytical performance of the described piezoelectric biosensors is, of course, a condition for the implementation of this technology [8].

9.3 Properties of biopolymers for biosensing Biopolymers are polymeric biomolecules formed by living organisms. Unlike their synthetic equivalents with a modest and random structure, biopolymers have a three-dimensional structure, which is vital for their function. Biopolymers display excellent monodispersity in comparison to polydispersity shown by the synthetic polymers. Biopolymers are environmentally friendly compounds because they are transformed to their constituents by microorganisms or enzymes. The absolute product of the natural decomposition of these biopolymers can be reabsorbed in the environment, leaving the lowest carbon footprints. Biopolymers, such as chitosan, alginate, cellulose, pectin, gelatin, and acacia gum, have been widely applied in the development of biosensors. These biopolymers possess several advantages as biosensors, which will be discussed in the following sections [8].

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Biocompatibility

Given their natural source, biopolymers have a favorable interaction with living systems and help to protect the biorecognition unit of the biosensor. The high water content in biopolymer hydrogels offers a quasi-native environment, which could prevent the denaturation of the embedded bioreceptor [29]. For example, Ding et al. developed an Au NPs-chitosan composite film for the decoration and electrochemical study of K562 leukemia cells. The cells were capable of adhering to the biopolymer composite film, preserving their viability and multiplying on the film upon extended culture [16]. In another example, Amarnath and co-workers investigated the utilization of biopolymer pectin to stabilize polyaniline NPs and form polyaniline-Ag nanocomposite (Ag@PANI-PEC) [30]. In addition, owing to the use of biopolymer PEC, the Ag@PANI-PEC displayed biocompatibility and the presence of Ag NPs on Ag@PANI-PEC afforded antibacterial property. In vitro biocompatibility results using the MTT test showed that the cell capability increased with an increase in the amount of pectin. The pectin stabilized polyaniline NPs were further applied in the development of glucose biosensors and the detection of bacteria [31, 32].

9.3.2

Immobilization matrix

Biopolymers act as excellent immobilization matrices for trapping biorecognition units such as enzymes and whole cells. The immobilization can be performed using physical trap of the biological sorts in the biopolymer [8]. Biopolymers cause excellent adhesion of the composite to the electrode for performing sensing measurements. They have good water permeability and thus permit effective to-and-fro diffusion of electrolytes across the biosensor surface. These features reduce the problems associated with the diffusion barrier [8].

9.3.3

Bioresponsiveness

Several biopolymers are bioresponsive, that is, they display alterations in their properties owing to incentives by biologically related molecules, such as glucose, ATP, enzymes, and antibodies [33]. Such a trend improves trigger changes in the molecular interactions in the biopolymer, which finally translate into macroscopic responses, such as solution-to-gel transitions, swelling, or downfall of the biopolymer. Bioresponsive biopolymers are capable of answering selectively to key molecules [8].

9.4

Biopolymer-based metal nanoparticles for biosensing

Biopolymers alone are not suitable for biosensor applications because of their low mechanical and chemical resistance. Biopolymers are premade polymers,

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which tend to absorb water. Many of these problems can be solved by making composites of biopolymers with functional materials such as metal and metal oxide NPs [8].

9.4.1 Chitosan-based biosensors In the past few years, chitosan (CS) has been extensively applied in the preparation of biosensor films owing to its renewable, biodegradable, and nontoxic nature [33, 34]. Chitosan is a significant natural polysaccharide for immobilization of various materials such as metal and metal oxide NPs due to its good film forming capability, mechanical strength, high permeability, biocompatibility, nontoxicity, easy accessibility, and economy. The presence of dNH2 and dOH groups in CS structure (Fig. 9.5) makes it more versatile and offers hydrophilic conditions for the biomolecules [35–37]. Several chemical properties of chitosan are shown in Fig. 9.6 [35]. Considering the multiple functionalities of chitosan (presence of NH2 and OH groups), it can be cross-linked with nanomaterials in film forming [38–40]. Metal and metal oxide NPs such as gold, silver, iron oxide, zinc oxide, and cerium oxide have been proposed in several studies as promising matrices for sensing applications [41–44]. Iron oxide NPs have attracted much attention as electrochemical transducers owing to their

FIG. 9.5 Structure of chitosan [35].

FIG. 9.6 Schematic representation of chemical properties of chitosan [35].

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capability to improve conductivity, superparamagnetic nature, signal amplification, and favorable microenvironment for protein adhesion. Therefore they enhance sensitivity and selectivity. Furthermore, the problems of aggregation and fast biodegradation of iron oxide nanoparticles (IONPs) on a matrix can be solved by dispersing IONPs in a biopolymer matrix of chitosan to make them appropriate for biosensor applications [45]. There are several reports on chitosan-based metal NPs as appropriate biosensors for various applications. For example, Kaushik et al. developed the synthesis method for an efficient glucose biosensor based on chitosan [46]. They used dispersion of Fe3O4 NPs in chitosan (CH) solution to make a nanocomposite film on indium-tin oxide (ITO) glass plate (CH-Fe3O4/ITO) and glucose oxidase (GOx) decorated on CH-Fe3O4/ITO electrode (Fig. 9.7). Chitosan used as a stabilizing agent prevents the aggregation of Fe3O4 NPs without changing its optical and electrical properties. The decorated GOx shows good catalytic property to glucose. In addition, Fe3O4 NPs not only provide a friendly environment to decorate GOx in the biosensing interface but also increase the electron transfer between analyte (glucose) and CH-Fe3O4/ITO electrode surface. The synthesized biosensor showed both excellent reproducibility and long-term stability.

Fe3O4 nanoparticle

Chitosan + +

+

+ –

+

– + – –

+

+ ITO +

+

+

+

O H HO

O HO

NH

+

–

NH2 NH2 NH2 NH2

GOx/CH-Fe3O4/ITO bioelectrode

H

H H O

H H

– + – – + –

CH3

OH H

NH2 GOx

+

+

HO

–

– + –

NH2

O

H

NH2

0.8

OH

0.2

Chitosan

FIG. 9.7 Suggested mechanism for formation of CH-Fe3O4 nanocomposite and decoration of GOx on nanocomposite matrix. (Reproduced with permission from Kaushik A, Khan R, Solanki PR, Pandey P, Alam J, Ahmad S, Malhotra BD. Iron oxide nanoparticles-chitosan composite based glucose biosensor. Biosens Bioelectron 2008;24:676–683.)

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The electrochemical sensing of cholesterol through ChOx/PANI-Au-CH/ ITO as an efficient biosensor was reported by Srivastava and co-workers [47]. They used chitosan with the PANI-Au nanocomposite as the decoration matrix for cholesterol oxidase (ChOx) to develop a sensitive and stable cholesterol biosensor. Chitosan is applied as a stabilizing agent for enzyme immobilization owing to its good film production capability, mechanical strength, biocompatibility, cost effectiveness, etc. In addition, Huang et al. investigated an efficient and simple dopamine (DA) biosensor based on Au@carbon dots (Au@CDs)-chitosan-modified glassy carbon electrode (Au@CDs-CS/GCE) [48]. The CDs had carboxyl groups with negative charges, which not only afforded excellent stability but also allowed interaction with amine functional groups in DA over electrostatic interaction to multiply recognition of DA with high specificity. Therefore Au NPs could make the surface of the electrode more conductive. In another study, Atif and colleagues investigated the synthesis of a potentiometric urea biosensor based on Fe3O4-CH nanobiocomposite by the decoration of the urease enzyme [49]. The experimental results showed that the biosensor had an excellent performance in terms of stability, sensitivity, selectivity, and reproducibility since the reasonable biosensor presents an output response of approximately 12 s. Furthermore, the synthesized biosensor can be used as an efficient device for monitoring and balancing urea concentrations for various industrial applications, such as the food industry, environmental safety, pharmaceutical industry, and fabrication of fertilizers, its most noteworthy applications being in clinical and biomedical analysis. Furthermore, Wang et al. developed the synthesis of an efficient and novel tyrosinase biosensor based on Fe3O4 NPs-chitosan nanocomposite for the detection of phenolic compounds, which are important contaminants [50]. The experimental results displayed a high loading of tyrosinase enzyme due to the large surface area of Fe3O4 NPs and the porous morphology of chitosan. The synthesized biosensor was applied to determine phenolic compounds via amperometric detection of the biocatalytically liberated quinone at 0.2 V vs saturated calomel electrode (SCE). The tyrosinase biosensor showed excellent reproducibility and stability. In another work, Zeng and co-workers investigated a glucose biosensor by functionalization of graphene (GR) with chitosan (CS) to enhance its biocompatibility and hydrophilicity for the fabrication of biosensors [51]. The CSgrafted GR (CS-GR) rendered water soluble nanocomposites, which were simply immobilized with palladium nanoparticles (Pd NPs) by using in situ reduction. A new glucose biosensor was then established over covalently decorating glucose oxidase (GOD) on a glassy carbon electrode modified with the PdNPs/CS-GR nanocomposite film. Given the synergistic effect of Pd NPs and GR, the Pd NPs/CS-GR nanocomposite film displayed good electrocatalytical activity toward H2O2 and facilitated high loading of enzymes.

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In addition, Şenel et al. successfully developed an efficient, simple and economic method for the synthesis of a novel H2O2 biosensor based on horseradish peroxidase (HRP) decorated into CoFe2O4-chitosan nanocomposite for the detection of hydrogen peroxide (Fig. 9.8) [52]. For this purpose, they used entrapping of HRP into the CoFe2O4-chitosan nanocomposite film and the decorated enzyme could maintain its bioactivity. The synthesized biosensor displayed a fast amperometric response to H2O2. Other examples of chitosan-based metal NPs for biosensing applications are listed in Table 9.1.

9.4.2

Cellulose-based biosensors

Cellulose is a fibrous, renewable biopolymer containing β-1,4-linked anhydroD-glucose units. It is the essential structural constituent of plants and can be formed by marine animals, algae, fungi, bacteria, invertebrates, and amoeba, making it the most abundant organic polymer in the nature [71, 72]. Cellulose is a polysaccharide broadly present in the environment, for example, in cotton, wood, cereals, fibers, and bacteria. There are several kinds of cellulose, which are appropriate for the preparation of nanocomposites, namely vegetable cellulose (VC), bacterial cellulose (BC) and nanofibrillated cellulose (NFC). Although they have similar chemistry and molecular structures, the diverse types of cellulose display significant differences in terms of morphology and mechanical behavior. For example, BC and NFC are composed of fibers with nanosized dimensions compared to VC, which might impart novel features, and in some cases changes to the subsequent nanocomposite materials [73, 74]. While cellulosic materials display unique and advantageous properties, they have poor electrical conductivity and cannot offer suitable sensitivity for biosensor applications. Additionally, cellulose is very hydrophilic and is not compatible with some sensing molecules. Therefore it must be modified for application as an appropriate supporting material for biosensor applications [75]. A combination of biomolecules with nanomaterials can be accomplished through chemisorption on their surface or using a bifunctional linker [76]. Metal and metal oxide NPs have attracted growing attention in recent years owing to their specific properties and wide applications in the field of biosensors, catalysis, antimicrobials, and optoelectronics [77–79]. Among different metal and metal oxide NPs, Au NPs are one of the most exciting NPs due to their high catalytic activity in a diversity of chemical reactions [80]. Cellulose-based biosensors have a wide range of applications in different fields, such as medical diagnosis, environmental control, and food safety. It is significant in the development of materials, which display excellent electron transferability, biocompatibility, stability, and easy availability toward the analyte [81]. Cellulose-based sensors are low-cost, disposable, and eco-friendly. These materials transport liquids via capillary action with no necessity to

FIG. 9.8 Chitosan, chitosan-CoFe2O4 nanocomposite and HRP-chitosan-CoFe2O4 nanocomposite-coated glassy carbon electrode (GCE) [52].

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TABLE 9.1 Different kinds of chitosan-based metal NPs for biosensing applications for detection of analytes. Entry

Biosensor matrix

Analytes

Response time

Ref.

1

Chitosan/gold NPs film

Glucose