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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

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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
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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 bio-
degradable plastics include polybutylene adipate terephthalate (PBAT) and
polycaprolactone (PCL). Some plastics such as polylactic acid (PLA), polyhy-
droxyalkanoates (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 micro-
organisms to form carbon dioxide, methane, water, biomass and various other
natural substances, which can be easily eliminated. The biodegradation mech-
anism 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 gen-
erally 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 com-
mercial 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 conven-
tional and biobased plastics. In addition, there are some logos showing the capa-
bility 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 mate-
rials in mass production are low-price, processability, appropriate performance,

Bioplastic symbol

vs. vs.

Recyclable 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, mate-
rial choices, and eventually foaming. The variety of biomaterials, number of
material combinations, processing technologies, and applications offer tremen-
dous opportunities. However, there are many challenges, which must be met
during the development of bioplastics to meet the demands of different indus-
trial sectors [10, 14, 16].

1.2 Degradation of bioplastics

A plastic can be considered biodegradable if a significant change in the chem-
ical 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., photodegrada-
tion) to shorter oligomers, dimmers, or monomers. These shorter units are small
enough to pass through the cell walls of microorganisms and be used as sub-
strates 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 1 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 mol-
ecules, preparing them for further degradation by intracellular enzymes. As bio-
degradation 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 compo-
nents 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 objec-
tive 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, inor-
ganic compounds, and biomass at a rate consistent with other known compost-
able 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 biodegrada-
tion could be achieved at the interface of water-sediment since the environmen-
tal 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

Habitats Temperature

Bioplastic
biodegradation
in aquatic
systems

Micro Polymer
organisms 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, photosyn-
thetic bacteria, archaebacterial, and lower eukaryotic present in different envi-
ronmental 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 con-
taining 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 enzy-
matic degradation of bioplastics [19, 26, 27]. Depolymerase enzymes from Rho-
dospirillum rubrum and Bacillus megaterium are responsible for degrading
polyhydroxybutyrate (PHB) [27, 28]. Degradation of PHB results in the transi-
tion of PHB granules in the intracellular compartment from an amorphous to a
denatured semicrystalline state. Lemoigne first discovered that Bacillus mega-
terium releases PHB in an aqueous environment. It is now known that such
secretion is due to the activity of PHB depolymerase. The commercial produc-
tion 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 1 7

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 fumi-
gatus, Mortierella sp., Doratomyces microspores present in both soil and com-
post 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 micro-
organisms 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 bur-
ied 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 adja-
cent 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 poly-
merization 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 Karaman-
lioglu 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 Bio-
deterior Biodegradation 2014;95:301–310.)
TABLE 1.1 Isolated bioplastic-degrading microorganisms from different environments.
Environmental Type of Name of
conditions microorganism Microorganism bioplastic Ref.
Soil Bacteria Amycolatopsis sp., Amycolatopsis thailandensis, Thermoactinomyces sp., PLA [33–37]
Laceyella sp., Nonomuraea sp., Bacillus licheniformis, Actinomadura
keratinilytica, Micromonospora sp., Streptomyces sp., Bortetella petrii,
Paenibacillus amylolyticus, Paenibacillus sp.
Bacteria Bacillus stearthermophilus PDLAa [38]

Bacteria Streptomyces bangladeshensis PHB [39]

Bacteria Pseudomonas aerogusina, Bacillus subtilis PHA [40]
Bacteria Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas PHA [41, 42]
aeruginosa, Pseudomonas sp.
Bacteria Pseudomonas lemoignei PHB [43]
b
Bacteria Actinomadura sp. PHBV [44]
Bacteria Clostridium acetobutylicum Starch-based [45]
c
Bacteria Laceyella sacchari PLLA + Starch- [46]
based
Bacteria Stenotrophomonas Nylon 4 (PA) [47]
Bacteria Amycolatopsis sp., Streptomyces sp., Streptomyces thermovioaceus, PCL [31, 37]
Paenibacillus sp.
Bacteria Paenibacillus amylolyticus PCL [33]
Continued
TABLE 1.1 Isolated bioplastic-degrading microorganisms from different environments—cont’d

Environmental Type of Name of

conditions microorganism Microorganism bioplastic Ref.
Bacteria Amycolatopsis sp., Streptomyces sp., Paenibacillus sp., Paenibacillus PBS [33, 37]
amylolyticus
Bacteria Paenibacillus amylolyticus, Pseudomonas aeruginosa, Burkholderia PBSAd [26, 33,
cepacia, Bacillus pumilus 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, PHB [52]
Cogronella sp., Acremonium recifei
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 PBS [37,
niger, Fusarium solani 54–56]
Fungi Aspergillus clavatus PESe [57]

Compost/soil 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. PHB [52, 61]
Mycobacterium sp., Nocardiopsis sp.
Bacteria Streptomyces sp. PCL [61]
Bacteria Pseudomonas putida, Leptothrix sp., Variovorax sp. PHA [23]

Bacteria Enterobacter sp., Bacillus sp., Gracilibacillus sp. PHB [25]

b
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]
e
Bacteria Streptomyces sp. PES [61]
e
Bacteria Bacillus pumilus PES [26]
a
Poly-D-lactide.
b
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.
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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249 and

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