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Textbook Ebook Biopolymer Based Metal Nanoparticle Chemistry For Sustainable Applications Mahmoud Nasrollahzadeh All Chapter PDF
Textbook Ebook Biopolymer Based Metal Nanoparticle Chemistry For Sustainable Applications Mahmoud Nasrollahzadeh All Chapter PDF
Mahmoud Nasrollahzadeh
Department of Chemistry, Faculty of Science, University of Qom,
Qom, Iran
Elsevier
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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].
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.
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].
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
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].
Habitats Temperature
Bioplastic
biodegradation
in aquatic
systems
Micro Polymer
organisms shape
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].
1.3.1 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]
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 suf-
fers 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 add-
ing 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 maxi-
mum 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 copoly-
mer 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 nutri-
ents, including sulfate, magnesium, nitrogen, phosphate, and oxygen. Depend-
ing 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 appli-
cations, and other disposable items such as bottles, cups, plates, and cutlery,
which can be composted but not recycled [13].
Application of biopolymers in bioplastics Chapter 1 15
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 thermo-
plastic 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 bot-
tle. 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 insol-
uble in water and exhibits a high degree of polymerization. Being chiral, the
monomers can be used for the synthesis of complex chiral pharmaceutical com-
pounds. 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
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 applica-
tion 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 com-
posites 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].
I.
II.
III.