A Comprehensive Review On Recent Advances in Preparation, Physicochemical Characterization, and Bioengineering Applications of Biopolymers
A Comprehensive Review On Recent Advances in Preparation, Physicochemical Characterization, and Bioengineering Applications of Biopolymers
A Comprehensive Review On Recent Advances in Preparation, Physicochemical Characterization, and Bioengineering Applications of Biopolymers
https://doi.org/10.1007/s00289-022-04443-4
REVIEW PAPER
Abstract
Biopolymers are mainly the polymers which are created or obtained from living
creatures such as plants and bacteria rather than petroleum, which has traditionally
been the source of polymers. Biopolymers are chain-like molecules composed of
repeated chemical blocks derived from renewable resources that may decay in the
environment. The usage of biomaterials is becoming more popular as a means of
reducing the use of non-renewable resources and reducing environmental pollu-
tion produced by synthetic materials. Biopolymers’ biodegradability and non-toxic
nature help to maintain our environment clean and safe. This study discusses how
to improve the mechanical and physical characteristics of biopolymers, particularly
in the realm of bioengineering. The paper begins with a fundamental introduction
and progresses to a detailed examination of synthesis and a unique investigation of
several recent focused biopolymers with mechanical, physical, and biological char-
acterization. Biopolymers’ unique non-toxicity, biodegradability, biocompatibility,
and eco-friendly features are boosting their applications, especially in bioengineer-
ing fields, including agriculture, pharmaceuticals, biomedical, ecological, industrial,
aqua treatment, and food packaging, among others, at the end of this paper. The pur-
pose of this paper is to provide an overview of the relevance of biopolymers in smart
and novel bioengineering applications.
* Nabakumar Pramanik
[email protected]
1
Department of Chemistry, National Institute of Technology, Arunachal Pradesh, Jote,
Arunachal Pradesh 791113, India
2
Department of Chemistry, Nalanda College of Engineering, Nalanda, Bihar 803108, India
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Graphical abstract
The Graphical abstract represents the biological sources and applications of biopol-
ymers. Plants, bacteria, animals, agriculture wastes, and fossils are all biological
sources for biopolymers, which are chemically manufactured from biological mon-
omer units, including sugars, amino acids, natural fats and oils, and nucleotides.
Biopolymer modification (chemical or physical) is recognized as a crucial technique
for modifying physical and chemical characteristics, resulting in novel materials
with improved capabilities and allowing them to be explored to their full potential
in many fields of application such as tissue engineering, drug delivery, agriculture,
biomedical, food industries, and industrial applications.
Abbreviations
PA Polyamide
PVC Polyvinylchloride
PP Polypropylene
PE Polyethylene
PMMA Poly(methyl methacrylate)
PGA Poly(glycolic acid)
PLA Poly(lactic acid)
PCL Polycaprolactone
PHB Polyhydroxy butyrate
PPF Polypropylene fumigates
PDS Polydioxanone
DS Degree of substation
DDSA Dodecenyl succinic anhydride
CDs Cyclodextrins
PPV Poly(p-phenylenevinylene)
POB Poly-3-hydroxybutyrate
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PAC Polyaluminum-chloride
COD Chemical oxygen demand
SS Suspended solids
PA Polyamide
PEGDA Poly(ethylene glycol) diacrylate
MCC Microcrystalline cellulose
BNC Bacterial nanocellulose
LDPE Low-density polyethylene
EAA Poly(ethyleneco-acrylic acid)
HPMC Hydroxy propyl methyl cellulose
CAB Cellulose acetate butyrate
PHAs Polyhydroxyalkanoates
PVAP Poly(vinyl alcohol phosphate)
TPP Tripolyphosphate
GSH Glutathione
PEG Poly(ethylene oxide)
CaP Calcium phosphate
SC Supercapacitor
PHA Polyhydroxyalkanoates
MO Methyl orange
GG Guar Gum
XG Xanthan Gum
CN Cellulose nitrate
MC Methyl cellulose
AgNPs Silver oxide nanoparticles
5-FU 5-Fluorouracil
Introduction
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utilize novel materials, and products should be produced based on those features.
They are beginning to appear as a result of this for being more responsible in car-
ing for the planet we live in. New biodegradable polymers with good skeletal and
mechanical characteristics have been the focus of recent study. Biopolymers orig-
inating from natural organisms have been manufactured in enormous quantities.
The biodegradability of biopolymers has been linked to the presence of certain
microorganisms and enzymes with distinct degradable characteristics [3]. The
biodegradability of biopolymers is facile, because the biopolymers are bearing
the oxygen and nitrogen atom in their skeletal backbone. Biopolymer is converted
to CO2, water, biomass, humid water, and other natural components during bio-
degradation. Biodegradable polymers offer a wide range of applications in bioen-
gineering, including tissue engineering, drug delivery systems, and wound dress-
ing, among others [4]. Biopolymers have a distinctive helical structure, stiffness,
charge-free chains, and a strong resistance to salt and cold; thus, they thicken and
stabilize better under harsh pool conditions [5].
Monomers are small molecules, most of which are organic, that may combine
with other monomers to produce larger molecules, known as polymers. Every
monomer molecule has the ability to make chemical connections with at least
two other monomers. Polymers are a type of synthetic material made up of sev-
eral smaller pieces known as monomers. Polymers are chains of monomeric units
with an undetermined number of them. Polymerization is a chemical reaction
in which a large number of monomer molecules combine to produce a polymer
(Fig. 1). A polymerization can yield macromolecules with a linear or branching
structure. They can also take the form of a three-dimensional complicated net-
work. The basic approach for converting monomer to polymer is shown in the
diagram depicted below.
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Natural biopolymer
Protein
Proteins are big, complex molecules that serve a number of important functions in
the human body. Proteins are made up of hundreds or thousands of smaller com-
ponents known as amino acids that are linked in lengthy chains. They perform the
majority of the work in cells and are essential for the construction, function, and
control of the body’s tissues and organs. A protein is made up of 20 distinct types
of amino acids that may be combined in different ways. Plant proteins, such as those
Monomers
(Basic Unit)
Polymers
(Occurs by Polymerization
of Monomers)
Biopolymers (naturally
occurring compounds produced
by green plants, animals,
microbes, and fungus during
their life cycles)
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found in foods like wheat, corn, and soybeans, are more immunogenic than animal
proteins. Plant proteins have a low molecular weight and a large net negative charge,
which makes them ideal for effective medication delivery. Proteins are hydrophilic
in nature because they include polar amino acids, which attract cells sympatheti-
cally. Natural biopolymers such as collagen, silk, and fibrinogens are accessible;
commercially available collagens are utilized as injections for skin sensitization and
antibody responses, as well as immunological uses [7]. Proteins’ main structure is
made up of peptide bonds and disulfide bonds. A peptide bond is produced when the
carboxyl group of one molecule combines with the amino group of the other mole-
cule, releasing a molecule of water in the process (H2O). This is a condensation pro-
cess (also known as a dehydration synthesis reaction) that happens between amino
acids. The mechanism of a peptide bond is seen in the diagram below (Fig. 3).
Polysaccharide
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Synthetic biopolymer
Synthetic biopolymers are polymers that have been modified from natural polymers
or chemically produced from synthetic monomers such that they can degrade natu-
rally without leaving residues that are hazardous to living things and the ecosystem.
Synthetic biopolymers have received a lot of interest in recent years due to their
significant advantages over natural polymers in terms of stability and flexibility
to fit a wide range of applications. Synthetic biopolymers, on the other hand, are
preferred over synthetic polymers due to their biodegradable qualities and environ-
mental safety. Synthetic biopolymer synthesis may now be tuned to match specific
applications thanks to breakthroughs in new molecular designing tools and polymer
chemistry. Because of some of its unique qualities, including as stability, controlled
release, no immunogenicity, and removal from the body, synthetic biopolymers have
found one of their most important uses in the medical industry, which matches their
application in human bodies. In comparison with ceramic and metal particles, syn-
thetic biopolymers are easier to produce in many shapes and sizes. They are used
in industry and have cheap production costs, and they play a vital part in our daily
lives. Enzymes and live cells generally carry out biopolymer synthesis to the target
biopolymer molecules [9]. Synthetic biopolymers are generally classified into two
categories, i.e., non-biodegradable biopolymers and degradable biopolymers.
Non‑biodegradable biopolymer
Biodegradable biopolymer
Biodegradable polymers are those that breakdown when exposed to the elements.
Biopolymer’s biodegradability makes it a viable alternative for replacing petrochem-
ical-based packaging materials. Synthetically biodegradable polymers are made in a
controlled environment and have consistent skeletal and mechanical characteristics,
such as rigidity and accomplished modulus. When compared to biological scaffolds,
they are less expensive to make and promote contact with endothelial cells [11].
Artificially generated biodegradable synthetic polymers serve an important role in
tissue engineering and other biological fields. The decomposition of synthetic poly-
mers is accomplished by simple hydrolysis [12]. PGA, PLA, PCL, PHB, PPF, PDS,
etc., which are the synthetically biodegradable polymers have been used in medi-
cine and pharmaceuticals process. The hydrophilicity of PGA is extensively greater
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than that of PLA, leading to higher crystallinity; thus, it was used as evolutionary of
entire initially synthetic adsorbable structure [13].
Properties of biopolymers
Biopolymers are a type of polymer made from biological resources. Because of their
abundance, high tolerance, high thermal stability, non-toxicity, antibacterial activ-
ity, antifungal activity, biocompatibility, biodegradability, and other unique qualities
such as strong adsorption capacities and ease of functionalization, they have been
studied for a variety of applications in the industrial, biomedical, pharmaceutical,
drug-delivery, tissue engineering, medications, tablets, adhesives, paper, food, cot-
ton, and rayon sectors, including sorption [5].
• Esterification of biopolymers
• Dehydration of biopolymers
• Polycondensation of biopolymers
• Hydrolysis of biopolymers
• Granulation of biopolymers etc.
Esterification of biopolymer
Esterification is a chemical process that occurs during the ester’s synthesis. Esterifi-
cation is a chemical reaction that produces an ester (RCOOR) and water by combin-
ing alcohol (ROH) with an organic acid (RCOOH). Through an esterification reac-
tion between a carboxylic acid and an alcohol, this chemical reaction produces at
least one ester product. The esterification of following biopolymer starch, cellulose,
and hemicelluloses is given below.
Esterification of cellulose
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Esterification of starch
As an esterification reagent, acetic acid and acetic anhydride are used to make starch
acetate. The pH, time interval, and the presence of a catalytic agent all influence the
incorporation of acetyl groups into starch molecules. For low (0.01–0.2), medium
(0.2–1.5), and high (1.5–3) acetyl starch, the degree of substation (DS) ranges
from 0.01 to 0.2. The alkenyl succinic anhydride DDSA is a unique alkenyl suc-
cinic anhydride. The esterification of DDSA starch in an aqueous solution produces
a water-resistant product that is widely utilized in the film and paper industries [15].
Esterification of hemicellulose
Hemicellulose is a polymer present in plant dell cells and cell walls. Hemicelluloses,
a biopolymer used to make films and hydrogels, has been employed in biomedical
applications such as medication delivery and tissue engineering. Chemical synthe-
sis of hemicellulose yields furfural, xylitol, ethanol, and lactic acid. The eco-friend-
liness, low hydrophobicity, higher electrochemical and thermal balance, and faster
reaction rate of biomaterials such as cationic hemicelluloses, carboxymethyl hemi-
celluloses, lauroylated hemicelluloses, and acylated hemicelluloses are the homog-
enous upgradation of hemicellulose. The esterification of xylan-rich hemicelluloses
with maleic anhydride in the presence of a catalyst, LiOH, in an ionic liquid medium
under homogeneous conditions with a degree of substation (DS) of (0.095–0.75) has
a wide range of applications in agriculture, food, waste water treatment, and phar-
maceutical industries [16].
Dehydration of biopolymers
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of biopolymers. The shrinking of the film during the dehydration process causes a
change in the structure of the polymer film. Adhesives, coatings, food industry, and
drug delivery in the pharmaceuticals sectors have all leveraged the kinetics of dehy-
dration of diverse biopolymers [19].
Polycondensation of biopolymers
Hydrolysis of biopolymer
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Granulation of biopolymer
The biopolymer’s granular production method has become speculative and uncer-
tain. The bio granulation of biopolymers dominates the prospective applicabil-
ity, which includes greater toxicity tolerance, treatment of high-loaded carbon/
nutrient load pollutants, high-grade settleability, and increased biomass with hold-
ing, among other things [25]. Granulation produces EPS, which include proteins,
lipids, humic acids, polysaccharides, and nucleic acids that keep microorganisms
together. For full granulation of biopolymer, a long time period of roughly 308 days
is required, which accelerates through two phases, phase-1 and phase-2. Phase
1 takes day 0 ~ 182–220 for low granular mechanism, whereas phase 2 takes pale
after 182–220 days for steady granular mechanism. Granulation under local micro-
bial composition improves the stability of ALE, which aids in subsequent qualitative
research for industrial use [26].
Chitosan (CS)
Rouget, who discovered chitosan in 1859, discovered it when chitin was heated in
an alkaline medium. However, Hoppe-name Seyler’s was first used in 1894 [27].
CS is an a linear amino polysaccharide biopolymer derived naturally from shrimp
and crab exoskeletons. Hoppe-alkaline Seyler’s deacetylation of chitin to produce
chitosan. CS is a heterogeneous polymer with a well-defined chemical structure that
consists of 1–4 connected 2-acetamido-2-deoxy-β-D-glucopyranose and 2-amino-
2-deoxy-β-D-glucopyranose. The structure and processing of chitosan is given in
Fig. 4.
CS’s biocompatibility and degradability make it useful in biomedical applications
such as wound healing and tissue engineering. CS’s unique structural and antibac-
terial qualities make it suitable for use in film or membrane fabrication as well as
medication administration. Chitosan is water insoluble but soluble in acidic media.
In the presence of a nucleophilic amino group, Chitosan has three reactive groups
that cause a nucleophilic substitution process. CS’s potential actions, such as dis-
infection, non-toxicity, antibacterial, and antimicrobial qualities, make it a good fit
for biopesticides and the food industries as cited in Fig. 5 [28]. When human serum
albumin is exposed to peroxyl radicals, CS has a similar potency to vitamin C in that
it prevents the formation of carbonyl and hydroperoxide groups. Because CS has a
low molecular weight, it limits neutrophil activation and serum albumin oxidation,
which reduces oxidative stress. The availability of high molecular weight chitosan
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will lower cholesterol (TC) and apolipoprotein (AI) levels while increasing lipopro-
tein density (HDL) [29].
With increasing antimicrobial action, the degree of deacetylation (DDA) of CS
rises. CS is a biomolecule with a DDA of 70 percent or less, whereas water-soluble
chitosan has a DDA of 50 percent or less. Protonation is facilitated by the amino
group (R-NH2) rather than the acetamido group (R-NH-C(O)-CH3) at the C2 posi-
tion of chitosan, which has a higher DDA value. When the protonation half-life
period occurs, chitosan delivers a positive charge, resulting in a reduction in pH
when the protonated group attaches to its cytoskeletal molecular body [30]. CS is
a polysaccharide-rich in bonding hydrogen that degrades before reaching the glass
transition. CS solution is used to make films, gels, fibers, and sponges as a result of
this phenomenon. The dissociation potential of CS in acidic solution will be dem-
onstrated by its polyelectrolyte charters and polycationic nature (pKa). The value
of pKa at zero charge of chitosan varies from 6.46 to 7.32, depending on the degree
of acetylation (DA) [31]. CS, which is found in mango and also in guava, inhibits
the growth of bulk bacteria, resulting in a decrease in weight and respiration rate
[32]. CS-based hydrogels are used for sensory detection. Hydrogel is a biocom-
patible biopolymer with a high fluid absorbability property that may be utilized
to make a base biosensor. A CS-based hydrogel was used to detect certain target
chemicals electrochemically. Furthermore, because to their difficult cell–matrix
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interaction, chitosan-based nanofibers play a significant role in drug delivery and tis-
sue engineering, as evidenced by the formation of doxorubicin (DOX)-incorporated
hydroxyapatite (HAp)-chitosan (CS) nanocomposite induced on osteosarcoma cells
[33]. Life cycle of other biopolymers is depicted in Figs. 6, 7, and 8.
CS derivatives are used in the textile industry for antimicrobial finishing of bioac-
tive textiles and in the paper industry to increase paper weight strength [34]. Because
the green biopolymer CS contains antibacterial agents, it limits surface contamina-
tion of meat and fish. According to recent study, the antibacterial capabilities of CS
film against L-monocytogenes make roast beef suitable for food consumption [35].
CS’s biocidal qualities have been employed to prevent the growth of spoilage micro-
organisms, making it useful for food preservation and food safety [36].
Gelatin
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cooled to form a jelly structure. In the presence of functional groups, gelatin biopol-
ymers’ particular properties to water produce hydrogels (OH, N H2, COOH). The
hydrolytic reaction produces two forms of gelatins (A&B), which are generated by
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acidic hydrolysis of pig skin and basic hydrolysis of bones, with positive and nega-
tive properties for animal skins, respectively. At particular pH levels, the presence of
charge on the gelatin body affects biocompatibility [38, 39]. Recent study has shown
that gelatin produced from the kumakuma (Brachyplatystoma filamentosum) spe-
cies is suitable for response surface technique (RSM) [40]. Also, gelatin biopolymer
extraction from the lamina of lizard fish. In a conventional laboratory process, the
Zhou and Regenstein method will detect the percentage of yield concentration of
gelatin biopolymer, whereas the Biuret method using bovine serum albumin would
detect the concentration of protein in the extract solution [41]. Bovine and porcine
gelatin biopolymer are the most common sources for gelatin extraction and manu-
facture. Chitosan is utilized in vitamin encapsulation, plasma replacements, capsule
and tablet binder, and other biomedical science applications. The special qualities
of gelatin form gelation are employed in food sectors for chewing, gelling, sanitary
food packaging, and dairy product manufacture. It is also used to make film coat-
ings, printer ink, and colored sheets [42]. Biomimetically preparing gelatin and HAp
composites under coprecipitation results in well-organized pore architectures with
significant tissue scaffolding potential. Biopolymer gelatins have a higher propensity
for hydrophilicity and gas barrier, making them suitable for tissue engineering appli-
cations. However, their lower skeletal strength makes them unsuitable for usage in
packing materials [43].
Starch (ST)
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starch by increasing the urea plasticizer concentration within that film [49]. Phlo-
roglucinol, also known as 1,3,5-trihydroxybenzene, is a phenolic compound that is
antagonistic to marine brown seaweeds (phaeophyceae). In the perinuclear region of
microbes, acetyl-malonate is used in the biosynthesis of phloroglucinol. Phloroglu-
cinol monomeric units bind together to form the backbone of over 700 secondary
metabolites. Antiplasmodic, antibacterial, antiviral, antimalarial, antioxidant, anti-
depressant, and anticarcinogenic properties have been demonstrated for phloroglu-
cinol and its derivatives. The encapsulation of soluble starch provides significant
protection to phloroglucinol, extending its control release potential [50].
Cellulose
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Fig. 12 The fundamental biochemical structure of cellulose derivatives can be mono-, di-, or tri-substi-
tuted depending on -R group
Derivatives of cellulose
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Cellulose nitrate Cellulose nitrate (CN) is a polynitrate ester that is derived from
cellulose. Its structure typically contains 2.2–2.8 nitrate groups for per glucose
unit. A powerful nitrating agent is used to nitrate cellulose derived from wood pulp
or cotton linters (e.g., nitric acid). The electrophilic assault of NO2+ ions on the
OH moieties of cellulose replaces the hydroxyl groups with nitrate esters during
the nitration process.
The use of commercial lateral flow assay (LFA) kits, which are based on anti-
bodies or nucleic acids immobilized on a CN membrane, makes it possible to
identify particular biomolecules within the materials that are being examined.
This makes it possible to provide an accessible platform for prenatal testing, test-
ing for oncogene mutations, the diagnosis of infectious disorders, and the identi-
fication of microorganisms. NC/PCL membranes are utilized in bioengineering
for the detection of Zika virus and enzyme-linked immunosorbent assays, among
other applications (ELISA) [60].
Methyl cellulose Methyl cellulose (MC) is a major cellulose ether. MC is the sim-
plest alkyl ether that may be made in an alkaline media using a methylating agent,
such as methyl chloride or dimethyl sulfate. No matter how much you substitute
for the water in an organic solvent, you’ll still be able to dissolve methyl cellulose.
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For example, MC dissolves in water when the degree of substitution is between 1.4
and 2.0, and it is typically soluble in water and several organic solvents when this
degree is between 2.4 and 2.8.
During the hydrogelation process, silver oxide nanoparticles (AgNPs)
were synthesized in situ from Ag + ions using a silver acetate precursor salt
(CH3COOAg). Both the burn wounds and the skin regeneration were improved by
the use of hybrid materials that were successfully evaluated. Post-surgery tissue
adhesion is minimized thanks to the polymeric blend’s lubricant coatings, such as
those seen on the CMC/PEG/MC composites.
It is also beneficial for medication delivery systems because of its role as an
emulsifying agent. For biological applications such as tissue engineering, wound
healing, and pharmaceutical formulations, methyl cellulose is most often utilized
[61].
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Konjac glucomannan (KGM) is the key ingredient of konjac tubers, which are a
longstanding Araceae plant. Konjac glucomannan has been shown in biomedical
studies to improve health by limiting cholesterol in the blood and striving to improve
carbohydrate metabolic activity, bowel movement, and colonic ecosystems. KGM
is a staple ingredient that is commonly used to thicken and bind gravies, curries,
sauces, animal fat, and livestock. In an alkaline medium or when coupled with
certain other hydrocolloids like as xanthan gum or k-carrageenan, KGM can form
hydro gel. These gels are essential building blocks in a variety of food implementa-
tions, including jelly, noodles, tofu, and snacks. Collagen and KGM have been used
to transport drugs in living organisms. The combined emulsion effect of collagen
and konjac glucomannan can improve collagen dissolution in aqueous. The physical
properties of collagen, KGM, polyphenols, and ginsenoside Rb1 with polyphenols
and ginsenoside Rb1 may influence the ability to control release of drug. Further-
more, the appearance of these polymers in the complex can aid in the bioactivity and
storage of polyphenols and ginsenoside [63].
KGM is a naturally existing substance polysaccharide retrieved from the tubers of
Amorphophallus konjac. It is a copolymer made up of of β-(1,4)-linked D-glucose
and D-mannose residues in a molar ratio of 1:1.6 with a lower degree of acetyl moi-
eties at the C-6 position (1 in 17 residues, approximately). The structural representa-
tion of KGM is given in Fig. 13.
Because of the appearance of very active primary hydroxyl (CH2OH) func-
tional groups at the C-6 position of KGM, a variety of chemical treatment, includ-
ing graft polymerization, are conceivable. KGM is extensively used in pharmaceuti-
cal and food applications due to its high viscosity, extremely good water retention
capabilities, gelling potency, non-toxicity, biocompatibility and biodegradability.
Recently, a KGM-based superabsorbent polymer (KSAP) was created by grafting
acrylic acid (AA) onto a KGM template and irradiating it with 60Co-g at room tem-
perature. FTIR spectroscopy and SEM imaging data analysis were used to character-
ize KSAP. The transplant of AA onto KGM was revealed by the large effect in bands
in the FTIR spectra of KSAP, KGM, and AA. XRD patterns revealed that crystalline
structure in KSAP was lower than in native KGM. SEM images revealed a rough
surface in the case of KGM and a micro porosity in the case of KSAP. The relatively
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hydrophilic nature of KSAP resulted in greater velocity and abilities for water
absorption. Graft copolymers compiled with an amount of radiation of 5.0 kGy and
a monomer to KGM ratio of 5 could accumulate 625 times their dry weight in water.
Ions, especially multivalent positively charged ions, considerably lowered KSAP’s
water permeability power [64]. In comparison with many other thermoreversible
gels, KGM forms a thermally balance gel after the addition of an alkaline agglom-
eration, and the gelation of KGM is aided by heating. Gelation happen as a conse-
quence of the arrangement of a network structure of crossing zones that are thought
to be established by hydrogen bonding. The green pharmaceutical characteristics of
KGM that contribute for its behavior in nanotechnology based drug delivery mecha-
nism include its elevated concentrations of mannose, which effectually enables the
communication of KGM with biotic surfaces that really are extremely lucrative in
mannose synapses, such as M-cells enveloping Peyer’s fragments and phagocyto-
sis. Ionic gelatinization of chitosan with TPP (chitosan/TPP ratio values of 3/1 and
6/1) yielded chitosan nanoparticles [65, 66]. By solubilizing phosphorylated KGM
in the nanoparticle rescinding medium, it was possible to incorporate it onto the
nanoparticle configuration. Intra—molecular hydrogen bonds, as well as electro-
static interactions among oppositely charged groups in phosphorylated KGM deriva-
tive and free – NH3+ in chitosan, are responsible for the heterotypic relationship in
this co-gelled system. As the chitosan/konjac glucomannan ratio changes from 6/6
to 6/24, the nanoparticles’ hydrodynamic diameter decreases from 800 to 400 nm.
Regardless of the CS/ KGM ratio, the zeta potential of these nanoparticles was close
to the expected neutral value, ranging from − 0.4 to − 2.3 mV for about the same
content. This has been explained as a result of the plant polysaccharide shielding the
chitosan charges. The addition of KGM fiber to a diet may enhance metabolic func-
tional capacity in humans, and rats with low levels of KGM have lower plasma cho-
lesterol. KGM can also be fabricated into films or formed into blend film for coating
and packaging implementations, and KGM gels have considerable potential applica-
tions in a controlled release matrix [67, 68].
Lignin
Lignin is the second most prevalent biomaterial in plant species after cellulose and
is a fundamental natural biopolymer found in the cell walls of woody materials. This
is one of the basic components with a high potential for use in the production of
bio fuels, and it can be used as an operational polymer in the synthesis of bio-based
polymer blends [69].
Lignin is among the most common natural polymer found in plants. Lignin,
the second most prevalent renewable bio-resource after cellulose, is regarded as
a solid waste in a variety of industrial processes. Attempts to valorize lignin have
been posted in a large number of articles and reports in recent years. The significant
characteristics of lignin, such as its abundance, inexpensive, and biodegradability,
increasing carbon content, aromaticity, and reinforcing abilities, make it an excel-
lent candidate as a potential component for bio-composites. Over 50 million tons of
lignin are produced as a by-product of bio refineries each year, with 98 percent of it
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being burned to generate energy. Only 2% of the lignin has been used for other pur-
poses, primarily as dispersants, adhesives, and fillers. Commercial lignin consists
primarily of lignosulfonates from sulfite pulp mills (approximately 1 mill. ton/year)
and less than 100,000 tons/year of Kraft lignin (KL) [70].
Depending on the application, lignin can be used as a factor in biocomposites
with or without modification. Acetylated KL was used to optimize its affinity with
PLA. The incarnation of Kraft lignin, on the other hand, diminished the tensile ulti-
mate strength of the PLA with rising lignin loadings of 10% and 20%. Additionally,
when acetylated lignin was combined with a thermoplastic, the tensile strength was
increased. Lignin can be integrated directly into a polymeric matrix without recon-
figuration, such as a UV-light stabilizer, antioxidant, flame retardant, plasticizer, and
flow enhancer, to reduce the cost of manufacture, plastic, and potentially enhance
mechanical characteristics. Lignin can also be used as a coupling agent in bio com-
posites made from natural fibers. Lignin can act as a cross-linking agent between
hydrophilic fibers and hydrophobic matrix polymers, thereby reinforcing the fiber
matrix interface. Lignin therapies of hemp and flax fibers have been shown to
improve the compatibility of the fibers with the thermoset matrix, thereby enhancing
the mechanical strength of the biocomposites. When compression-molded PLA-cot-
ton composites were treated with lignin, the tensile properties improved. Lignins are
formed through the polymerization of cinnamyl alcohols (monolignols), the struc-
ture of which varies depending on the plant type Coniferous wood lignin is almost
entirely composed of coniferyl alcohol (G-units), with minor amounts of coumaryl
alcohol (H-units) present. The latter, on the other hand, is a major component of
condensing wood lignin. In wood fibers, however, both coniferyl alcohol and sinapyl
alcohol (S-units) are used as building blocks, and all three alcohols are used as
lignin precursors in monocotyledonous tissue [71, 72]. The chemical structure of
lignin is given in Fig. 14.
Coniferous wood lignin is almost entirely made up of coniferyl alcohol (G-units),
with only trace amounts of coumaryl alcohol (H-units). In contrast, the latter is a
crucial constituent of condensing wood lignin. Coniferyl alcohol and sinapyl alcohol
(S-units) are both used as fundamental building blocks in wood fibers, and all three
alcohols are lignin blueprints in monocotyledonous tissue [72].
The polyurethane (PU) reaction is used to stabilize the soil for building engineer-
ing, in which two types of solution were implanted deep into the earth before tun-
neling and then the soil was exhumed after the reaction was completed. This strat-
egy is beneficial when removing a large amount of soil with an excavator because it
relieves the risk of collapse. However, the eliminated soil that has been cross-linked
by synthetic polymers is not biodegradable. To address the aforementioned issue, an
attempt was made to use lignin polyol to stabilize sand. The quantity of lignin polyol
used is less than 5% of the total sand, and a crystallized sand block can be obtained.
It has also attempted to develop PU composite encapsulated fertilizers that can be
kept in the soil for a longer period of time by releasing slowly [73].
The Mannich reaction was used to make a low-cost, environmentally friendly,
and magnetic lignin-based nano-adsorbent. Phosphate was effectively removed from
solution via adsorption. Furthermore, the nutrients in magnetic adsorbent nanoparti-
cles, such as recycled phosphate and chelated iron, can be reused as a multielement
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fertilizer. The release behaviors revealed that the Fe and phosphorus release rates
from M/ALFeP increased steadily over time, reaching 69.1% and 67.2 percent after
30 days in neutral soil, respectively. Batch experiments on cycle adsorption revealed
that M/ALFe has good recyclability and reusability, lowering costs and avoiding soil
pollution. As a result, a method for making lignin-based high-value-added nanoma-
terials in wastewater treatment has been developed, and phosphate-laden nanoparti-
cles as Nano fertilizers show promise in sustainable agriculture [74]. A number of
bio-based composites based on starch, lignin and cellulose were fabricated from an
ionic liquid, 1-allyl-3-methylimidazolium chloride and coagulated in a system with-
out solvent. The study found that the mechanical strength of the biocomposites was
evidently depending on the contents of lignin, starch and cellulose, resulting from
the mutual supplement among different components. High gas barrier ability and
great thermal stability were clearly observed in the biocomposites. Holocellulose
and acid insoluble lignin of Pecan nutshell fiber were utilized as reinforcements of
PLA-based bioplastics. Because of its radical scavenging activity, lignin can act as a
stabilizer in protein-lignin bioplastics. Thermal molding was used to incorporate KL
and WG into materials. During material mixing, the results suggested that KL has a
radical phagocytic action toward thiyl radicals.
The good connection of WG and KL was confirmed by size isolation HPLC. To
improve the physical and functional properties of the bioplastics, different concen-
trations of alkali lignin and lignosulfonates were added to enzymatically modified
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soy protein. Alkaline lignin and lignosulfonates showed typical radical scouting
activity when compared to commercial butylated hydroxytoluene, suggesting that
they could be used in active packaging. The blends with alkaline lignin had a strong
UV-blocking ability due to the color of the lignin. Thermal stability and tensile sta-
bility of the lignin-added films were significantly improved when compared to the
control films without lignin [75].
Agar
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most bacterial species. As a result, it will remain stable, and microbial deterioration
will be low. Its high crystallinity guarantees a high level of strength and stiffness.
The food-grade agar used in this investigation was made by Urban Platter in Mum-
bai, India. Gelation hysteresis is a unique feature of agar biopolymer. As a result,
the temperatures at which it melts and gels varies significantly. The temperature at
which agar begins to dissolve in water is roughly 85 °C, while the actual temperature
varies depending on the agar source. When the temperature goes below 30–40 °C,
the viscosity of an agar solution increases, and it forms a stiff unyielding gel. By
combining agar with soil in the form of a heated solution and enabling it to gel
within the porous medium of the soil sample, this feature of agar was used to gener-
ate homogeneous soil specimens [78, 79].
The biopolymer agar has lately been investigated for soil erosion management
and improved hydraulic conductivity. Among biopolymers, agar has the maximum
mechanical strength. Within the soil mass, it can create a three-dimensional gel net-
work, forming a thick film and covering the soil particles. Furthermore, the agar
biopolymer’s complicated structure assures that it is less biodegradable. It has a long
history of safe food consumption, which supports its environmental friendliness
[80].
Seaweed-based nanoparticles were utilized to construct and test the effect of
using seaweed nanoparticles filler in agar-based biopolymer composite on improv-
ing physical water vapor barrier, mechanical, and biodegradable qualities, according
to recent research. When agar-based biopolymer is reinforced with seaweed nano-
particles, the characteristics of the biopolymer alter, although there are no visible
changes in the water vapor transfer rate (WVTR). The mechanical strength of the
agar-based biopolymer was increased by increasing the concentration of seaweed
nanoparticles, indicating that the agar-based biopolymer composite incorporating
seaweed nanoparticles could be used in food industrial applications such as food
packaging to replace petrochemical-based plastics [81].
Proteins (beans, seaweeds like agar–agar, and seeds), starches (pectins and gums),
and certain other plant tissues are employed to stabilize emulsions in longer-lasting
suspensions. Dressings, frozen desserts, jellies, mousses, pickles, puddings, salad
dressings, sauces, and yoghurt are all common uses for stabilizers [82].
Agar is the most often used microorganism growth medium. Because of the ease
with which agar may be moved (dry, dissolved, and gelled), it is widely used in
modern laboratories. When fed with adequate nutrients, solid agar plates can pro-
mote microbial growth or be used for antibiotic selection. Agar medium is vital for
the study of microorganisms and molecular biology, and it is frequently employed
in pathogen cultivation and detection from contaminated food and water [83]. Agar
is also commonly employed in biomolecular separation and purification due to its
porous 3D architecture. Agar is a basic medium that is commonly used in gel elec-
trophoresis, gel bead chromatography, and size exclusion chromatography. Aside
from being used as a solid growth medium, agar has been manufactured in various
forms (e.g., microspheres and films) to encapsulate molecules for continuous drug
administration or to immobilize proteins for tissue engineering. Because of agar’s
gelation capability, it is most commonly utilized as a hydrogel. To provide long-term
medication administration, agar hydrogels were modified by including additional
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Poly(vinyl alcohol)
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The activity of biological microbes degrades it. Because of its increased crystal-
linity, it is extremely soluble in water. Many polymer end goods, such as liquors,
surgical threads, and food packaging, are made with PVA. It is a polymer that is
strong, ductile, and extremely flexible. PVA is a biodegradable and non-toxic poly-
mer that is used in food packaging. Contact lenses, heart surgery, medication admin-
istration, and wound dressing are just a few examples of biomedical uses [88, 89].
Other polymers, such as food additives like citric acid, succinic acid, and tar-
taric acid, could be blended with the biopolymer PVA. In the packaging industry,
PVA blended with poly(3-hydroxybutyrate) (PHB) can be used. PVA/CS films have
mechanical, water vapor barrier, and antibacterial qualities that make them suitable
for use in food packaging. For food packaging applications, PVA has been investi-
gated active packaging with grapefruit seed extract (GSE) and PVA. Active films
from apple pomace and PVA for antibacterial activities during food packaging
applications have been discovered in recent hybrid study [90, 91].
Halloysite nanotube (HNT) is a non-toxic material used largely for medicine
delivery in medical applications and food packaging. As a result, HNTs were used in
this study as natural reinforcement for a feasible poly(vinyl alchol)/starch/glycerol/
Halloysite nanotube, (PVA/ST/GL/HNT) nanocomposite film to enhance its water
resistance and water contact angle, as well as its mechanical and thermal behavior,
serving as a novel application for food packaging in the industries [92].
Although PVA hydrogels have been the most extensively studied biomaterials
for articular cartilage replacement due to their biocompatibility, permeability, load-
bearing characteristics, and ease of preparation, it has been discovered that they lack
the surface lubrication and biomechanical strength that natural cartilage requires.
The use of doxorubicin-encapsulated hydroxyapatite-polyvinyl alcohol (DOX-HAp-
PVA) nanocomposite for osteosarcoma-affected bone tissue healing has been dem-
onstrated in the recent study [93, 94]. In recent years, PVA or its extracts hydrogel
microparticles and NPs have been reported for a variety of drug carriers, includ-
ing PVA NPs encapsulated by poly(lactide-co-glycolic acid) (PLGA) microparticles
and paclitaxel-loaded PVA-g-PLGA NPs for the treatment of restenosis, as well as
DNA nanocarriers obtained by a modified solvent displacement method. Since the
late 1990s, PVA in the form of hydrogel NPs has been employed for protein/peptide
medication delivery [95]. The novelty production of a homogeneous microstruc-
tured HAp/PVAP nanocomposite might have applications in bone implantation [96].
Polycaprolactone (PCL)
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7278 Polymer Bulletin (2023) 80:7247–7312
(A) (B)
Fig. 19 Chemical structure of A PCL and B PCL monomer unit
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Polymer Bulletin (2023) 80:7247–7312 7279
process should be examined due to the variations in soft and hard tissues and their
needs. Recent research on the usage of PCL-based scaffolds in tissue engineering
applications are discussed in the next section [100]. The details of applications, ori-
gin of various biopolymers have been discussed in tabular form later (Table 2).
13
Table 2 Targeted biopolymers in advance applications, with their origin and diagrammatic representation of their chemical structure
7280
13
1 Chitosan Sources: crustacean shells, such as lobsters, crabs, and shrimp, as Biomedical applications, bioplastics, nanocomposites, textile [101]
well as fish scales and a variety of other creatures (insects and industries, packaging of food, fuel cell, Wastewater treatment,
fungi)
2 Gelatin Sources: Pig (porcine skins) and cow bones or beef hides, malian Food industry, crime scenes, fingerprints, gelling agent, cosmet- [102]
skins, biovin hides fishes, salmon, catfish, squid, bigeye snapper, ics (bath salts, shampoos, sunscreens, body lotions, hair spray
cuttlefish, lizardfish, etc. and facial cream), medical industry, pharmaceutical industry,
medicine, wine and beer, controlled drug delivery, wound dress-
ing, etc.
3 Starch Sources: Maize, wheat, rice, potatoes, banana, cassava, etc. Food industry (baked foods, confectioneries, pastas, soups [103]
and sauces, and mayonnaises), medicine, textile, paper, fine
chemicals, petroleum engineering, agriculture, and construction
engineering, physical and chemical modifications, drug delivery
applications, pharmaceuticals industries, etc.
4 Cellulose Sources: Agro-waste, domestic-waste, wood, plant, paper, Bio-fuels, consumables, film-forming agent, thickener, blocker, [104]
bamboo, sugar beet, banana rachis, potato tubers, cotton, fique, sustained-release agent, blending agent and suspending agent,
kapok, agave, jute, kenaf, flax, hemp, vine, sisal, coconut, grass, wound dressing, drug carrier, pharmaceutical applications, food,
wheat, rice and barley, etc. drug delivery, coating of solid dosage, scaffolding, biomedical
implants such as cardiovascular implants, Bone and connective
tissue repair, etc.
5 KGM Source: roots of the elephant yam, bulb of the konjac plant Improve metabolic control, lowering plasma cholesterol in rats, [68]
formation of films and blend membranes, coating and packag-
ing, controlled release matrix, food additives, thermoreversible
gels
6 Lignin Sources: agricultural residues, hemp, cotton, woody biomass, and Pharmaceutical industries, wound dressing, wound healing, medi- [105]
energy crops, jute, wood pulp, etc. cine, photocatalyst, drug delivery, controlling disease, immune
booster, electrospinning, water treatment, power sources,
electrochemical energy materials, synthesis of polymers, dyes,
adhesives and fertilizers 3-D printing- plastic composite, etc.
Polymer Bulletin (2023) 80:7247–7312
Table 2 (continued)
Sl. No Biopolymers Origin: Sources/synthesis Applications Refs.
7 Agar Sources: Found in the cell walls of certain species of red algae Antibiotic selection, culture and detection of pathogens from con- [106]
such as Gracilaria and Gelidium taminated food and water, bimolecular separation and purifica-
tion, gel electrophoresis, gel bead chromatography, drug release,
tissue engineering, drug delivery, vaginal capsules, bacteriologi-
cal culture, food industries,
8 PVA Synthesis: Obtained by the polymerization of vinyl acetate mono- Textile, paper industry, and food packaging industry, gene therapy [107, 108]
mers followed by partial hydrolysis
9 PCL Synthesis: Using a catalyst such as stannous octanoate, PCL is Plastics, weather resistance, drug delivery, tissue engineering, [109]
Polymer Bulletin (2023) 80:7247–7312
made via ring-opening polymerization of ℰ-caprolactone additives, food industry, textile industry, chemical factory, steel
manufacturing, automobile industries, paper industries, etc.
10 PLA Source: wheat, straw, corn, and sorghum etc. Tissue engineering, bone re generation, implants, industries, drug [110]
Synthesis: ring opening polymerization of lactate delivery, food industry, medical devices, dialysis, plastics, 3- D
printing, etc.
11 Gallen Gum Source: It naturally occurs on water lilies, secreted by the microor- Thickener, binder, and stabilizer in different food applications, [111]
ganism Sphingomonas elodea, stabilizes the water-based gels, such as desserts and drinking
Synthesis: synthesis chemically by fermenting sugar with a certain jellies, yogurt and sour cream in vegan items, bone repair and
bacterium strain cartilaginous tissue regeneration
12 Pullulan Source: Produced aerobically by growing a yeast like fungus Food industry (coating or packaging material of dried foods, [112]
Aureobasidium pullulans including nuts, noodles, confectionaries, vegetables and
meat), binder for (tobacco, seed coatings and plant fertilizers),
adhesives, pharmaceutical industry (tablets, pills, granules),
flocculating agent, rayon industries, paper industries, printing
and writing, photographic, lithographic and electronic applica-
tions , etc.
13 Dextran Synthesis: synthesized by the action of the bacterium Leuconostoc Anticoagulant, treatment against shocks, surgery, trauma, burn, [113]
mesenteroides drug, etc
7281
13
Table 2 (continued)
7282
13
14 Curdlan Source: Produced by bacteria, such as Alcaligenes spp., Agrobac- Food (pasta, canned meat) and Dairy products, Therapeutic [114]
terium spp., Paenibacillus spp., Rhizobium spp., Saccharomyces products, Adjuvant, Antioxidant and anti-inflammation agent,
cerevisiae, Candida spp., and fungal sources like Aureobasidium Protection against hyperglycemia, immunomodulation, anti-
pullulan, Poria cocos, etc. Synthesis: Biosynthesis of curdlan allergic activity, etc
from glucose (uridine diphosphate (UDP)- glucose as primary
precursor in the presence of enzyme UDP-glucose pyrophos-
phorylase)
15 Scleroglucan Sources: Produced by various filamentous fungi especially of Oil industry for thickening, discharge of drilling mud’s and [115]
the genus Sclerotium, belonging to the phylum basidiomycota. enhanced oil recovery, construction engineering, adhesives,
Industrially it obtained from, S. rolfsii and Sclerotium glucani- water colors, printing inks and liquid animal feed composition,
cum, Schizophyllum commune, Botrytis cinerea, and Epicoccum thickener in paintings, stabilizer in fire drencher foams and in
nigrum pesticides used in agriculture, food industry (stabilization of
dressings and ice creams), cosmetics, creams and protective
lotions, pharmaceutical products, drug delivery, antitumor, anti-
viral and antimicrobial compound, immune-stimulator , etc
Polymer Bulletin (2023) 80:7247–7312
Polymer Bulletin (2023) 80:7247–7312 7283
Gellan gum
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7284 Polymer Bulletin (2023) 80:7247–7312
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Polymer Bulletin (2023) 80:7247–7312 7285
Pullulan
Fig. 24 Chemical structure of pullulan, bears α-(1, 4) linkage and α-(1, 6) linkage
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7286 Polymer Bulletin (2023) 80:7247–7312
Pullulan and its derivatives, like other polysaccharides, can be utilized to improve
the biocompatibility of different nanoparticles as well as their colloidal stability
[139, 140].
When compared to direct application on the food surface, the benefit of integrat-
ing antimicrobials into pullulan films is the control and gradual release of the com-
pounds over time. There are three benefits to employing pullulan packaging films
as an antibacterial delivery technique for meat and poultry products. When antimi-
crobials are included into pullulan films and coatings, less antimicrobial is required
to inhibit microorganisms on food surfaces. Furthermore, antimicrobial-containing
pullulan films exhibited long-term inhibitory efficacy and allowed for regulated anti-
microbial component transfer from the film to the food product [141].
Dextran
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Polymer Bulletin (2023) 80:7247–7312 7287
Curdlan
Scleroglucan
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7288 Polymer Bulletin (2023) 80:7247–7312
Table 3 Recent chemical modification of some specific biopolymers with specific reagents and their
modified structures
SI No Biopolymer Modifying agent Modified biopolymer Refs
1 [148]
2 [148]
4 [149]
5 [150]
6 [151]
7 [152]
8 [153]
9 [154]
the fungus that forms linear rod-like triple helices that are kept together by intermo-
lecular hydrogen bonds [161]. The chemical structure of scleroglucan is represented
in Fig. 27.
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Scleroglucan has a variety of industrial uses, but it was first utilized in the oil
sector for thickening, discharge of drilling muds, and increased oil recovery, where
it outperformed xanthan and other polymers in terms of efficiency and durabil-
ity. In building engineering, scleroglucan and other pseudoplastic biopolymers are
used. Adhesives, water colors, printing inks, and liquid animal feed formulation are
among the other industrial applications. Scleroglucan would be ideal for the stability
of sauces and ice creams in the food business. However, food safety law in Europe
and the USA has yet to authorize scleroglucan [115].
Characterization of biopolymers
The capacity to correctly assess and validate the structures and purity of biopoly-
mers is provided through characterization. When novel materials are being synthe-
sized, a competitor product is being analyzed, or a product’s performance has to be
enhanced, biopolymer characterization is critical. The molecular weight distribu-
tion, molecular structure, shape of biopolymers, thermal characteristics, mechanical
properties, and any additions are all part of polymer characterization. Microscopy
methods, FTIR spectroscopy, NMR spectroscopy, and XRD are all covered in the
physicochemical characterization section. Physical characterizations of biopolymer
membranes and films, such as swelling, degradation/erosion degree, and Porosity
measurements, are then explained. Finally, the primary biological characterizations,
such as cytotoxicity and antimicrobial research, are presented.
Physicochemical characterization
For the determination of polymer structures and the presence of functional groups in
polymer chains, NMR is the most sensitive and powerful enabling technology. NMR
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7290 Polymer Bulletin (2023) 80:7247–7312
XRD
SEM
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Polymer Bulletin (2023) 80:7247–7312 7291
sample, creating various signals that are collected by detectors. Because biopoly-
mers are non-conductive, SEM examination requires the sputtering of a thin coating
of metal [172].
The SEM method is utilized for surface and fracture investigation in biopoly-
mer films and membranes, allowing for the determination of sample structure and
morphology features. The surface of biopolymer films and membranes is gener-
ally smooth and uniform, especially when created using the casting process [173].
Depending on the film preparation technique and/or biopolymer mixing, a porous
structure can be observed by SEM on the surface and fracture analysis in some cir-
cumstances. SEM may be employed as an essential tool to validate the structure of
the sample on silk fibroin/gelatin multilayered films, according to a recent study.
This approach is important because it offers three-dimensional images of the eye’s
interior, which aids knowledge of component components’ surface morphology
[174, 175].
TEM
FTIR
Infrared spectrometry is for investigating how matter interacts with light radia-
tion, especially infrared radiation in the electromagnetic spectrum. Chemi-
cal substances and materials can be identified and characterized using infrared
spectroscopy. In biopolymers, FTIR may be utilized to investigate the different
functional groups and interactions. Hydrogen bonding, amide linkage, and other
interactions may be easily spotted by studying the spectra [180]. Attenuated total
reflection (ATR) sampling device-based Fourier transform infrared (ATR-FTIR)
spectroscopy is one of the methodologies being studied. It needs minimum sam-
ple preparation, allows for simultaneous estimation in both lab and field settings,
and is simple to use. Variable-temperature Fourier transform infrared (FTIR)
absorption spectroscopy was used to explore the thermotropic phase behavior of
a group of recently created self-forming synthetic biopolymers [181]. The FTIR
method has been extensively utilized to investigate the physical and mechanical
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Physical characterizations
Swelling degree
Polymer swelling is a mass transfer process caused by fluid diffusion into the sub-
stance. The tendency of polymeric systems to absorb the solution of interest, quanti-
fied in mass or volume is termed as swelling degree. Polymer swelling capacity is
determined by the nature of the polymer, the solvent/polymer interaction, and the
polymer structure, and it is a quality that has a direct impact on its use. Because of
their natural source and hydrophilicity, most biopolymers are more vulnerable to the
action of water (swelling characteristic) [185].
Swelling degree studies typically include measuring the sample’s initial mass and
the mass after ‘t’ time in contact with the solution of interest. The swelling degree is
expressed as a percentage in Eq. (2):
Wt − W0
Swelling Degree (%) = × 100% (2)
W0
W0 is the initial sample mass and Wt is the sample mass after ‘t’ time.
The swelling degree of biopolymers is a useful parameter for determining mate-
rial behavior after application. Low swelling qualities are required for food packag-
ing applications, since they provide better barrier features [186]. Swelling behavior
is an important feature in rehydration and exudates absorption for wound-healing
applications. For the optimum wound-healing environment, enough moisture must
be given to prevent dehydration, bacterial development, and infection [187, 188].
Degradation
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caused by ultraviolet (UV) light and radiation; mechanical degradation is the effect
of mechanical forces on polymer stability; thermal degradation is the degradation of
the polymer caused by temperature changes; and chemical degradation is the degra-
dation of the polymer caused by hydrolysis, enzymatic degradation, or pH change
[189].
Sample mass loss and mechanical property loss are the most typical criteria used
to assess biopolymer degradation. Degradation degree by sample mass is calculated
by Eq. (3)
Wi − Wt
Degradation(%) = × 100% (3)
Wi
where Wi and Wt are the dry weight of the sample with respect to time ‘t.’
The degradation degree is computed by measuring the mass or mechanical char-
acteristics of a sample in a simulated application environment (simulating chemi-
cal composition, pH, and temperature). Microscopy (in general, SEM method) may
also be used to see biopolymer erosion since deterioration destroys the biopolymer
structure. For a wide range of applications, determining the degree of degradation/
erosion of biopolymer membranes and films is critical. Degradation can be a goal
attribute depending on the application, for as in biodegradable bags and skin tissue
engineering [190–192].
Porosity measurements
(4)
( ) ( )
Porosity (P) = W2 − W1 ∕ 𝜌V1
where W1 and W2 are the weight of the film before and after immersing in the
alcohol solution, respectively. V1 is the volume of the solution taken before the
immersing the film and ρ is the density of the solution.
Biological characterization
Cytotoxicity
Nowadays, most tests are carried out in vitro, in accordance with international rec-
ommendations to reduce in vivo testing. To evaluate the effect induced by the bio-
material’s exposure to the cells, the first three biocompatibility tests can be done
using cell cultures, either primary or cell lines. The cytotoxicity test, which is done
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Antimicrobial activity
Applications of biopolymers
Water treatment
Novel approaches for water purification have been developed by researchers. Water
recycling solutions that include green water treatment are also being researched.
Due to the remarkable qualities of biopolymers, using natural polymers in mem-
brane synthesis, manufacturing, and production to create entirely biodegradable
membrane materials becomes perfect and appealing [198]. The adsorption–desorp-
tion process has recently been utilized to remove chlorophenoxyacetic acid herbi-
cides from water using orange peel-activated carbon. As a result, chlorophenoxy-
acetic acid herbicides were considerably absorbed from water by this bio-sourced
activated carbon. Membranes may be adjusted using these biopolymers. Because of
their abundance of polysaccharides, cellulose polymers have been widely used in
water applications [199]. Membranes made from carboxymethyl cellulose (CMC),
cellulose nanofibrils (CNF), and bacterial cellulose (BC) modified cellulose with
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various functions. As a result, the azo and anthraquinone dyes were effectively
removed from wastewater using these modified membranes [200].
The electrospun cellulose acetate nanofibrous membrane may filter out chro-
mium, metal ions, and hazardous organic compounds in addition to microorganisms.
For the removal of lead from contaminated water, magnetic nanoparticles immobi-
lized on cellulose acetate nanofibrous membranes were created [201]. The densely
interconnected porous cellulose acetate nanofibers membrane with homogenous dis-
tribution over the polymer bodies has been discovered to have a unique use in water
filtering. The cellulose acetate nanofibrous membrane has an average fiber diam-
eter of 30–110 nm. As a result, the electrospun cellulose acetate membrane contains
homogeneous, continuous, smooth, and interconnected porous nanosized fibers,
which are mostly used to filter microorganisms in water [202].
Biopolymer-based flocculants have the promise to be scaled up for commercial
use. A triangle assessment model was designed to evaluate the effectiveness of
biopolymer-based flocculants in wastewater treatment in terms of economic sustain-
ability [203]. Chemical flocculants such as polyaluminum chloride (PAC) were uti-
lized in the removal of chemical oxygen demand (COD), suspended solids (SS), and
aluminum (Al3+) from unclean water during water treatment. CS composite floccu-
lants produced utilizing a mixture of CS, polyaluminum chloride, and silicate were
shown to be more effective in eliminating contaminants than standard flocculants
[204]. Tanfloc, a natural polymer derived from Black acacia, was compared to the
commercial synthetic polymers Flopam and Zetag for flocculation of microalgae,
Nannochloropsis oculata, and Chlorella vulgaris. Both commercial and biopolymers
effectively treated both fresh and marine water, showing that Tanfloc, a natural poly-
mer, can be used as a promising polymer due to its cheap cost and environmentally
benign properties [205].
Chitosan has a number of intriguing features, including the ability to form a gel,
increased adsorption capacity, superior biodegradability, exceptionally high biocom-
patibility, and non-cytotoxicity, as well as enhanced biological qualities including
antifungal, antibacterial, and antitumor activity. Because of its strong cell adhesion,
cell survival, cell interaction, and neurite outgrowth, the hydrogel form of chitosan
is most commonly utilized in tissue engineering. Long-term stability, elasticity, self-
assembly, and biological activity are all characteristics of elastin, a structural pro-
tein. Elastin is a protein that provides elasticity to organs and tissues. It is found
in organs, particularly elastic ligaments, blood vessels, skin, and the lungs, where
elasticity is important. Where the elastic effect in parts of our body, such as skin
and blood vessels, is visible, the insertion of elastin inside biomaterials is extremely
important. As a result, it is more commonly employed for soft tissue regeneration
[206, 207].
In the recent decade, interest in DNA- and RNA-based scaffolds has grown at
an exponential rate. DNA-derived polymers can build nanostructures or tridimen-
sional networks among hybridized DNA or RNA chains, in addition to serving as
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Drug delivery
The qualities of biopolymers and their derivatives were superior in terms of func-
tionality, water solubility, non-toxicity, biodegradability, and biocompatibility. Fur-
thermore, by releasing drugs in a regulated manner, these biopolymers can lessen
medication toxicity. Collagen is the most prevalent protein in the animal kingdom,
consisting of a glycine–proline–hydroxyproline repeating unit in a triple helix shape.
It has been used in drug delivery applications as microparticles, coatings, and films
due to its good biocompatibility [210].
The most ubiquitous biopolymer, cellulose, has outstanding mechanical and
biological features such as biocompatibility, low cytotoxicity and biodegradability.
Microcrystalline cellulose (MCC), cellulose nanomaterials (CNC and CNF), and
bacterial nanocellulose (BNC) are examples of materials with different aspect ratios
that are good prospects for drug delivery systems [211]. Chitosan-drug conjugation
is among the most effective drug delivery methods. Various molecular weights of
chitosan were utilized for conjugation formation, and the cleaving condition might
be pH or GSH (glutathione) sensitive depending on the drug type. For any sensitive
protein or gene delivery, chitosan hydrogel production is another option [212].
Agriculture applications
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7298 Polymer Bulletin (2023) 80:7247–7312
Food packaging
polyhydroxyalkanoates (PHAs) are now one of the most abilities of different to fos-
sil-derived polymers in the Bioeconomy, with the greatest potential to replace poly-
olefins in packaging applications, due to their biocompatibility and physical quali-
ties,. Although cellulose acetate’s gas and moisture barrier qualities are not ideal
for food packaging, it is ideal for items that require a lot of moisture since it allows
for breathing and avoids fogging [218, 219]. According to recent study, PE and PP
packaging foils coated with CS and polyphenol colloidal formulations have a lot
of promise as active (antioxidant and antibacterial) packaging in the food business
[220].
Biopolymers are used to study polymer electrolytes. Membranes holding ions dis-
solved in polymer serve as polymer electrolytes. Ionic conduction requires the pres-
ence of electron donor atoms, such as N, O, or S, in the polymer. The dissolved
salt cations have just a weak interaction with these atoms. Conductivity in poly-
mer electrolytes is influenced by both cations and anions. Biopolymers Only two
of the compound’s atoms, O and N, have a lone pair of electrons. Since chitosan’s
backbone comprises hydroxyl, ether (C–O–C) and amine functional groups, it may
be designed to address the needs of a particular application. The presence of polar
functional groups in their structure explains their water-attracting abilities [221].
Dissolving CS in acetic acid produces a membrane layer with extremely low
room temperature conductivity (− 10−10 to 10−9 S cm−1). It may, however, func-
tion as a matrix for ionic conduction because of its strong film-forming capacity and
ability to solvate numerous inorganic salts. Adding lithium salt or ammonium salt
to chitosan for proton conduction improves the conductivity at room temperature.
An very high conductivity (2.42 ± 0.01) × 105 (S c m−1) was achieved using the phth-
aloylation combination of 70% phthaloyl chitosan–30%NH4SCN (S c m−1) [222].
Glucose molecules with three hydroxyl functional groups are bonded to form
the polymer cellulose. It is defined as the average number of substituted hydroxyl
groups per glucose in the specified form of methyl cellulose. Because of the pres-
ence of lone pair electrons on the oxygen atoms in methyl cellulose, these atoms
13
Polymer Bulletin (2023) 80:7247–7312 7299
may function as complexation sites and interact with salt cations in a weak way.
An electrolyte based on methylcellulose exhibits ionic conductivity when com-
posed of 63.75 weight percent methylcellulose, 21.25 weight percent NH4NO3,
and 15 weight percent PEG, as well as 75 weight percent methylcellulose, 25
weight percent NH4NO3 − 1.1 × 10−4, and 2.10 × 10−5 (S cm−1), respectively
[223].
Recently, it has been shown that polymer electrolyte membranes are very
efficient and dense in energy. By using biopolymer in polymer electrolyte fuel
cells (Fig. 31), less C O2 is released into the atmosphere, which benefits the
environment.
Solid gellan gum (GG) polymer electrolyte for energy use has been shown
in recent study. Solid gel electrolyte synthesis based on carbohydrate polymer
(Phytagel/GG) was established in this work. As a dye-sensitive solar cell mate-
rial, this substance might be used (DSSC) [224].
In chemistry, physics, materials, and microelectronics, biopolymers are
employed in FETs. Material applications expand beyond sophisticated biologi-
cal devices to electrical/electronic materials, making them unique for electronic
switches, storage devices, gates, biosensors, and biologic transistors. Due to
their vast surface area, excellent electrical conductivity, and porous nanostruc-
tures, biopolymers are being employed to produce Supercapacitor (SC) (more ion
adsorption and active sites for the charge transfer reactions). Biopolymer dielec-
trics boost supercapacitor efficiency. Due to their cheap cost and photolytic eco-
friendliness, biopolymers are employed in LED, PV, and photodetector systems
[225].
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7300 Polymer Bulletin (2023) 80:7247–7312
Environmental application
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Polymer Bulletin (2023) 80:7247–7312 7301
and resistance to wear and tear [230, 231]. The administration of drug delivery,
the creation of hydrogels, and tissue engineering all benefit from the use of poly-
esteramides. These include surgical masks, gloves, surgical gowns, towels, sanitary
napkins and diapers as well as surgical headgear, panties shielded and antimicro-
bial textiles for surgical curtains and surgical curtains as well as wipes. In surgi-
cal gowns, bio-based PET may be used in lieu of cotton, polyester, and PE [232].
Due to the adaptability of polylactic acid, it may be used to create a wide variety
of items, including but not limited to hats, gowns, and masks. For its remarkable
absorption properties, thermoplastic starch is an essential ingredient in the manu-
facture of diapers for young children. Alginate fibers, catgut, collagen, chitosan, and
superabsorbent polymer are just a few of the biomaterials often used in medical and
hygienic applications [233].
13
7302 Polymer Bulletin (2023) 80:7247–7312
Conclusion
Over the last few decades, there has been a progressive development in industry
interest in biopolymers and biopolymer-based green goods. Biopolymers are renew-
able, non-toxic, environmentally friendly, biodegradable, lightweight, easy to man-
ufacture and have a high skeletal behavior that improves mechanical strength and
stiffness and can be customized to meet a variety of performance needs. Many fac-
tors influence the qualities of hybrid biopolymer-based materials, including chemi-
cal composition, specific temperature, environmental effect, particle size, and sur-
face area. The comprehensive study showed that biopolymers are acceptable with
tissue engineering, drug control, agricultural, pharmaceutical, biomedical, bioengi-
neering, and food sectors, as well as that they have a wide range of uses. Further
research on biopolymer-based products has the potential to replace conventional
harmful non-biodegradable materials in the near future. When these bioproducts
grow more durable and function better, there is the potential for the establishment
of new markets. Continuous research into performance and life-cycle evaluation is
required to determine the biopolymers’ usefulness.
Acknowledgements The authors are grateful to the Council of Scientific and Industrial Research (CSIR),
New Delhi, for providing financial support (Project Grant No. 22(0847)/20/EMR-II, dated: 10.12.2020).
The authors also gratefully acknowledge to National Institute of Technology (NIT), Arunachal Pradesh,
India, for assistance and support.
13
Polymer Bulletin (2023) 80:7247–7312 7303
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