A Review On Chitosan and Chitosan-Based Bionanocomposites Promising

International Journal of Biological Macromolecules 185 (2021) 832–848
Contents lists available at ScienceDirect
International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac
Review
A review on chitosan and chitosan-based bionanocomposites: Promising

material for combatting global issues and its applications
Motia Azmana a, Syed Mahmood b, c, *, Ayah Rebhi Hilles d, Azizur Rahman e,
Mohd Azmir Bin Arifin a, Shakeeb Ahmed f
a
Faculty of Chemical and Process Engineering Technology, Universiti Malaysia Pahang, 26300 Gambang, Pahang, Malaysia
b
Department of Pharmaceutical Technology, Faculty of Pharmacy, Universiti Malaya, 50603 Kuala Lumpur, Malaysia
c
Centre for Natural Products Research and Drug Discovery (CENAR), Universiti Malaya, 50603 Kuala Lumpur, Malaysia
d
Faculty of Health Sciences, Department of Medical Science and Technology, PICOMS International University College of Medical Sciences, 68100 Kuala Lumpur,
Malaysia
e
Department of Clinical Pharmacy, Faculty of Pharmaceutical Sciences, UCSI University, 56000, Kuala Lumpur, Malaysia
f
Faculty of Pharmacy, Jamia Hamdard, 110062 New Delhi, India
A R T I C L E I N F O A B S T R A C T
Keywords: Over the last few years, several attempts have been made to replace petrochemical products with renewable and
Chitosan-based bionanocomposites biodegradable components. The most challenging part of this approach is to obtain bio-based materials with
Drug delivery properties and functions equivalent to those of synthetic products. Various naturally occurring polymers such as
Biodegradable
starch, collagen, alginate, cellulose, and chitin represent attractive candidates as they could reduce dependence
Nanomaterials
on synthetic products and consequently positively impact the environment. Chitosan is also a unique bio-based
Hybrid materials
polymer with excellent intrinsic properties. It is known for its anti-bacterial and film-forming properties, has high
mechanical strength and good thermal stability. Nanotechnology has also applied chitosan-based materials in its
most recent achievements. Therefore, numerous chitosan-based bionanocomposites with improved physical and
chemical characteristics have been developed in an eco-friendly and cost-effective approach. This review dis
cusses various sources of chitosan, its properties and methods of modification. Also, this work focuses on diverse
preparation techniques of chitosan-based bionanocomposites and their emerging application in various sectors.
Additionally, this review sheds light on future research scope with some drawbacks and challenges to motivate
the researchers for future outstanding research works.
1. Introduction interest in bionanocomposites is growing dramatically worldwide as

they are cost-effective, biodegradable, eco-friendly and easy to prepare.
Nowadays, Polymer matrix-based nanocomposites have received Among all biopolymers, polysaccharides are the most important
much interest in the field of nanotechnology. Even Though artificial choices because of their renewable and recyclable nature and biode
petroleum-based polymers have been broadly employed in composite gradability. They constitute an abundant portion of the biomass. Chi
products for various applications over the last half-century, their poor tosan is one of the most extensively used polysaccharides in a variety of
biodegradability has made them a key source of waste disposal troubles. applications because of its properties that are affected by environmental
So, Special attention has been given to replacing traditional petroleum- variables such as electric field, pH, and ionic strength [2]. However,
based plastics with substances based on biopolymers, such as biode chitosan-based bionanocomposites are considered to be non-toxic and
gradable polyesters, polysaccharides or proteins [1]. Bio have a remarkable affinity to proteins. Due to their exceptional biolog
nanocomposites are a class of hybrid materials consisting of biopolymers ical activity, nontoxicity, biocompatibility, and biodegradability, these
and inorganic solids with at least one dimension in the nanometer range bionanocomposites have gained immense popularity in biological sci
(1–100 nm). The addition of nano-sized inorganic fillers leads to ences. They are widely being used as therapeutic aids, functional coat
modification and enhancement of properties of biopolymers. The ings, food products and anti-microbial packaging materials. They are
* Corresponding author at: Department of Pharmaceutical Technology, Faculty of Pharmacy, Universiti Malaya, 50603 Kuala Lumpur, Malaysia.
E-mail addresses: syedmahmood@um.edu.my, syed872011@yahoo.co.in (S. Mahmood).
https://doi.org/10.1016/j.ijbiomac.2021.07.023
Received 4 June 2021; Received in revised form 26 June 2021; Accepted 2 July 2021
Available online 5 July 2021
0141-8130/© 2021 Elsevier B.V. All rights reserved.
M. Azmana et al. International Journal of Biological Macromolecules 185 (2021) 832–848
also being used in tissue-engineering [3], agriculture and textile in transparency, and so forth due to the surface functionality and nature of
dustries [4], and wastewater treatment [5]. the nanofillers. In this case, the nanoscale dispersion is responsible,
Since the application and future scope of chitosan-based bio leading to the higher aspect ratio besides the higher surface area of
nanocomposite is growing in different fields, this article presents a respective bionanocomposites. These nano-sized biocomposites with
detailed investigation regarding these matters. It represents uniqueness chitosan exhibit more robust and stable bionanocomposites matrices
than previous review research work. However, it is organized nicely by materials by reducing reinforcement efficiency slightly than usual
discussing chitosan-based bionanocomposite and their chemical struc nanocomposites. As a result, chitosan-based bionanocomposites also
ture in Section 2. After that, it reveals some vital information about the resemble biocompatible and bioactive matrices with exceptional me
source and properties of chitosan and modification of chitosan with the chanical properties [1].
necessary graphical presentation by Sections 3 and 4, respectively. It Besides, bionanocomposites have been identified as the most viable
also presents the most suitable methods and techniques for producing hybrid products made by incorporating nano-sized inorganic fillers into
chitosan-based bionanocomposites through Section 5 to make it more biopolymeric matrix under controlled conditions. The formation of
informative. In addition, the novelty of this article enhanced by accu chitosan-based bionanocomposites is represented in Fig. 1. The prefix
mulating important information about the application for different “bio” signifies that these are biodegradable and environmentally
purposes with benefits and drawbacks elaborately by Sections 6 and 7. friendly. Since chitosan is a natural biopolymer, it has become an
Before concluding this article, the future research direction also given by attractive alternative to synthetic plastic polymers hazardous to the
Section 8 to advance and enhance its application for various purposes environment. The most popular biopolymer matrices are poly
soon. saccharides, polynucleic acids, proteins and aliphatic polyesters, along
with nanofillers. Generally, nanotube-hydroxyapatite (HA), clay nano
2. Chitosan-based bionanocomposites particles, metal nanoparticles, and nanofibers are used as nanofillers
[6].
Over the years, chitosan has gathered attention from researchers due
to its polycationic nature, biological versatility, and exceptional physi 3. Chitosan source and properties
cochemical properties.
Chitosan-based bionanocomposites are extensively utilised as bio- Chitin (β-(1–4)-poly-N-acetyl-D-glucosamine) is the most abundant
materials for tissue engineering and drug delivery systems, dressing natural polymer. It can be found in the exoskeletons of shrimps, crabs,
for wound and burns. Their biocompatibility, non-toxicity, and versa cuticles of insects, and cell walls of fungi [7,8]. For biomedical appli
tility favour their usage in various industrial sectors. Chitosan has also cations, chitin is converted to its deacetylated derivative, chitosan, by
found application in the food industry and has emerged as a promising chemical or enzymatic hydrolysis [9] (Fig. 2).
candidate for anti-microbial packaging materials. The hydrophilic (D- Chitosan is an FDA (Food and Drugs Administration)-approved
glucosamine) and hydrophobic parts (N-acetylated residues) in chitosan copolymer composed of β-1,4-linked 2-amino-2-deoxy-β-D-glucose
molecules allow it to form emulsion systems; therefore, used as an (deacetylated D-glucosamine) and N-acetyl-D-glucosamine units with
emulsifier in the food industry. less molecular weight (MW) and crystallinity than chitin (MW > 100
Moreover, bionanocomposites could show exceptional characteris kDa) [10,11]. Its structure is similar to cellulose except for the hydroxyl
tics, for example, superior mechanical, barrier properties, greater group (-OH) at position C-2 in cellulose is replaced by amino group
Fig. 1. Chitosan-based bionanocomposites.
833
Fig. 2. Chitosan from chitin by deacetylation [12].
(− NH2) in chitosan. Chitosan is a biologically compatible polymer other hand, the amino group becomes deprotonated at a pH of more than
approved for dietary use in Japan, Finland, and Italy. In 2005, chitosan 6, making chitosan insoluble [16]. Also, its solubility depends on the
obtained from shrimp was classified by the USFDA as GRAS (generally positioning of the acetyl groups along the chain, deacetylation methods,
accepted as safe), based on science protocols for food use in general, in and ionic strength. At an acidic pH, chitosan is capable of exhibiting
compliance with the Good Manufacturing Practice Regulations. chelating properties for several metal ions. Chelation occurs on free
amino groups (at near-neutral pH) or by electrostatic attraction on
protonated amino groups (acidic solutions).
3.1. Physicochemical properties
Chitosan is known for its wide range of distinct properties like che 3.2. Biological properties
lation, viscosity, solubility in different vehicles, film-forming and
mucoadhesivity, polyelectrolyte behaviour and polyoxysalt formation. Various studies have reported that chitosan is a non-toxic, biocom
It was found that the unbranched and linear form of chitosan has an patible, biodegradable polymer [17–20]. Both chitosan and its de
excellent viscosity; the viscosity of chitosan can be modified by altering rivatives exhibit exceptional biological properties like anti-
the deacetylation conditions. The structure of chitosan is of great sig inflammatory [21,22], anti-bacterial [23,24], anti-tumour [25,26],
nificance since it affects its physicochemical characteristics. The dis anti-fungal [27,28], haemostatic [29,30], and analgesic [31,32].
tinguishing characteristic of chitosan is its high degree of deacetylation Numerous experiments have concluded that chitosan has an
and low content of crystalline regions. This feature makes it an attractive outstanding anti-bacterial effect on a wide range of disease-causing
candidate for several practical applications, e.g., in pharmacy and bacteria due to its cationic nature, which permits the interaction be
biotechnology. The physicochemical characteristics of chitosan are tween negatively charged lipids and proteins present in the bacterial cell
influenced by several factors like the degree of deacetylation (DD), wall. The diffusion of chitosan into the cell membrane contributes to
crystallinity, MW, methods of degradation [13]. Depending on its MW, expansion and disruption of the membrane's permeability, which ulti
commercially available chitosan can be graded as high MW chitosan and mately induces cytoplasmic portion leakage and bacterial cell death. In
low MW chitosan. High MW chitosan ranges from 190 to 375 kDa with various in vitro experiments, it was studied that chitosan's anti-bacterial
DD > 75%, while low MW chitosan ranges from 20 to 190 kDa with DD function could result from its DNA binding capacity. It has been stated
< 75%. It was discovered that the degradation rate of chitosan is that when chitosan comes in contact with the nuclei of bacteria, it
inversely proportional to DD and is also dependent on the order and combines with DNA and prevents mRNA synthesis [33,34].
distribution of acetyl groups. Higher DD shows a significantly lower The anti-fungal property of chitosan is due to its electrostatic reac
degradation rate, while lower DD shows a quicker degradation rate tion with the cell membrane's negatively charged phospholipids. When
[14,15]. Chitosan consists of three reactive positions; one amino group the cell membrane is disrupted, chitosan can penetrate the cell and
and two hydroxyl groups in every glycosidic residue. However, the prevent DNA/RNA synthesis, thus causing cell death. The DD and MW
amino group has great significance as it is pH sensitive and is responsible play a crucial role in regulating the anti-fungal properties of chitosan.
for the cationic nature of chitosan and the regulation of its various Usually, chitosan's anti-fungal effect is enhanced when the DD is higher
physicochemical characteristics. The solubility of chitosan depends on and the MW is smaller [35].
the pH-responsive amino groups protonated at lower pH, permitting It has been clinically proved that chitosan exhibits anti-inflammatory
chitosan to dissolve and form soluble cationic polysaccharides. On the action by reducing the release of interleukin-8 (IL-8) and tumour
834
necrosis factor (TNF) from mast cells [36]. Chitosan has an advantage polymers are facilitated by the acid solvent employed for processing
over NSAIDs (the conventional medications for various inflammatory these blends. Molecular interaction improves the properties of the
conditions). It does not produce gastric side effects because the free component polymers and chitosan/PVA blend, extensively utilised in
amino groups create a defensive shield over the stomach. Chitosan also food applications [48]. Besides, chitosan mixed with PVA has demon
can heal connective tissues. When chitosan undergoes acid hydrolysis, strated excellent mechanical characteristics for medicinal products and
glucosamine monosaccharides are produced, forming the proteoglycan controlled drug-delivery system.
structural units of connective tissues and cartilage, thus aiding tissue
repair [15,37]. 4.2. Chemical modification
Chitoligosaccharides are chitosan derivatives that exhibit anti-
tumour activity. However, the precise mechanism is unclear. Some re The presence of reactive amino (-NH2) and hydroxyl (-OH) groups in
searchers stated that the anti-tumour effects were due to the increased the polymer chain facilitate convenient chemical modification of the
activity of natural killer lymphocytes. It is hypothesised that chitoligo chitosan molecule. However, the process does not alter the basic frame
saccharides cause differentiation and proliferation of T-cells by stimu of the chitosan molecule [49]. The modification of chitosan can be done
lating the lymphocyte-activating factor. Some studies have also by different chemical reactions stated in the following portions.
suggested that chitoligosaccharides effectively enhance immune re
sponses and modulate the functions of immunocompetent cells [38]. 4.2.1. Phosphorylation
Chitosan (poly-N-acetyl glucosamine) shows a haemostatic effect by In this technique, the surface of the chitosan membrane is phos
accelerating erythrocyte accumulation [39]. The positive charge on phorylated by Et3PO4 (triethyl phosphate), butanol, H3PO4 (phosphoric
chitosan promotes erythrocyte adhesion, fibrinogen adsorption, and acid), or P2O5 (phosphorus pentoxide) (Fig. 3A). A phosphorylated
platelet adhesion and activation. The hemostatic property of chitosan is chitosan membrane possesses increased ammonium ion concentration
due to its polycationic content and non-specific plasma membrane compared to an intact membrane. This amended chitosan membrane is
binding [40]. amphoteric applied to elevate cell propagation [50] (Fig. 3A). Gogoi's
In vitro studies have shown that the main analgesic effect of chitosan research team prepared curcumin-(±) α-lipoic acid coloaded phos
is by reducing the concentration of inflammatory mediators (bradyki phorylated chitosan nanoparticles by ionic gelation technique. These
nin) at the site of injury. It also absorbs proton ions released at the in nanoparticles showed improved drug loading efficacy, better swelling
flammatory site to control pain. [41]. degree and improved release rate in acidic pH. Trypan blue dye exclu
sion assay was performed to confirm the anti-cancer activity of the
4. Modification of chitosan nanoparticles. The properties of the nanoparticles recommended their
possible application as anti-cancer agents [51].
Chitosan is considered to be a biofunctional polysaccharide with
immense potential for applications in various fields. Its exceptional 4.2.2. Thiolation
properties and biological activities have favoured its popularity in Thiolated chitosan can be achieved by the covalent bond formation
various sectors like food, cosmetic, pharmaceutical and biomedical. of the thiol group (-SH) with the chitosan skeleton. This thiolated
However, their applications are limited by their solubility in many polar polymer demonstrates improved paracellular transportation of hydro
solvents and water. Overcoming this issue is possible by modifying the philic molecules and better penetration abilities [52] (Fig. 3B). Kaur's
chitosan molecule through chemical/enzymatic methods to produce research group synthesised gemcitabine loaded thiolated chitosan
new depolymerised derivatives. The modifications of chitosan are nanoparticles that show better encapsulation efficiency, ~1.2-fold
influenced by several factors such as MW of chitosan, viscosity, and greater mucoadhesion, ~4.34-fold greater effective permeation, and 50
reaction conditions. times increased cytotoxicity [53].
The amino and hydroxyl groups in the chitosan structure form the
basis of their association with other polymers and bio-molecules. Several 4.2.3. Hydroxyalkylation
methods have been studied to modify chitosan, for example, polymer Hydroxyalkyl chitosan can be prepared by hydroxylalkylation. In
blending, curing, and graft copolymerisation. During blending, two this method, chitosan reacts with epoxides (ethylene oxide, butylenes
polymers are combined to generate new material with different physical oxide, propylene oxide) and glycidol. The reaction may occur either at
properties. Curing is a chemical process that involves the hardening of a alcohol or amino group producing O-hydroxyalkyl or N-hydroxyalkyl
polymer material by cross-linking polymer chains. Grafting imparts a chitosans or a combination of both. This alteration enhances the water
variety of functional groups to a polymer. During this process, mono solubility of the polymers [54]. To further illustrate this, hydroxybutyl
mers are covalently bonded and polymerised as side chains onto the chitosan (HBCS) was prepared by attaching the hydroxybutyl group to
main polymer chain [42]. the chitosan molecule via etherification. The resultant polymeric ma
terial of HBSC showed outstanding hygroscopicity and moisture reten
4.1. Physical modification tion, promoted immunocompetence activity, and exhibited better anti-
microbial effects against gram-positive and gram-negative bacteria [55].
Physical modification is the easiest way to modify polymers. It is
usually done by mixing or blending two polymers and creating new 4.2.4. Sulfation
material with different and distinctive physical properties. Polymer During sulfation of chitosan, sulfamate groups and sulfate ester
blending is generally intended to produce materials with optimal groups are introduced into the carbohydrate skeleton of the molecule.
chemical, mechanical, structural, biological, and morphological prop Sulfated chitosan is a water-soluble anionic chitosan derivative with
erties. This technique is considered feasible and economical compared to anti-viral, anti-microbial, and osteogenic activity. This derivative also
other available techniques and is less time-consuming [43–45]. Chitosan blocks malignant human melanoma cells. They are also used to absorb
is known to blend well with certain hydrophilic polymers such as PVA metal ions, drug delivery, blood anticoagulation, and haemagglutina
(polyvinyl alcohol), PEO (polyethyl oxide), and PVP (polyvinyl pyrro tion resistance [56] (Fig. 4A). Sulfated chitosan polymers exert antico
lidone). Several experiments have shown that PVP and chitosan's agulant activity due to their structural similarity with heparin.
mixture is very suitable for preparing the blend material. Similarly,
chitosan and synthetic PVA are also considered ideal for blending pur 4.2.5. Carboxyalkylation
poses as they enhance the mechanical and barrier properties of chito Various carboxy-polymers like carboxymethyl chitosan, carbox
san/PVA mixing films [46,47]. Molecular reactions between the yethyl chitosan are produced by this modification. The derivatives have
835
Fig. 3. Chitosan modification by A. Phosphorylation B. Thiolation.
Fig. 4. Chitosan modification by A. Sulfation B. Alkylation.
836
better solubility and accumulation properties and are widely used in 4.2.10. Enzymatic modification
various drug delivery systems [57]. Recently, Manimohan and his group Chitosan modification with enzymes is fascinating to researchers
produced water-soluble hydrazide-based O-carboxymethyl chitosan, because of its specificity and environmental benefits compared to
which exhibited enhanced anti-inflammatory, anti-oxidant, and anti- chemical modification. In 1999, Payne and his colleagues studied
diabetic effects [58]. enzymatic grafting of phenolic molecules into chitosan. The enzyme
tyrosinase causes oxidation of the phenolic reactants, yielding O-qui
4.2.6. Alkylation nones highly reactive and electrophilic. It was observed that when thin
During this modification, an alkyl group is introduced in the chitosan chitosan films were treated with tyrosinase and a phenolic reactant, the
skeleton producing an alkyl group-containing derivative. N-alkylation ultraviolet-visible spectra and the acid-base properties of the films were
occurs via alkylation of the C2–NH2 group, whereas O-alkylation occurs markedly changed.
through alkylation of C6–OH or C3–OH groups in the chitosan molecule. In another experiment, the cloroperoxidase enzyme was used to
The introduction of alkyl group in chitosan leads to the weakening of convert quercetin into reactive quinones, further attached to chitosan.
intermolecular hydrogen bonds, thus improving the solubility of the The resultant molecules exhibited an improvement in their anti-oxidant
resultant polymer. Alkylation of chitosan produces amphiphilic de and anti-microbial potential, and thermal degradability properties were
rivatives, used in paper-making as additives [59] (Fig. 4B). Alkylated also improved [66].
chitosan can be used in wound dressings due to its coagulation and anti-
bacterial properties. It can also be used to absorb anionic surfactants in 5. Methods and techniques for producing chitosan-based
water purification systems [60]. bionanocomposites
4.2.7. Quaternisation Typical methods commonly used to prepare the chitosan-based

Chitosan quaternisation is carried out by incorporating a quaternary bionanocomposites are described below, along with their preparation
ammonium group into the hydroxyl or amino group of chitosan. Qua techniques, properties, and applications (Table 1).
ternary ammonium salts of chitosan possess enhanced solubility and
anti-bacterial properties, favouring their utilisation in biomedical fields 5.1. Solution-casting method
(Fig. 5). Hydroxypropyltrimethyl ammonium chloride chitosan is widely
used in biomedicine and bioengineering as it can alter the mitochondrial The solution-casting method is the easiest method to make polymer
membrane property and affect the respiratory activity of mitochondria nanocomposites. In this method, there are three stages for the prepa
[61]. ration of nanocomposites. The fillers are initially dissolved or dispersed
in a suitable solvent via mechanical agitation or sonication. The resul
4.2.8. Oligomerisation tant polymer is then melted in a similar solvent. Lastly, the solution
Chitosan oligomers are produced by chemical and enzymatic hy containing fillers is mixed with the polymer solution at an appropriate
drolysis. These oligomers are water-soluble and have low viscosity. temperature. Casting or precipitation of this mixture results in the
Chemical hydrolysis can be carried out by nitrous acid deamination of generation of bionanocomposites. In 2015, Regiel-Futyra and his
depolymerisation chitosan. The resultant molecules have enhanced anti- research team fabricated chitosan–gold bionanocomposites using a
fungal properties, which can further be increased by decreasing the solution-casting technique [67].
degree of polymerisation of chitosan oligomers. Enzymatic modification
of the polymers is carried out in the presence of chitin deacetylases.
5.2. In situ technique
Fawzya's research group synthesised chitosan oligomers by hydrolysis of
chitosan using a chitosanase enzyme from Aeromonas media KLU 11.16
The in situ technique is the most effective method to produce bio
for better anti-fungal activity [62].
nanocomposites with uniformly dispersed filler components. In this
technique, filler compounds are distributed in monomers either in the
4.2.9. Graft copolymerisation
presence or absence of solvent. Subsequently, the curing agent is
Graft copolymers have been prepared through the free-radical
incorporated at the required temperature for perfect polymerisation. In
polymerisation in water-acetic acid solutions of chitosan in the pres
2014, Hebeish's research group successfully produced chitosan-based
ence of an initiator. Various initiators have been examined for grafting
nanocomposites by using this technique. Chitosan-grafted-poly acrylo
like ceric ion, Fenton's reagent, and γ-irradiation. This approach alters
nitrile silver nanocomposites were produced by chemical reduction of
the polysaccharide backbone resulting in complex grafted chitosan de
silver ions in graft copolymerisation of acrylonitrile onto chitosan films
rivatives [63] (Fig. 6). These grafted derivatives are extensively used in
[68].
tissue engineering, gene transfer, and drug delivery systems [64]. Ex
periments were conducted to synthesise modified chitosan flocculants
by grafting. The grafted copolymers showed outstanding oil rejection 5.3. Electrospinning technique
efficiency and were used as nanocomposite membranes in oily waste
water treatment [65]. The electrospinning technique can generate excellent and thin fibres,
as thin as tens of nanometers in diameter. Electrospinning instruments
have three main components: a high-voltage electricity source, multi-
needle containing spinneret, and a grounded conductor that acts as a
Fig. 5. Chitosan modification by quaternisation.
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Fig. 6. Chitosan modification by graft copolymerisation.
Table 1
Preparation technique of chitosan-based bionanocomposite with their applications.
System Preparation technique Expected outcome Application References
Improved biocompatibility by chelation of

Carboxymethyl chitosan/ZnO Biomedical applications, anti-bacterial
Spray drying carboxymethyl chitosan with Zn2+ ions, the [70]
nanocomposite agent
stronger anti-microbial activity of ZnO
The enhanced surface concentration of Fluconazole Quick estimation of fluconazole in
Yolk shell Fe3O4 @PA-Ni@Pd/ Ultrasound-assisted in situ
by ion-exchange and due to amino and hydroxyl pharmaceutical products, urine, and [71,72]
Chitosan nanocomposite surface polymerisation
groups of chitosan serum
Biocompatible semiconductor, increased
crystallinity of Cu and Zn-nanocomposites,
Fe3O4-MXOY/Chitosan
improved the interaction of H2O/O2 with
nanocomposite Solution Casting Method Wastewater treatment [73]
produced electron-hole pair on catalyst shell and
(M = Ni, Zn, Cr, Co, Cu)
finally degraded the Polycyclic-aromatic-
hydrocarbons in sunlight
Plasticized Chitosan:AgNO3: Highest DC conductivity, maximum dielectric Used as electrolyte and separator in
Solution Casting Method [74]
Al2O3 nanocomposites constant, and the lowest electric modulus electrochemical double-layer capacitor
Graphene oxide-Chitosan and
Enhanced anti-microbial action against all infective Water purification, anti-bacterial, dye
Graphene oxide-EDTA [75]
microbes removal
nanocomposites
ZnO/Chitosan, ZnO/Chitosan/ Decreased stiffness and strength and enhanced
glycerol, ZnO/Chitosan/ strain of plain chitosan, improved mechanical
Reflux-solution method Anti-microbial packaging applications [76]
polyvinyl alcohol performance and barrier, and sufficient anti-
nanocomposites film microbial properties
Increased oxygen and moisture permeability of
Application in green and profitable
films, enhanced anti-fungal activity and
EVA/Chitosan-based PEG-PCL agriculture area by decreasing the use of
Solvent casting method temperature-sensitive drug release performance [77]
micelles nanocomposite films pesticide and synthetic bagging, pre-
and were found to increase the quality of grapes by
harvest treatment of grapes
pre-harvest spraying
MCM-41-NH2-graft-
polyarcrylamide-co- Wastewater treatment, removal of Pb (II)
In situ polymerisation Enhanced absorptive capability to Pb (II) [78]
polyacrylic acid-graft- from aqueous solution
Chitosan nanocomposite
Utilised as a possible sorbent for
Chitosan-based silver Chemical precipitation Improved the efficiency of chromium elimination,
hexavalent chromium deletion from [79]
nanocomposite beads method reduced sorption efficacy
artificial and industrial wastes
Linezolid@ Chitosan/3, 5-dini Increased release efficiency and inhibition zone, Potential delivery of linezolid as anti-
Microwave synthesis [80]
trosalyslic acid nanostructure improved potentially microbes -specific activity microbial agents
Chitosan-based composite Increased specific surface area and pore diameter,
Modified Hummers method Wastewater treatment. [81]
hydrogels improved adsorptive capacity
Greener approach involving Used as potential supplies for biomedical
Chitosan/PVA/ZnO Thermally stable, increased photoluminescent
mixing, solution casting, and and environmental applications, [82]
nanocomposites film properties and adsorptive capability
solvent evaporation method elimination of organic dye
Chitosan-cobalt and Chitosan- Probe (horn) sonication
Enhanced corrosion inhibition potential Used as a corrosion inhibitor of mild steel [83]
SnS2 composites technique
Favorable substance for packaging of
Enhanced physicochemical, anti-microbial, and
CS/AgNPs nanocomposite film food, pharmaceutical, and related [84]
anti-oxidant properties
products
Chitosan/clay/glycerol Maximum strength and stiffness, improved thermal
Solution casting technique Alternative food packing materials. [85]
nanocomposite film stability, best water resistance
Chitosan-cl-poly(AA)/ZrPO4 Sol-gel polymerisation Non-toxic and biocompatible, promising anti-
Wastewater treatment. [86]
nanocomposite technique microbial nature
Polyacrylic acid-based and Chemical cross-linking Enhanced nitrogen-containing active sites and Used as alternative adsorbents for the
[87]
Chitosan-based hydrogels approach cadmium adsorption capability adsorption and elimination of cadmium
Chitosan/Montmorillonite/ Higher adsorption capability, enhanced removal Elimination of ferric ion from aqueous
Graft polymerisation [88]
melamine efficiency, and selectivity solution
Chitosan/montmorillonite/
Casting and solvent Better thermal stability, decreased surface
glutaraldehyde Used as a flame retardant [89]
evaporation method roughness, and enhanced hydrophobic character
nanocomposite film
Chitosan/amino multiwalled Improved mechanical strength and thermal
purification of blood as an effective
carbon nanotubes (CS/ Phase-inversion method stability, higher adsorption capability, and [90]
adsorbent for bilirubin
AMWCNT) composite beads outstanding hemocompatibility
838
collector. The liquid for electrospinning is filled into a syringe and changer material in the field of advanced wound care, pharmaceuti
loaded at a specific rate governed by the syringe pump. A continuous jet cals and cosmetic industries, agriculture and food processing industries.
is produced by immobilising charges on the surface of a liquid droplet. Details are mentioned in Fig. 7 and Table 2.
Accelerated whipping and stretching of the fluid filament lead to the
formation of nanofibers. Naseri's research team used this technique to 6.1. Pharmaceuticals and medical industry
produce chitosan/polyethene oxide-based fiber mats by reinforcing
chitin nanocrystals [69]. Chitosan-based bionanocomposites are considered promising can
didates for biomedical applications due to their nontoxicity, biocom
5.4. Freeze-drying technique patibility, biodegradability, and anti-bacterial properties.
A uniform blend of polymer and filler solution is poured into a 6.1.1. Drug delivery
copper mould and quenched in liquid nitrogen at extremely low tem The cationic properties of chitosan and the presence of primary
peratures. The polymer scaffold is then freeze-dried to eliminate the amino groups make it the most important polysaccharide for various
solvents. The prepared scaffold has a porosity of 90% and pore size drug delivery purposes. These are responsible for their many properties,
ranges 15 to 35 μm. These scaffolds have gained immense popularity in such as mucoadhesion, permeation enhancement, in situ gelations, and
tissue engineering. In 2013, Liu's research group used a combination of controlled drug release [92]. The use of ≤100 nm-sized biomaterials or
freeze-drying and solution-casting technique to fabricate chitosan-based biopolymers in the formulation of chitosan-based bionanocomposites
bionanocomposite with halloysite nanotubes [91]. offers improved haemostatic potential. Some nanomaterials/nano
particles have found application in treating infections and various ocular
6. Applications of chitosan-based bionanocomposites diseases [93]. Biopolymer-clay composites can deliver the therapeutic
ingredient at the target site and maintain a significant concentration
Chitosan has many exceptional properties that make it a game- level. These nanomaterials exhibit extraordinary properties required for
Fig. 7. Broadened application of chitosan-based bionanocomposites.
839
Table 2 drug delivery by creating a giant biopolymer and precisely tailoring

Available chitosan-based bionanocomposite with application prospects. drug release kinetics within a porous carrier matrix [94]. These ad
Chitosan-based Researcher Application purpose References vancements in the drug delivery field are escalating the researcher in
bionanocomposite name and terest significantly and giving us a clear message to develop
products year sophisticated and enhanced nanomaterials/nanodevices using chitosan-
Anti-oxidant, anti- based bionanocomposites for improving drug delivery efficiency.
Impregnated hybrid Annu et al. microbial, and
[123]
chitosan-nanosilver (2021) anticervical cancer 6.1.2. Anti-tumour and anti-cancer therapy
activity
Chitosan with Riccio et al.
Chitosan-based bionanocomposites can selectively permeate through
Wound dressings [124] cancer cell membranes and exhibit anti-cancer activity via various
nanocellulose (2021)
Chitosan-tragacanth enzymatic, antiangiogenic, immune-enhancing mechanisms, and
Mallakpour Tissue engineering and
gum/silica@silver
et al. (2020) Anti-bacterial activity
[125] apoptotic pathways. They get sequestered from non-cancer cells and
(CT-TG/SiO2@Ag)
provide their enhanced bioavailability in cancer cells in a sustained
Poly(trimethyl Providing optical,
hexamethylene Sarwar et al. mechanical, and manner. The magnetic response of bionanocomposites expedites the
[126] intravenous distribution of the anti-cancer agent and minimises systemic
terephthalamide)/ (2020) thermomechanical for
silicon dioxide specific use. toxicity [95]. Magnetic hyperthermia is a promising approach for cancer
Chitosan (CTS)/ therapy. The targeting of magnetic nanoparticles in hyperthermia was
epoxidized natural Raju et al.
rubber (ENR) (2020)
Agriculture [127] improved using chitosan-coating. These chitosan-coated magnetic
(20phrCTS-t-ENR) nanoparticles can be promising materials for use in magnetic targeted
Polypyrrole grafted Photocatalytic, anti- hyperthermia.
Ahmad et al.
ZnO/Chitosan (Ppy/
(2019)
cancer, and anti- [128] Antitumor activity of chitosan-metal complexes is due to their
C/Z) bacterial activity
interaction with cellular DNA and free radicals scavenging behaviour.
Chitosan-entrapped
carbon nanotubes with Soluble forms with low MW chitosan oligosaccharides have been re
ZrO2 and Cabarcas et al. ported to cause suppression of tumour growth [96]. However, drug
Biosensor [129]
organophosphorus (2019) carriers, bioavailability, and scavenging properties with multiple fea
hydrolase (CS-ZrO2- tures of chitosan-based bionanocomposites for anti-cancer and anti-
CNT/OPH GCE)
tumour treatment may open a new horizon for developing new drugs
Chitosan–gelatin
Covarrubias and approaches soon to mitigate these issues outstandingly.
polymer with Bone repair scaffolds [130]
et al. (2018)
bioactive glass
Chitosan-g- PMMA(poly
Pradhan et al. Bioadhesive bone- 6.1.3. Nucleic acid delivery and gene therapy
methyl- [131]
(2018) cement implants Chitosan-based biopolymers are highly cationic, and due to their
methacrylate)/Kaolin
Chitosan–magnetite Sureshkumar cationic property, they are regarded as excellent candidates for intra
Removal of chromium [132] cellular delivery of nucleic acids. These genetic materials (ribonucleic
nanocomposite strip et al. (2016)
Graphene Maleki et al. For nanocatalyst
[133]
acid and deoxyribonucleic acid) are responsible for curing multiple
oxide–Chitosan (2015) activity disorders like Parkinson's and cystic fibrosis. The process of gene de
Chitosan with saponite Postnova et al. For extreme
[134] livery involves multiple steps like a condensation of nucleic acids, pro
and sepiolite clay (2015) mechanical properties
Zinc oxide-neem oil- Sanuja et al. tection against degradation, stabilisation in physiological conditions,
Food packaging [135]
Chitosan (2014) cellular internalisation, endolysosomal release, unpacking and delivery
Polypyrrole- zinc oxide-
Ebrahimiasl
Provide stiffness and of the genetic material to the nucleus [97,98]. As a result, chitosan-
Chitosan (Ppy/ZnO/ antimicrobial [136]
et al. (2014) based bionanocomposites shows hope for gene therapy and nucleic
CS) properties
Chitosan‑magnesium
acid delivery to treat genetic disorders. Hopefully, future research on its
Sanuja et al. formulation enhancement may advance the features and improve the
oxide with clove Anti-bacterial activity [137]
(2013)
essential oil delivery of nucleic acid and gene therapy on targeted cells.
Glucose oxidase/Pt
nanoparticles/ Liu et al.
Biosensor [138] 6.1.4. Anti-microbial wound dressing
graphene-Chitosan (2013)
(GOD/PtNPs/GR-Chit) Chitosan-based bionanocomposites are being used as hemostatic and
Grafted Chitosan– Kumari et al. Drug-delivery and wound healing materials. These bionanocomposites provide extrinsic
[139]
Co3O4–Fe3O4 hybrid (2013) tissue engineering anti-microbial agents to treat the wound or burn area [99]. Mi et al.
Grafted Chitosan Kumari et al. Nanohybrid scaffold
[140] confirmed through various histological tests that the chitosan-based
–Au–Fe3O4 hybrid (2013) for drug delivery
Adsorbents for
bionanocomposites helped in wound healing by increasing the epi
removing or thelialisation process and deposition of collagen over the dermis layer of
Montmorillonite (SWy- Celis et al.
2)-Chitosan (SW-CH) (2012)
immobilising anionic [141] skin [100–102]. The skin wound healing process by chitosan-based
pesticides to the mild bionanocomposites is presented in detail in Fig. 8. Anticipating that
acidic soil or water
very soon, the researcher may develop more enhanced chitosan-based
Controlled drug
Chitosan-g-lactic acid Depan et al.
release and cell [142] bionanocomposites by adding bionanofillers for wound healing pur
and montmorillonite (2009)
proliferation poses by accelerating reepithelialization and increasing bacterial clear
Chitosan-graft-
Jere et al.
Akt1 siRNA delivery ance capabilities in the wound area.
polyethylenimine for treatments of lung [143]
(2009)
(CHI-g-PEI) cancers
Chitosan/Nano‑silver, 6.2. Food and packaging industry
Chitosan/Nano- silver
Rhim et al. Anti-microbial
zeolite, and Chitosan/
(2006) functionality
[144] Due to growing awareness among people regarding hygiene and
Nano- safety, there is a high demand in the food market regarding food safety
montmorillonites
and quality. Chitosan biopolymers have rapidly replaced food packaging
materials made from plastic polymers. The traditional packaging of
plastic is considered to be hazardous for health and the environment.
Chitosan, on the other hand, is natural, non-toxic and biodegradable.
840
Fig. 8. Wound skin healing process using chitosan-based bionanocomposites.
Chitosan-based bionanocomposites have excellent film-forming capa regenerative effect on the gum tissue [64].
bilities that can preserve food and extend their shelf-life by inhibiting
water loss. Another important aspect is that in the chitosan-based bio 6.3.3. Bioimaging
nanocomposite matrix, the added nanomaterials are dispersed perfectly; Chitosan-based bionanocomposites also have an excellent scope as
thus, it helps to huddle gas penetration by providing outstanding barrier bioimaging agents. Photoluminescent behaviour of chitosan was inves
properties for packaging applications [99]. These natural polymers with tigated for bioimaging, and it exhibited photoluminescence in aqueous
film-forming properties also allow the convenient incorporation of ad solutions. A magnetic core-shell nanocomposite was devised for bio
ditives in packaged food material. Since plastic packaging items are imaging by Salehizadeh's research group after combining Fe3O4-gold
currently deteriorating the environment dangerously and making the nanoparticles (NPs) with stabilising agent chitosan. Fe3O4 exhibits super
earth unlivable. Chitosan-based bionanocomposites contained magnetic properties ensuring magnetic resonance for imaging, and op
environment-friendly packaging items may decrease plastic items' de tical properties are elicited by gold NPs, which act as photothermal-
pendency significantly. Also, the negative impact of these items could be converters [105].
minimized dramatically if possible to reduce the production price and Afore discussed matter indicates that the biomedical sector is a
readily available for the general people besides raising public promising sector to assist and expedite the treatment process due to the
awareness. diversified functionalities of chitosan-based bionanocomposites. But till
today, lots of challenging issues remain indisputable. That could be
6.3. Biomedical sector solvable by conducting extensive clinical trials, further characterization
with the optimization of the morphologies, orientations, shape, di
6.3.1. Biosensor ameters, and sizes of upgraded chitosan-based bionanocomposites.
Recent years have witnessed ever expanding use of biosensors in
pharmaceutical fields. To produce reliable biosensors, good quality 6.4. Cosmetic industry
immobilisation of biological recognition elements is essential. Chitosan
and its nanocomposites have emerged as an excellent immobilisation Usually, cosmetics are used for whitening, protection, tanning, de
matrix. As a natural polysaccharide, chitosan has many valuable char odorants, anti-aging, anti-wrinkling, nail and hair care [106]. Primarily
acteristics, such as cross-linking with various nanomaterials, high synthetic compounds are used as an active ingredient in these cosmetic
permeability and mechanical strength, low cost and easy availability products. Prolonged use of such substances is likely to cause skin irri
[103]. These chitosan nanocomposite-based biosensors have led to the tation, itching, phototoxicity, and photoallergy [107]. Nowadays, nat
possibility of developing new instruments for early-stage disease iden ural ingredients attract much attention in the cosmetic industry to
tification and detection of various biomarkers. The nanocomposite films overcome these side effects. But, it is very costly to extract these natural
of graphene/gold nanoparticle/chitosan (GAuCS) have been used for compounds from raw sources. So, the researchers are more interested in
glucose biosensing by Shan's research group. The sensor focused on the chitosan and its bionanocomposites for preparing cosmetics products;
immobilisation of glucose oxidase at the gold electrode in thin films of the chitosan can be easily extracted from naturally abundant chitin. For
the GAuCS nanocomposite [104]. example, Chen et al. (2017) designed a novel antiageing cream that
contained Quaternized carboxymethyl chitosan/organic montmoril
6.3.2. Bone tissue engineering lonite nanocomposite, which had excellent UV-protection capability as
In bone tissue engineering, chitosan-based bionanocomposites can well as moisture-absorption retention capacity [108]. Furthermore, in
serve as a substitute for synthetic polymers. As contrary to many syn 2020, Petrick et al. prepared chitosan/TiO2 nanocomposite as a multi-
thetic polymers, chitosan has a hydrophilic surface that promotes cell functional sunscreen cream with the capacity of removing bacteria up
adhesion and proliferation. The chitosan molecules are highly versatile to 99.7% within 2 h [109]. Most recently, Kim's research group (2021)
and are easily transformed into thin films and scaffolds, which have synthesised layered double hydroxide nanosheet and chitosan
wide-ranging applications in cell transplantation and tissue regenera biopolymer nanocomposite for the delivery of liposome into the skin,
tion [7]. Chitosan can be processed in multiple ways to produce a variety leading to increased efficacy of cosmetics [110]. However, the demand
of 3-dimensional scaffolds with different pore structures for bone tissue for cosmetics items of skincare, haircare, oral hygiene till today is
engineering. Chitosan-based scaffolds promote the proliferation of bone- growing, and chitosan-based bionanocomposite also contributes signif
forming osteoblast cells as well as the formation of a mineralised bone icantly. But the problem is proper characterization, and multi-functional
matrix. As these biomaterials are osteogenic, they have shown a behaviour study is lacking to lead to any unexpected complexities. So,
841
accurate and extensive characterization and multi-functional behaviour papermaking additive for improving the wet and dry strength of paper.
study could increase user's faith and promote the cosmetics industry Chitosan and its derivatives appear to be good retention and drainage
growth. agents, which are important wet-end additives in the papermaking
process. Meanwhile, the inherent anti-microbial and film-forming
6.5. Agricultural sector properties have helped in fabricating functional anti-bacterial and
greaseproof papers. Other applications of chitosan in the papermaking-
There is an enormous opportunity for nanotechnology to revolu related industries have also been studied, such as blending with cellulose
tionise this sector. Currently, nanoagriculture focuses on farming by to prepare chitosan/cellulose blend beads. They crosslink cellulose
employing bionanocomposites with superior properties to improve nanofibers to form nanopaper with water-resistant properties used in
livestock and crop production [111,112]. For sustainable intensifica paper-based packaging materials. Furthermore, Chitosan has the char
tion, nanotechnology seems to have the ability to protect and track plant acteristics of both a coagulant and a flocculant with high cationic charge
growth, diagnose animal and plant diseases, increase food supply and density and has been used in pulp and paper mill wastewater treatment
quality, and minimise waste generation. [120]. However, the pulp and paper industry is a very important sector
Aflatoxins are a family of toxins that destroy crops like maise, cotton contributing to social and economic advancement. So, the researcher
seed, and tree nuts. These are produced by certain fungi like Aspergillus could perform extensive research to produce low-cost paper and pulp
parasiticus and Aspergillus flavus. Chitosan has been proposed to reduce products and additives with higher and enhanced properties, i.e.,
fungal contamination as an application of natural products since these greaseproof, dry strength, wet strength, etc.
are known to exert an anti-microbial effect on a wide variety of micro
organisms. Cota-Arriola et al. examined the fungistatic behaviour of 6.8. Wastewater treatment
chitosan-based bionanocomposites against A. parasiticus and came to a
satisfactory conclusion [113]. These nanocomposites have also been A massive amount of industrial wastewater is discarded in the open
used as nutrient and ion-exchange membranes for water treatment [99]. daily, leading to water and environmental pollution. Many procedures
However, to continue the commercial and industrial progress, agricul and methods are available to remove harmful chemicals and compounds
tural advancement is a prerequisite, which could be possible by utilizing from the wastewater by using polysaccharides. In contrast with other
chitosan-based bionanocomposites or similar environment-friendly polysaccharides, due to the presence of -NH2 and -OH groups, chitosan
nanomaterials, i.e., nanoformulation of fertilizers, pest controller. But has gained popularity as a successful adsorbent in water purification.
before that, the researcher needs extensive research study to ensure Chitosan-based bionanocomposites can chelate toxic pollutants such as
whether that is helpful for agriculture. dyes and heavy metals [63,121]. After the cationisation of amino
groups, the -NH2 of chitosan-based bionanocomposites can adsorb
6.6. Textile industry anionic dyes by electrostatic attraction in the acidic media [122]. But
still, there is uncertainty about the existence of harmful contaminants, i.
With changing time, the human protection and rapid advancement of e. toxic metals, drugs, dyes, pesticides in the water and escalating the
environmental, health and safety legislation urge to increase technical scarcity of drinking water. In this case, cost-effective, environmental-
features of textile products for various purposes, like stitches, bandages, friendly, and non-toxic materials urgently needed, and chitosan-based
wound dressings, masks, surgical gowns, hospital linen, gauze, and so bionanocomposites could be alternative among available water treat
forth. The usage of anti-microbial facilities content fabrics and garments ment materials. So, the researcher needs further research to develop
is essential to provide proper care for the people with a pleasant and low-cost and higher pollutant removal bionanocomposites with
healthy living environment. In this case, the diversity of chemical chitosan.
components has been utilised in industrial practice to ensure anti-
bacterial action on textiles. The textile industry and various research 7. Benefits and drawback of chitosan-based bionanocomposites
teams continue to explore eco-friendly chemicals instead of harmful
textile chemicals. Many of these compounds are hazardous to people and 7.1. Benefits
do not dissolve quickly in the natural environment. In this case,
chitosan-based bionanocomposites are the most suitable chemical and 7.1.1. Biocompatibility
used to produce desired textiles purposes as mentioned above [114]. The most prominent feature of these chitosan-based bio
However, Chitosan-based bionanocomposite is used in the textile in nanocomposites is their biocompatibility, favouring their application in
dustry to improve biocompatibility, anti-microbial activity, wash dura medicine, cosmetics, food packaging, and wastewater purification. This
bility, and air-permeability of fabrics. In 2012, Rajendran et al. property exerts between the positively charged chitosan's ammonium
produced neem chitosan nanocomposite treated fabrics which exhibited groups (− NH3+) and the negatively charged groups by establishing
enhanced anti-bacterial properties [115]. In 2014, Chandrasekar's hydrogen bonds with electrostatic attraction. Therefore, these estab
research team showed that the anti-microbial effect and durable prop lished robust bonds affirm the high biocompatibility of chitosan-based
erties were better in the chitosan nanocomposite finished fabrics than bionanocomposites [145].
the bulk finished fabrics [116]. Additionally, chitosan-based bio
nanocomposite is used in the textile industry to remove organic dyes 7.1.2. Nontoxicity
from Wastewater Effluents [117,118]. These advancements in the textile Another beneficial property of chitosan-based bionanocomposites is
industry have become possible due to conducting profound research to low/non-toxicity. Various animal studies have confirmed that chitosan
develop such composites. There is a great possibility of developing and derivatives do not exhibit any chronic toxicity. Also, no deaths or other
upgrading these composites to further enhance the textiles product toxicity signs were observed in rats during per-oral treatment with
tensile strengths, thermo-responsive and other properties to more different chitosan derivatives [146].
advanced this industry.
7.1.3. Biodegradability
6.7. Pulp and paper industry Polymers can be regarded as biodegradable if they get decomposed
under aerobic or anaerobic conditions due to the action of microor
Chitosan was first used in the papermaking industry in 1936 [119]. ganism/enzymes. Similarly, for chitosan-based bionanocomposites, the
In recent years, studies focused on investigating the applications of degradation process in the human body is carried out by the enzyme N-
chitosan as a colour-fixing agent for coloured papers and as a acetyl-b-D-glucosaminidase (NAGase) lysozyme. This feature has
842
attracted the stakeholders into making these materials available for range of pH, inhibiting the microorganism strain's growth at the desired
human use, considering that it would not cause any damage to the point. As a result, the shelf life of the fruits is possible to prolong by 2 to 3
human body [6]. times if store at room temperature [152].
7.1.4. Excellent film-forming ability 7.2. Drawbacks and challenges

Chitosan-based bionanocomposites are capable of forming thin films
that can be used as packaging materials for food items. Tensile strength Despite possessing exceptional biological and physiochemical prop
is an essential element in the film-forming process; fragile films are more erties, certain drawbacks in the molecule pose significant challenges and
prone to cracks and cause contamination of the food items. It was found limit its application in some prominent sectors. The most notable dis
that chitosan-based bionanocomposite films provide strength to the advantages which need to be solved very urgently are listed below.
packaging material and protect the products from degradation [147].
1. It has low solubility due to physiological pH, which could cause
7.1.5. Thermal stability limitation in the medicinal field [6].
It was observed earlier that chitosan couldn't withstand high- 2. Although the FDA has approved it as food-contact material, the Eu
temperature conditions ranging from 200 to 220 ◦ C. This was due to ropean Food Safety Authority doesn't support it [151]. So the ques
the low thermal expansion coefficient for dimensional constancy of pure tion about hygiene and safety is still unanswered.
polymer or biopolymer. However, the chitosan bionanocomposites have 3. Another notable drawback of chitosan-based bionanocomposites is
outstanding thermal stability. For example, nanoclay, nanofibrillated that their colloidal stability is low, hindering the application on a
cellulose, hydroxyapatite, calcium carbonate, and so forth compounds larger scale for drug delivery purposes [94].
ensured the excellent thermal stability can exert by the chitosan-based 4. The high elasticity of chitosan-based bionanocomposites is another
bionanocomposite [145]. drawback that limits their application [153].
5. Since the chitosan-based bionanocomposite shows satisfactory out
7.1.6. Excellent mechanical and barrier facility comes for some cases of medical purposes, especially for drug de
The inclusion of nanoparticles throughout the biopolymer matrix livery. Still, researchers face difficulties regarding drug release
improves the mechanical properties (rigidity and tensile strength) of the effectiveness, drug loading capacity, degradation rate used binano
bionanocomposites [6]. Similarly, in chitosan-based bionanocomposite, compsites materials, delivery duration, and many others [154].
several strategies were used to strengthen the barrier and mechanical 6. Finally, industrial processing centres still have an economic problem
properties of the polymer films. Researchers found that hybridisation of to introduce commercial feasibility of sustainable biopolymer in the
nanofillers and surface-functionalised nanofillers successfully improves real market.
the mechanical properties of chitosan-based bionanocomposites [148].
For example, poly N-vinyl pyrrolidone, polyvinyl alcohol, polyethylene The discussion on the application scope and benefits of chitosan-
glycol, polyethylene oxide, collagen, cellulose, carboxymethyl cellulose, based bionanocomposites seems a promising biopolymer to mitigate
sulfonated cellulose fibres, and cellulose acetate may aid in improving possible global issues in the future. However, some portrayed drawbacks
the mechanical property [149]. and challenges need to be solved urgently to ensure its availability for
any purpose in different fields.
7.1.7. Strong anti-microbial activity
Chitosan bionanocomposites exhibit anti-microbial activity against a 8. Directions for future research
wide range of microorganisms like yeast, filamentous fungi, gram-
negative and gram-positive bacteria. This activity depends on the type The significance of chitosan-based bionanocomposites is increasing
of chitosan and its concentration, MW and DD. It is believed that DD is excessively due to its beneficial aspects. However, in some cases, it has
the most influential factor that accelerates or deaccelerates the anti- challenges that need to be resolved. Several aspects of future research
microbial activity of chitosan-based bionanocomposites as it relates to are outlined below.
the number of free amino groups in the molecule. Also, Rodrigues's
research team found that, in an acid medium, it has excellent possibil 8.1. Advancement of agricultural fields
ities to exhibits good anti-microbial activity because it can transfer the
proton to ammonium (NH3+) [150]. Until now, the agricultural sector is in the budding phase, and chi
tosan could be a key changer for advancing this sector by taking a long-
7.1.8. Anti-oxidant potential term research plan. Because recently conducted in vitro and in vivo
Another significant benefit of chitosan-based bionanocomposites is studies shows significant outcomes to preserve, grow and protect the
that it has excellent anti-oxidant properties. Due to its radical scav agro products. Researchers anticipating that very soon, nanotechnology
enging ability, it is used to treat oxidative stress and certain diseases. A could be a game-changer in agri-economics by advancing agricultural
research group found that rosehip seed oil in chitosan film significantly fields. In this case, nanochitosan could be a prime weapon to deliver eco-
improved the radical scavenging activity and anti-oxidant properties friendly nanochemicals or nonaoagro fertilizer. They can be utilised for
[151]. growing crops, controlling pest, increasing fish production, meat pro
duction, seeds preservation, developing innate immune system crops,
7.1.9. Anti-fungal potential drought resistance crops, salinity resistance crops, and so forth. Also,
The biocidal action of chitosan against microorganisms shows great synthetic chemicals indiscriminate in the agricultural field to control
commercial potential in the medical and agricultural sectors. Further microbial growth hinder the environment and threaten our existence.
more, many studies have shown that the anti-microbial effect of chitosan So, in this case, chitosan-based bionanocomposite could be a robust and
is carried out by targeting the cell surface and disrupting cellular energy, viable alternative to protect our nature, environment, and cultivating
which suggests that chitosan is a good alternative approach for anti- farm.
fungal therapy.
In the agricultural sector, the anti-fungal properties of chitosan- 8.2. Advancement of chitosan carrier for brain drug delivery
based bionanocomposites help control plant diseases caused by fungi.
Anti-fungal properties of chitosan-based bionanocomposites help to Last few decades many research has been conducted on drug delivery
control fruit and crop diseases. These features happened due to a wide and similarly chitosan-based carrier, nanocarrier also currently being
843
used for drug delivery on targeted cell successfully. Especially for brain Because primary materials (chitosan) for chitosan-based bio
drug delivery, it attains excellent attention, and much research has been nanocomposites extracted from natural resources using acidic and alkali
conducted on it and achieved satisfactory outcomes. However, anti treatment process. But the use of acidic and alkali for producing the raw
bodies conjugated with chitosan-based nanocarrier as a potential materials is a questionable matter and threat to the environment. Also,
approach, but a mere in-vivo study performed showing their formula more eco-friendly and budget-friendly ways of extraction need to be
tion conjugation with antibodies [155] and evaluating long-time developed in competitive industrial instances.
toxicity. So, the researcher concentrated the future research study on
these areas. 9. Conclusion
8.3. Wound healing using UV with CS/ZnO The adverse impact of non-biodegradable materials on humans and
the environment has peaked scientists and environmentalists interest in
CS/ZnO bionanocomposite with ultraviolet (UV) irradiation could be biodegradable materials. Therefore, bionanocomposites have become a
an important research topic in future for wound healing purposes focus of intense research because of their intrinsic qualities such as
because ZnO's unique semiconducting and optical properties with UV's biocompatibility, biodegradability, and nontoxicity and their improved
photocatalytic reactions can enhance bacteriostatic properties. But in structural and functional features Chitosan-based bionanocomposites
[156], researchers studied that clinical studies showed that the wound are the most prominent items in the current times. They possess
healing process hindered by UV due to inhibition of epithelial formation. numerous outstanding properties and benefits.
So, whether CS/ZnO with UV irradiation works for the healing process in This review discussed the chitosan-based bionanocomposites and the
the wounded area could be revealed by future research work. reason behind their outstanding properties. It further elaborated various
chitosan sources, modification methods, and production techniques.
8.4. Heterogeneous nanocatalyst Global applications, benefits and drawbacks of the biopolymer are listed
in detail. This review also points out certain areas for future research and
The excellent therapeutic and pharmacological functionalities can be motivates the researchers to work on ways to enhance the physi
exerted by the synthesised 1,4-dyhdropyridine, 1,8-dioxo-decahy ochemical attributes of the chitosan-based bionanocomposites. Finally,
droacridine, and polyhydroquinoline derivatives for anticancer, ger this review concludes that chitosan-based bionanocomposites have a
oprotective, antitubercular, antidiabetic, and analgesic activities. In this robust future with enhanced unique properties such as mechanical,
case, some conventional catalysts, i. e. iBr, CTAB, CuBr, salicylic acid, L- thermal, barrier properties, crystallisation and degradation rate, which
proline, and so forth, are used for this synthesis, where these conven signifies their speciality in the medical sector, industrial sector, agri
tional catalysts have some drawbacks. Such as inefficiency, impotent cultural sector, water purification, and so forth.
and low yield catalyst. In this case, chitosan and chitosan -based bio
nanocomposite could be an excellent future research option as a het CRediT authorship contribution statement
erogeneous bio nanocatalyst because recently, Asgharnasl et al. attained
promising outcomes from magnetic chitosan-terephthaloyl-creatine Motia Azmana: Writing, Editing
bionanocomposite [157]. Syed Mahmood: Conceptualizing, Supervision
Ayah Rebhi Hilles: Writing, Editing
8.5. Enhancing the properties for medical application Azizur Rahman: Editing, paraphrasing
Mohd Azmir Bin Arifin,: Editing, supervision
During our extensive study, we found that in some cases, the Shakeeb Ahmed: Art work and editing
chitosan-based bionanocomposites exhibit low solubility due to physi
ological pH. In this case, researchers should focus on developing new
bionanocomposites materials with chitosan that can exert enhanced Declaration of competing interest
solubility. Also, the possibility of using it for drug delivery is rising
tremendously, but in some cases, drug delivery to the desired organ isn't None.
achieved at satisfactory levels [104]. Their colloidal instability is also a
hindrance for large-scale drug delivery applications [94]. These features
require focus and improvisation. Acknowledgement
8.6. Flexible elasticity enhancement We would like to thanks Universiti Malaysia Pahang (UMP) for
providing facilities and financial support through internal grant PGRS-
As mentioned previously, the high elasticity of this material limits its 2003128. In addition, we extend our gratitude towards the Ministry of
application. In this case, researchers should focus on developing mate Education Malaysia (MOE) for providing a fundamental research grant
rials with flexible elasticity. scheme (grant no. FRGS/1/2019/STG05/UMP/02/9) and Universiti
Malaya for providing financial support.
8.7. Finding an alternative source
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International Journal of Biological Macromolecules 185 (2021) 832–848

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International Journal of Biological Macromolecules

A review on chitosan and chitosan-based bionanocomposites: Promising

1. Introduction interest in bionanocomposites is growing dramatically worldwide as

Fig. 1. Chitosan-based bionanocomposites.

Fig. 2. Chitosan from chitin by deacetylation [12].

Fig. 3. Chitosan modification by A. Phosphorylation B. Thiolation.

Fig. 4. Chitosan modification by A. Sulfation B. Alkylation.

4.2.7. Quaternisation Typical methods commonly used to prepare the chitosan-based

Fig. 5. Chitosan modification by quaternisation.

Fig. 6. Chitosan modification by graft copolymerisation.

Improved biocompatibility by chelation of

Fig. 7. Broadened application of chitosan-based bionanocomposites.

Table 2 drug delivery by creating a giant biopolymer and precisely tailoring

Fig. 8. Wound skin healing process using chitosan-based bionanocomposites.

7.1.4. Excellent film-forming ability 7.2. Drawbacks and challenges

and 1,8-dioxo-decahydroacridine derivatives, Int. J. Biol. Macromol. 144 (2020)

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