Chitosan As A Valuable Biomolecule From Seafood IndustryWaste in The Design of Green Food Packaging
Chitosan As A Valuable Biomolecule From Seafood IndustryWaste in The Design of Green Food Packaging
Chitosan As A Valuable Biomolecule From Seafood IndustryWaste in The Design of Green Food Packaging
net/publication/355787682
CITATIONS READS
27 8,005
2 authors:
All content following this page was uploaded by Bárbara Teixeira-Costa on 08 November 2021.
Review
Chitosan as a Valuable Biomolecule from Seafood Industry
Waste in the Design of Green Food Packaging
Barbara E. Teixeira-Costa 1,2, * and Cristina T. Andrade 1
Abstract: Chitosan is a versatile biomolecule with a broad range of applications in food and pharma-
ceutical products. It can be obtained by the alkaline deacetylation of chitin. This biomolecule can be
extracted using conventional or green methods from seafood industry residues, e.g., shrimp shells.
Chitin has limited applications because of its low solubility in organic solvents. Chitosan is soluble in
acidified solutions allowing its application in the food industry. Furthermore, biological properties,
such as antioxidant, antimicrobial, as well as its biodegradability, biocompatibility and nontoxicity
have contributed to its increasing application as active food packaging. Nevertheless, some physical
and mechanical features have limited a broader range of applications of chitosan-based films. Green
approaches may be used to address these limitations, leading to well-designed chitosan-based food
packaging, by employing principles of a circular and sustainable economy. In this review, we summa-
rize the properties of chitosan and present a novel green technology as an alternative to conventional
chitin extraction and to design environmentally friendly food packaging based on chitosan.
Citation: Teixeira-Costa, B.E.;
Andrade, C.T. Chitosan as a Valuable Keywords: chitin; chitosan; bioactive molecules; seafood industry residues; crustacean shells;
Biomolecule from Seafood Industry green solvents; plasticizer; biodegradable food packaging; coatings; polysaccharides
Waste in the Design of Green Food
Packaging. Biomolecules 2021, 11, 1599.
https://doi.org/10.3390/
biom11111599 1. Introduction
Natural biomolecules from renewable sources, such as chitosan, appear as good al-
Academic Editor: Diaa Youssef
ternatives for the development of biodegradable food packaging. Chitosan is a linear
Received: 4 October 2021
polymer obtained by alkaline deacetylation of chitin. This biopolymer is extracted from
Accepted: 24 October 2021 crustacean exoskeleton, provided by seafood industry waste [1,2]. The biomass of crus-
Published: 28 October 2021 taceans is comprised of proteins, calcium carbonate, chitin, pigments, and lipids [2]. The
extraction process leads close to 20–30% of chitin, by applying mechanical and chemical
Publisher’s Note: MDPI stays neutral treatments [2]. The alkali/acid conventional treatments of crustacean biomass to obtain
with regard to jurisdictional claims in chitin and chitosan can present low efficiency and may be considered disadvantageous
published maps and institutional affil- when looking at the environment and labor conditions. However, green solvents, such as
iations. 1-allyl-3-methylimidazolium bromide and 1-ethyl-3-methyl-imidazolium acetate, can be
used to replace those methods and improve the efficiency of chitin extraction and chemical
modification processes [3].
The use of natural materials has advantages, in addition to reducing the consumption
Copyright: © 2021 by the authors.
of petroleum-derived polymers and environmental pollution. These materials present good
Licensee MDPI, Basel, Switzerland. bioavailability, biocompatibility, and biodegradability. They also act as antioxidants, antimi-
This article is an open access article crobials, with low toxicity and low allergenicity [4,5]. In the development of biobased films,
distributed under the terms and their hydrophilic character should be considered, because humidity may be a problem
conditions of the Creative Commons to the shelf life of the product, as well as to the physical stability of the packaging. To
Attribution (CC BY) license (https:// overcome this issue, hydrophobic or less hydrophilic substances can be incorporated to
creativecommons.org/licenses/by/ the films modifying its physical properties. These substances, denominated plasticizers,
4.0/).
are responsible for increasing the matrix free volume and molecular mobility of amor-
phous biopolymers, competing with intermolecular H-bonding [6,7]. Glycerol, sorbitol,
polyethylene glycols (PEG), lipids and their derivatives are the most used plasticizers to
biobased films, although novel sustainable alternatives, e.g., deep eutectic solvents (DES),
have also been used [8–10]. These sustainable substances are obtained by complexation
of a hydrogen bond donor (HBD) with a quaternary ammonium salt (hydrogen bond
acceptor—HBA), producing liquids with physical and solvent properties analogue to ionic
liquids (ILs) [11,12]. The mixture between choline chloride and glycerol (ChCl-Gly) has
been the most used DES for plasticizing of chitosan-based coatings [8,9,13].
In this context, this review aims to summarize the application of waste from fishery
industries as a source for chitin, mainly from crustaceans’ shells. As the deacetylated
derivative chitosan is a bioactive molecule that can be used in several industrial processes,
its biological properties and novel green technologies to design environmentally friendly
food packaging are also reviewed.
Figure 1. Major types of marine crustaceans globally produced by capture over the last two decades.
Biomolecules 2021, 11, 1599 3 of 19
The intensive growing of the aquaculture industry, including crustaceans, fishes, mol-
luscs, and others, is related to higher rates of fish consumption, which is among the most
traded of food commodities [17]. However, a great number of challenges have shaken the
seafood industry, mainly related to its environmental and social unsustainability. Some of
these issues are due to the destruction of seabed when using bottom drag nets, overexploita-
tion and illegal fishing, lack of sanitary conditions on fishing boats, killing untargeted sea
animals that get trapped in fishing lines, disposition of inedible parts of sea animals directly
into the water, pollution, forced and analogous slavery works, among others [1,14,17].
Fishing activities are known for generating a high amount of waste, since bones, shells,
heads, skins, and visceral parts are not commonly eaten by humans. Between 2010 and
2014 the annual residue generated by global marine fisheries reached more than 9 Mt and
close to 45% of it was from capture using bottom dragging nets [1]. The loss of global fishes
was estimated to be close to 12 Mt per year, representing 10% of total seafood capture and
aquaculture [20]. A recent report indicated that around 60% of all processed fishes are
discarded, which are composed of ~20% muscles, ~18% viscera, ~15% bones, ~12% heads,
5% of scales and up to 3% of skin and fins [21]. However, the estimation of seafood losses
and waste have been reported to be conflicting, because of the lack of information and
uniformity in the assessment of data [15]. To these authors, waste generation is linked
to issues during the different steps in the processing chain, such as primary and post-
production, processing, distribution, and consumption, as well as a lack of uniformity in
the definition of loss type, such as physical, quality, nutritional losses and others.
These seafood by-products end up being majorly utilized as animal feed, agricultural
fertilizer, lipids extraction, biogas and biodiesel production [1,2]. Technological approaches
of the valorization of seafood by-products are needed since those materials are great sources
of bioactive compounds, such as amino acids and proteins, gelatin, collagen, vitamins,
pigments, calcium carbonate, polyunsaturated fatty acids, and chitin [1,14].
tions [31]. A substantial amount of waste is produced during seafood processing, making
the extraction of chitin from this residue a good opportunity to add value to this market
and to reduce the environment contamination.
However, chitin is an underutilized biomass resource, being mostly used for the
chemical production of chitosan. About 33 kg of shrimp shells (in a wet basis), 0.02 L of
diesel for bulldozer operation, 8 kg of HCl 32%, 1.3 kg of NaOH, 1.3 kWh of electricity and
around 170 L of freshwater, are needed to produce one kilogram of chitin [32]. To obtain
1 kg of chitosan, 1.4 kg of chitin, 5.18 kg of NaOH, around 1.1 kWh of energy and 250 L
of water are needed [32]. Although during the production of chitin and chitosan, some
chemicals and other resources are used, the use of seafood shells as raw materials helps
prevent the accumulation of composting materials that end up polluting the environment,
and could alter the sea life cycle, and save composting emissions such as ammonia [32].
As chitin is a highly acetylated polymer, insoluble in water, traditional methods, such
as chemical deacetylation, or enzymatic hydrolysis, are most commonly used to make it
less hydrophobic, which results in the production of chitosan [25,26,33,34]. Its chemical
deacetylation involves an alkaline treatment at high temperatures. Different factors, such
as alkali concentration, processing time, chitin:alkali ratio, temperature, and chitin source,
can affect the degree of N-acetylation (DA) of chitosan.
To overcome the use of hazardous chemicals during chitin extraction, an alterna-
tive green extraction method has been reported [35]. Some researchers have easily used
ionic liquids, such as 1-allyl-3-methylimidazolium bromide (AMIMBr), followed by dem-
ineralization by employing 1.5% of citric acid and subjecting it to different extraction
temperatures (80–120 ◦ C) for 6–48 h, achieving a chitosan yield up to 12.6% [36]. More-
over, according to some authors, 1-ethyl-3-methyl-imidazolium acetate was able to recover
higher amounts, around 94%, of chitin from shrimp shells [37]. To these authors, the
extracted chitin exhibited a higher Mw and the processing conditions were less harsh than
the conventional methods to chitin extraction. This result demonstrates the benefits of
using green solvents to improve chitin extraction.
Chitin is insoluble in many organic and inorganic solvents, due to its high intra and
intermolecular hydrogen bonds. Its dissolution is essential to estimate the molecular weight
(Mw ). However, the presence of aggregates in chitin dispersion trickles the measurements
by light scattering, which fails in determining molecular weight [38]. To bypass this, green
solvents as ionic liquids and deep eutectic solvents, e.g., 1-allyl-3-methylimidazolium
bromide, 1-ethyl-3-methylimidazolium alkanoates and others, have been recently used
for chitin solubilization [3]. A schematic summary of conventional and green extraction
techniques and potential applications of chitin/chitosan are presented in Figure 3.
Biomolecules 2021, 11, 1599 5 of 19
Chitosan is a natural polysaccharide derived from chitin. Both polysaccharides are the
most abundant biopolymers from an animal source [22]. The first work with chitosan dates
from the 1850s, when Charles Rouget reported that he had obtained a novel chitine modifiée
after treating chitin with a concentrated alkaline solution under reflux, making modified
chitin soluble in organic acids [24]. Many years later, in the 1890s, shells from crabs,
scorpions and spiders were treated by Felix Hoppe-Seyler with a solution of potassium
hydroxide at 180 ◦ C. This researcher obtained a soluble acid solution product named
chitosan [22,24]. Up to the 1950s, chitin and chitosan gained considerable attention due to
the increasing exploitation of natural polymers.
Chitosan is a versatile natural polymer with a broad range of applications in food
products, mainly because of its biodegradability, biocompatibility, nontoxicity, and bioac-
tive properties, such as antioxidant, antimicrobial, and anticancer activities [4]. Chitosan
is a linear random copolymer of N-acetyl-D-glucosamine (A-units) and deacetylated D-
glucosamine (D-units) units connected by β-1,4 glycosidic linkages (Figure 4), obtained
from the chemical alkaline deacetylation of chitin [4,33]. In each repeating unit, the chi-
tosan molecule has three functional groups, i.e., primary, and secondary hydroxyl groups
and amine groups. These groups allow chemical changes under pronation, and influence
its biological, mechanical, and physical-chemical characteristics, including solubility, hy-
drophilicity, and crystallinity [3,4]. The amine groups, NH2 , located on C-2 of the rings
on the D-glucosamine repeated units, may be pronated and induce changes on chitosan
chains under acidic conditions, acquiring a polycationic characteristic [4,28].
The properties of chitosan in solution depend on the degree of acetylation (DA), chain
length, and distribution of acetyl groups along the chain [26]. The DA is given by the
ratio between its acetylated and deacetylated units and is expressed as molar percentage
(mol%). The DA can range between 0.05 and 0.30. Below DA = 50%, chitosan is soluble
in aqueous acidic media [25,33]. The chitosan origin has an influence on its DA as well
as on its Mw . Generally, microbial chitosan exhibited a lower DA than those extracted
from the exoskeleton of crustaceans [34]. Heterogenous deacetylation played on solid-state
chitin may produce a block-wise distribution of acetyl groups causing chain linkage and
consequently affecting its dissolution and Mw quantification [38]. The DA and the Mw
are the most important factors contributing to the physicochemical identity of chitosan
Biomolecules 2021, 11, 1599 6 of 19
and influence its structure-properties relationships, e.g., solubility, viscosity, and gelling
abilities, among others [39,40].
The main characterization of chitosan starts with the determination of its molecular
weight in solution, followed by the DA quantification and finally the distribution of acetyl
groups along the backbone chain (by nuclear magnetic resonance—13 C NMR) [38]. Various
methods have been used to quantify the molecular weight of chitosan, e.g., viscosimetry,
light scattering, osmometry, size exclusion chromatography and more recently the multi-
detection asymmetric flow-field flow fractionation [39]. The chitosan DA can be determined
by infrared spectroscopy, potentiometric titration, and elementary analysis, although, 1 H
liquid state and solid-state 13 C NMR spectroscopy have been favored [38,40]. Besides
these parameters, the intrinsic viscosity, [η], is also an important factor to be considered
for chitosan characterization. The [η] may be determined by double extrapolation to zero
concentration of Huggins’ and Kraemer’s equations (Equations (1) and (2)) [28].
ηsp
= [η] + k 0 [η]2 C (1)
C
( Ln ηrel )
= [η] + k00 [η]2 C (2)
C
where ηrel and ηsp are the relative and specific viscosities, k0 and k” are the Huggins’ and
Kraemer’s coefficients, respectively, and C is the chitosan solution concentration.
The intrinsic viscosity is essential to determine the viscosity average molecular weight,
Mv , using the Mark-Houwink-Sakurada relationship as expressed in Equation (3) [28,38].
a
[η] mL g−1 = KMv (3)
where [η] is the intrinsic viscosity, K is the intercept and a is the equation slope, and M is
the viscosity average molecular weight for chitosan.
Brugnerotto et al. [41] characterized chitosan by steric exclusion chromatography with
different DA (0.5 to 25 mol%) and found values for the K and a constants varying from
0.080 to 0.068, and 0.796 to 0.800 (random coil), respectively, when the used solvent was
AcOH 0.3 M/AcONa 0.2 M at 25 ◦ C. High values (>0.800) of a coefficient indicates a semi-rigid
feature of the polysaccharide with a very stiff chain, and when a presents a low value (<0.650)
it is an indication that the chain has adopted a compact sphere conformation. This variation
affects their hydrodynamic volume, dimensions, and viscometrical properties [38]. However,
the most frequent values reported for the constant a ranged between 0.7 and 1.0, indicating
that chitosan behaves like a flexible or linear conformation depending on the solvent [42].
Chitosan is a versatile material, used for a wide range of applications. It is considered
an eco-friendly biopolymer since its biodegradability in various environments as other
natural polysaccharides (Figure 5). For environmental purposes, it can be used for wa-
Biomolecules 2021, 11, 1599 7 of 19
significant reduction (p < 0.05) in body weight and body fat of overweight/obese participants
that received CS supplementation [49]. However, studies aiming to investigate this question
may differ, as there are different sources and types of chitosan. Moreover, approaches using
different dosage, timing, methodologies to assess end points (weight loss vs. fat loss), lack of
well-constructed clinical trials, and other issues can affect these studies [50].
Another common utilization of CS by the food industry can be highlighted due to its
excellent antimicrobial/antioxidant properties. To this purpose, CS can be used in many
different forms and applications, e.g., as a solution, in powders, gels, beads/particles, fillers,
films, casting or sprayed coatings, as well as its blends. The use of chitosan for preservative
purposes of foods as an antimicrobial/antifungal agent has been well reported by many
authors [22,51–54]. CS has a broad range of antimicrobial activity against pathogenic
microorganisms, a bacteriostatic effect against Gram-positive and Gram-negative bacteria,
e.g., Escherichia coli, Vibrio cholerae and Shigella dysenteriae. CS also acts against yeasts and
molds, generally being more active against them than with bacteria [22,47,55]. A summary
of chitosan applications is listed in Table 1.
Mainly, the physical state as well as the solubility of chitosan are the most significant
factors that affect its antimicrobial activity. It was observed that microbial inhibition by
chitosan only occurred in acidic mediums, where it is soluble and has a net positive charge [53].
Although not completely elucidated, antimicrobial, antifungal, and antiviral properties have
been correlated to interaction with chitosan protonated groups, involving electrostatic stacking
at the cell surface, chelation of essential trace elements and metalloenzymes, protonation forms
and cell membranes disruption, and blockage of RNA transcription from DNA when chitosan
molecules are inside cell’s nucleus [22,25,34,51,56]. This electrostatic staking occurs by the
interaction between protonated amino groups of glucosamine and negative cell membrane
of microorganisms, affecting its integrity and permeability and consequently altering their
metabolism, which can lead to cell death [22]. Moreover, CS can prevent the production of
toxins and bind essential trace metals and spores acting as a chelating agent, which affects the
essential supply of nutrients, inhibiting microbial growth [22].
Other environment factors, such as molecular weight, DA, positive charge density,
pH, ionic strength, and temperature, can also influence its antimicrobial activities [53,55].
Furthermore, chitosan easily forms quaternary ammonium salts at low pH values. Thus, or-
ganic acids, such as acetic, formic, and lactic acids can dissolve it [27]. Acetic acid, generally
at 1% concentration, is the most common organic acid used for chitosan dissolution [57].
When chitosan is dissolved in an acidic media, generally below pH 6.5, its amino groups
in the main chain protonate and turns in to a cationic polysaccharide. These positively
charged groups, protonated amines, allow the interaction with a wide range of negative
charged molecules forming complexes. Some of these negative charged substances are an-
ionic synthetic or natural polymers, dyes, lipids, fats and cholesterol, metals ions, enzymes,
biological cells, DNA and RNA [3].
Table 1. Conts.
in the environment, also contributing to world pollution [79]. In addition to all of this,
packaging manufacturers face a new market challenge due to consumer demand for
biobased resources for food packaging [79,85]. Thus, all these circumstances have been
stimulating the search for new biobased materials and the development of biodegradable
packaging from renewable sources as strategies to mitigate pollution and sustain the planet.
In response to these challenges, there is a great opportunity for the development of novel
food packaging. In this context, biobased, biodegradable, compostable, edible, active and
intelligent packaging are innovative trends in the field.
Pure chitosan films can only be prepared via solvent casting. In this process, chitosan
is dissolved using enough solvent, mainly, acidified water, placed on a flat surface and let
to dry until constant weight. Generally, these pure films are reported to exhibit a smooth,
continuous, and compact surface, but are brittle and fragile possessing low mechanical
properties [26,33,92]. To overcome the low mechanical performance and high sensitivity
to water, the addition of plasticizers and other different approaches have been indicated.
Some of these use crosslinking, complexation, graft copolymerization, surface coating,
filler incorporation and others [22]. Blending chitosan with other polymers by solution
or extrusion blending to form composite films could also be a strategy. Binary or ternary
blends, e.g., CS-gelatin, CS-alginate, CS-gelatin-caprolactone, have been developed for
food and biomedical applications [33]. The formation of a cohesive film-forming material
resistant to rupture between CS and cellulose in the paper industry have also been reported,
as the wet strength of paper can be improved by CS addition [33]. In another study, CS
was used as a surface coating agent on printing paper, improving its mechanical properties,
such as its strength, and inhibited the growth of bacteria, such as E. coli [93].
Regarding the mechanical properties, tensile strength (TS) and elongation at break
(EB) are two of the most important characteristics for film applications [25]. TS is related
to the maximum tensile stress that a film can hold up [94]. Moreover, the TS of chitosan
films with high and low molecular weight was described as dependent on storage time
due to the conformational changes of chitosan molecules by the free volume reduction [95].
The type of solvent acid used to prepare chitosan-starch composite films also influenced
TS according to the following order: lactic acid < malic < acetic acid [96]. In another work,
chitosan film displayed a significantly lower TS, 18.252 MPa, but a higher EB, ~40%, than
gelatin and composite films [97]. In the development of chitosan-zein composite films,
Sun et al. [94] found that TS was influenced by different plasticizers, sorbitol < glycerol and
PEG-400; this result was explained by the number of hydroxyl groups in the plasticizer.
Sorbitol has the capacity of binding a higher number of water molecules. The TS values
may also decrease with the increase in pH because of a lower chitosan dissociation [57].
Furthermore, in chitosan composite films with quinoa protein, it was observed that TS and
EB were influenced by the presence of protein in the films [98]. Some application examples
of chitosan-based films are listed in Table 2.
Biomolecules 2021, 11, 1599 12 of 19
Table 2. Conts.
Water vapor and the oxygen barrier are relevant factors to consider in the development
of food packaging since both can influence the food quality and shelf life. The evaluation
of water vapor permeability (WVP) of polysaccharide-based films provides information
of diffusion and solubility of water molecules through the polymeric matrix and will be
influenced by its composition. In this context, the WVP of high and low molecular weight
chitosan films was investigated by Kerch and Korkhov [95]. They found that the high
molecular weight chitosan films exhibited higher permeability. The addition of a natural
phenolic antioxidant, protocatechuic acid, significantly decreased the WVP of chitosan
composite films [112]. Furthermore, the addition of vegetable olive and corn oils displayed
a significant effect decreasing the WVP by reducing the hydrophilic content of the film [103].
Different mechanical and barrier properties of chitosan films have been reported. These
properties are affected by chitosan molecular weight, solvent, plasticizer content, film
composition, and pH, which makes the comparison between them more challenging.
DESs contain large asymmetric ions of the HBA that have low lattice energy and so, low
melting points, caused by hydrogen bonding formation. A wide range of mixtures of sub-
stances can form DES, which was critically reviewed by Smith et al. [12]. For plasticizing film
packaging the most common DES used are the mixture of choline chloride-citric acid (ChCl-
CA), choline chloride-urea (ChCl-Urea) and choline chloride-glycerol (ChCl-Gly). The latter
has been used mainly for chitosan-based coatings [8,9,13]. Particularly, the eutectic mixtures
of ChCl:Gly at a molar ratio of 1:2 were found to efficiently plasticize starch and starch/zein
blends, and chitosan and chitosan/micro-crystalline cellulose/curcumin composites [9,10].
Many advantages can be pointed out from using DES as they are much cheaper,
safer and easier to manufacture than ionic liquids. Moreover, DES are chemically and
thermally stable, non-flammable, possessing high dissolution ability, lack of flammability,
low volatility, low melting point and tailorability, as well as being water neutral, and
low- or non-toxic. The DES toxicity, including cytotoxicity and phytotoxicity, is highly
dependent on the testing species used on the mixture and their responses, as well as their
physicochemical properties, concentration, and salts counteranion species [13]. In the work
of Mbous et al. [114], the toxicity of some DES was tested, and they found that pure ChCl
exhibited lower cytotoxic values than its aqueous solutions (EC50 30 ≥ ChClaq ≤ 40 mM),
suggesting that ChCl did not dissociate after crossing the cellular membrane, implying
a nontoxic profile of ChCl-based DES, although more in vivo or in vitro studies could be
further investigated [114]. As they are often biodegradable, they can be considered green
solvents. DESs are appropriate for biobased packaging processing and application. For the
preparation of polysaccharide films, the DES mixture should be separately prepared and
incorporated to the matrix materials or can be formed in situ after heat homogenization
with other components [13].
4. Conclusions
In this review, we discussed the increasing industrial seafood production and the chal-
lenges related to its growth, mainly due to the high waste generation and the consequences
of the environmental pollution. Valuable biomolecules for the food and pharmaceutical
industries, such as chitin and chitosan, can be extracted from these residues. Eastern mar-
kets have been leading the industrialization of these biopolymers. Japan may be cited as
an example for consuming more than 800 tonnes per year of both biopolymers. Chitin and
chitosan are linear polysaccharides. The first is insoluble in many organic and inorganic
solvents. This limitation is overcome by alkaline deacetylation forming chitosan, which is
soluble in acid solutions. Chitosan is a versatile biomolecule with a broad range of applica-
tions in food products, mainly because of its biodegradability, biocompatibility, nontoxicity,
and bioactive properties. These biological properties as well as their mechanical and
physicochemical characteristics depend on the chitosan acetylation degree, chain length,
and distribution of acetyl groups along the chains. Because of those versatile properties,
chitosan is among the most studied polysaccharides for the development of film/coating
packaging. The first reports on chitosan films are from the mid-1930s and until now it
has been applied differently in the development of biodegradable food packaging. One of
the main challenges for using chitosan to design food packaging is related to its physical
properties, e.g., water vapor permeability and processability. The use of green reagents
as DESs, are allies to defeat those difficulties and to improve the mechanical properties
of chitosan films. The most commonly used DES to plasticize chitosan-based films is
choline chloride-glycerol. Many advantages can be pointed out by using green solvents as
they can be safer, thermally stable, non-flammable, and easier to manufacture than other
conventional reagents and even ionic liquids. Moreover, DESs can exhibit low toxicity and
are considered biodegradable and nonpolluting, making them a valuable additive to the
development of chitosan-based films. Furthermore, the exploitation of chitin and chitosan
from seafood waste contributes to the seafood chain production by reducing the amount of
crustacean residues discarded in the environment. Indeed, this is an important approach in
a circular and sustainable economy. From another perspective, the conventional extraction
Biomolecules 2021, 11, 1599 15 of 19
of both biomolecules requires the use of hazardous chemicals, such as sodium hydroxide
and hydrochloric acid. However, innovative technological approaches, like the use of green
solvents, can once again be used to replace those, making the extraction process more
efficient and more environmentally friendly.
Author Contributions: Conceptualization, B.E.T.-C. and C.T.A.; literature data collection, B.E.T.-C.;
writing—original draft, B.E.T.-C.; writing—review and editing, B.E.T.-C. and C.T.A.; supervision,
C.T.A. All authors have read and agreed to the published version of the manuscript.
Funding: The authors acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico—
Brazil (CNPq) (Grant no. 306482/2019-3), Fundação de Amparo à Pesquisa do Estado do Rio de
Janeiro—Brazil (FAPERJ) (Grant no. E-26/010.000984/2019) and Coordenação de Aperfeiçoamento
de Pessoal de Nível Superior—Brasil (CAPES), Finance Code 001.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Ozogul, F.; Cagalj, M.; Šimat, V.; Ozogul, Y.; Tkaczewska, J.; Hassoun, A.; Kaddour, A.A.; Kuley, E.; Rathod, N.B.; Phadke, G.G.
Recent developments in valorisation of bioactive ingredients in discard/seafood processing by-products. Trends Food Sci. Technol.
2021, 116, 559–582. [CrossRef]
2. Schmitz, C.; González Auza, L.; Koberidze, D.; Rasche, S.; Fischer, R.; Bortesi, B. Conversion of Chitin to Defined Chitosan
Oligomers: Current Status and Future Prospects. Mar. Drugs 2019, 17, 452. [CrossRef] [PubMed]
3. Khayrova, A.; Lopatin, S.; Varlamov, V. Obtaining chitin, chitosan and their melanin complexes from insects. Int. J. Biol. Macromol.
2021, 167, 1319–1328. [CrossRef] [PubMed]
4. Mujtaba, M.; Morsi, R.E.; Kerch, G.; Elsabee, M.Z.; Kaya, M.; Labidi, J.; Khawar, K.M. Current advancements in chitosan-based
film production for food technology; A review. Int. J. Biol. Macromol. 2019, 121, 889–904. [CrossRef] [PubMed]
5. Tavassoli-Kafrani, E.; Shekarchizadeh, H.; Masoudpour-Behabadi, M. Development of edible films and coatings from alginates
and carrageenans. Carbohydr. Polym. 2016, 137, 360–374. [CrossRef] [PubMed]
6. Quirós-Sauceda, A.E.; Ayala-Zavala, J.F.; Olivas, G.I.; González-Aguilar, G.A. Edible coatings as encapsulating matrices for
bioactive compounds: A review. J. Food Sci. Technol. 2014, 51, 1674–1685. [CrossRef]
7. Rivero, S.; Damonte, L.; Garcia, M.A.; Pinotti, A. An Insight into the Role of Glycerol in Chitosan Films. Food Biophys. 2016, 11,
117–127. [CrossRef]
8. Almeida, C.M.R.; Magalhães, J.M.C.S.; Souza, H.K.S.; Gonçalves, M.P. The role of choline chloride-based deep eutectic solvent
and curcumin on chitosan films properties. Food Hydrocoll. 2018, 81, 456–466. [CrossRef]
9. Pereira, P.F.; Andrade, C.T. Optimized pH-responsive film based on a eutectic mixture-plasticized chitosan. Carbohydr. Polym.
2017, 165, 238–246. [CrossRef]
10. Sousa, A.M.M.; Souza, H.K.S.; Latona, N.; Liu, C.-K.; Gonçalves, M.P.; Liu, L. Choline chloride based ionic liquid analogues as
tool for the fabrication of agar films with improved mechanical properties. Carbohydr. Polym. 2014, 111, 206–214. [CrossRef]
[PubMed]
11. Abbott, A.P.; Harris, R.C.; Ryder, K.S.; D’Agostino, C.; Gladden, L.F.; Mantle, M.D. Glycerol eutectics as sustainable solvent
systems. Green Chem. 2011, 13, 82–90. [CrossRef]
12. Smith, E.L.; Abbott, A.P.; Ryder, K.S. Deep Eutectic Solvents (DESs) and Their Applications. Chem. Rev. 2014, 114, 11060–11082.
[CrossRef]
13. Zdanowicz, M.; Wilpiszewska, K.; Spychaj, T. Deep eutectic solvents for polysaccharides processing. A review. Carbohydr. Polym.
2018, 200, 361–380. [CrossRef]
14. Mathew, G.M.; Sukumaran, R.K.; Sindhu, R.; Binod, P.; Pandey, A. Green remediation of the potential hazardous shellfish wastes
generated from the processing industries and their bioprospecting. Environ. Technol. Innov. 2021, 24, 101979. [CrossRef]
15. Kruijssen, F.; Tedesco, I.; Ward, A.; Pincus, L.; Love, D.; Thorne-Lyman, A.L. Loss and waste in fish value chains: A review of the
evidence from low and middle-income countries. Glob. Food Sec. 2020, 26, 100434. [CrossRef]
16. Jouffray, J.-B.; Crona, B.; Wassénius, E.; Bebbington, J.; Scholtens, B. Leverage points in the financial sector for seafood sustainability.
Sci. Adv. 2019, 5, eaax3324. [CrossRef] [PubMed]
17. Shamshak, G.L.; Anderson, J.L.; Asche, F.; Garlock, T.; Love, D.C. U.S. seafood consumption. J. World Aquac. Soc. 2019, 50, 715–727.
[CrossRef]
18. Food and Agriculture Organization (FAO). Statistics Division. Commodity Balances—Livestock and Fish Primary Equivalent; FAO:
Rome, Italy, 2021; Available online: http://www.fao.org/faostat/en/#home (accessed on 26 April 2021).
Biomolecules 2021, 11, 1599 16 of 19
19. Food and Agriculture Organization (FAO). The State of World Fisheries and Aquaculture 2020—Sustainability in Action; FAO:
Rome, Italy, 2020. Available online: https://www.fao.org/documents/card/en/c/ca9229en (accessed on 18 October 2021).
20. Maulu, S.; Hasimuna, O.J.; Monde, C.; Mweemba, M. An assessment of post-harvest fish losses and preservation practices in
Siavonga district, Southern Zambia. Fish. Aquat. Sci. 2020, 23, 25. [CrossRef]
21. Tacias-Pascacio, V.G.; Castañeda-Valbuena, D.; Morellon-Sterling, R.; Tavano, O.; Berenguer-Murcia, Á.; Vela-Gutiérrez, G.; Rather,
I.A.; Fernandez-Lafuente, R. Bioactive peptides from fisheries residues: A review of use of papain in proteolysis reactions. Int. J.
Biol. Macromol. 2021, 184, 415–428. [CrossRef] [PubMed]
22. Haghighi, H.; Licciardello, F.; Fava, P.; Siesler, H.W.; Pulvirenti, A. Recent advances on chitosan-based films for sustainable food
packaging applications. Food Packag. Shelf Life 2020, 26, 100551–100567. [CrossRef]
23. Sanchez-Salvador, J.L.; Balea, A.; Monte, M.C.; Negro, C.; Blanco, A. Chitosan grafted/cross-linked with biodegradable polymers:
A review. Int. J. Biol. Macromol. 2021, 178, 325–343. [CrossRef] [PubMed]
24. Crini, G. Historical review on chitin and chitosan biopolymers. Environ. Chem. Lett. 2019, 17, 1623–1643. [CrossRef]
25. Van den Broek, L.A.M.; Knoop, R.J.I.; Kappen, F.H.J.; Boeriu, C.G. Chitosan films and blends for packaging material. Carbo-
hydr. Polym. 2015, 116, 237–242. [CrossRef]
26. Hoell, I.A.; Vaaje-Kolstad, G.; Eijsink, V.G.H. Structure and function of enzymes acting on chitin and chitosan. Biotechnol. Genet.
Eng. Rev. 2010, 27, 331–366. [CrossRef] [PubMed]
27. Abdel-Rahman, R.M.; Hrdina, R.; Abdel-Mohsen, A.M.; Fouda, M.M.G.; Soliman, A.Y.; Mohamed, F.K.; Mohsin, K.; Pinto, T.D.
Chitin and chitosan from Brazilian Atlantic Coast: Isolation, characterization and antibacterial activity. Int. J. Biol. Macromol. 2015,
80, 107–120. [CrossRef]
28. Bastos, D.S.; Barreto, B.N.; Souza, H.K.S.; Bastos, M.; Rocha-Leão, M.H.M.; Andrade, C.T.; Gonçalves, M.P. Characterization of a
chitosan sample extracted from Brazilian shrimps and its application to obtain insoluble complexes with a commercial whey
protein isolate. Food Hydrocoll. 2010, 24, 709–718. [CrossRef]
29. Morin-Crini, N.; Lichtfouse, E.; Torri, G.; Crini, G. Applications of chitosan in food, pharmaceuticals, medicine, cosmetics, agriculture,
textiles, pulp and paper, biotechnology, and environmental chemistry. Environ. Chem. Lett. 2019, 17, 1667–1692. [CrossRef]
30. Markets and Markets. Chitosan Market. 2018. Available online: https://www.marketsandmarkets.com/Market-Reports/
chitosan-market-202177578.html (accessed on 19 October 2021).
31. Pandit, A.; Indurkar, A.; Deshpande, C.; Jain, R.; Dandekar, P. A systematic review of physical techniques for chitosan degradation.
Carbohydr. Polym. Technol. Appl. 2021, 2, 100033.
32. Muñoz, I.; Rodríguez, C.; Gillet, D.; Moerschbacher, B.M. Life cycle assessment of chitosan production in India and Europe. Int. J.
Life Cycle Assess. 2018, 23, 1151–1160. [CrossRef]
33. Muxika, A.; Etxabide, A.; Uranga, J.; Guerrero, P.; de la Caba, K. Chitosan as a bioactive polymer: Processing, properties and
applications. Int. J. Biol. Macromol. 2017, 105, 1358–1368. [CrossRef]
34. Philibert, T.; Lee, B.H.; Fabien, N. Current Status and New Perspectives on Chitin and Chitosan as Functional Biopolymers.
Appl. Biochem. Biotechnol. 2017, 181, 1314–1337. [CrossRef] [PubMed]
35. Zhao, D.; Huang, W.-C.; Guo, N.; Zhang, S.; Xue, C.; Mao, X. Two-step separation of chitin from shrimp shells using citric acid
and deep eutectic solvents with the assistance of microwave. Polymers 2019, 11, 409. [CrossRef] [PubMed]
36. Setoguchi, T.; Kato, T.; Yamamoto, K.; Kadokawa, J. Facile production of chitin from crab shells using ionic liquid and citric acid.
Int. J. Biol. Macromol. 2012, 50, 861–864. [CrossRef] [PubMed]
37. Qin, Y.; Lu, X.; Sun, N.; Rogers, R.D. Dissolution or extraction of crustacean shells using ionic liquids to obtain high molecular
weight purified chitin and direct production of chitin films and fibers. Green Chem. 2010, 12, 968. [CrossRef]
38. Younes, I.; Rinaudo, M. Chitin and Chitosan Preparation from Marine Sources. Structure, Properties and Applications. Mar. Drugs
2015, 13, 1133–1174. [CrossRef]
39. González-Espinosa, Y.; Sabagh, B.; Moldenhauer, E.; Clarke, P.; Goycoolea, F.M. Characterisation of chitosan molecular weight
distribution by multi-detection asymmetric flow-field flow fractionation (AF4) and SEC. Int. J. Biol. Macromol. 2019, 136, 911–919.
[CrossRef]
40. Kasaai, M. A review of several reported procedures to determine the degree of N-acetylation for chitin and chitosan using
infrared spectroscopy. Carbohydr. Polym. 2008, 71, 497–508. [CrossRef]
41. Brugnerotto, J.; Desbrières, J.; Roberts, G.; Rinaudo, M. Characterization of chitosan by steric exclusion chromatography. Polymer
2001, 42, 09921–09927. [CrossRef]
42. Kasaai, M.R. Calculation of Mark-Houwink-Sakurada (MHS) equation viscometric constants for chitosan in any solvent-
temperature system using experimental reported viscometric constants data. Carbohydr. Polym. 2007, 68, 477–488. [CrossRef]
43. Annu Raja, A.N. Recent development in chitosan-based electrochemical sensors and its sensing application. Int. J. Biol. Macromol.
2020, 164, 4231–4244. [CrossRef]
44. Oliveira, H.C.; Gomes, B.C.R.; Pelegrino, M.T.; Seabra, A.B. Nitric oxide-releasing chitosan nanoparticles alleviate the effects of
salt stress in maize plants. Nitric Oxide 2016, 61, 10–19. [CrossRef]
45. EPA—Environmental Protection Agency of United States. Safer Chemical Ingredients List. Available online: https://www.epa.
gov/saferchoice/safer-ingredients#pop9012764 (accessed on 10 May 2021).
Biomolecules 2021, 11, 1599 17 of 19
46. ANVISA—Agência Nacional de Vigilância Sanitária. Alegações de Propriedade Funcional Aprovadas pela ANVISA. Avail-
able online: https://www.gov.br/agricultura/pt-br/assuntos/inspecao/produtos-vegetal/legislacao-1/biblioteca-de-normas-
vinhos-e-bebidas/alegacoes-de-propriedade-funcional-aprovadas_anvisa.pdf/view (accessed on 10 May 2021).
47. Lopez-Santamarina, A.; Mondragon, A.D.C.; Lamas, A.; Miranda, J.M.; Franco, C.M.; Cepeda, A. Animal-origin prebiotics based
on chitin: An alternative for the Future? A critical review. Foods 2020, 9, 782. [CrossRef]
48. Trivedi, V.; Satia, M.; Deschamps, A.; Maquet, V.; Shah, R.; Zinzuwadia, P.; Trivedi, J. Single-blind, placebo controlled randomised
clinical study of chitosan for body weight reduction. Nutr. J. 2016, 15, 1–12. [CrossRef]
49. Huang, H.; Liao, D.; Zou, Y.; Chi, H. The effects of chitosan supplementation on body weight and body composition: A systematic
review and meta-analysis of randomized controlled trials. Crit. Rev. Food Sci. Nutr. 2020, 60, 1815–1825. [CrossRef]
50. Preuss, H.; Kaats, G. Chitosan as a Dietary Supplement for Weight Loss: A Review. Curr. Nutr. Food Sci. 2006, 2, 297–311. [CrossRef]
51. Friedman, M.; Juneja, V.K. Review of antimicrobial and antioxidative activities of chitosans in food. J. Food Prot. 2010, 73,
1737–1761. [CrossRef]
52. Ma, Z.; Garrido-Maestu, A.; Jeong, K.C. Application, mode of action, and in vivo activity of chitosan and its micro- and
nanoparticles as antimicrobial agents: A review. Carbohydr. Polym. 2017, 176, 257–265. [CrossRef] [PubMed]
53. Sahariah, P.; Másson, M. Antimicrobial chitosan and chitosan derivatives: A review of the structure-activity relationship.
Biomacromolecules 2017, 18, 3846–3868. [CrossRef] [PubMed]
54. Verlee, A.; Mincke, S.; Stevens, C.V. Recent developments in antibacterial and antifungal chitosan and its derivatives. Carbo-
hydr. Polym. 2017, 164, 268–283. [CrossRef] [PubMed]
55. Muñoz-Bonilla, A.; Cerrada, M.L.; Fernández-García, M. Antimicrobial activity of chitosan in food, agriculture and biomedicine.
In Polymeric Materials with Antimicrobial Activity: From Synthesis to Applications; Muñoz-Bonilla, A., Cerrada, M.L., Fernández-
García, M., Eds.; Royal Society of Chemistry: Cambridge, UK, 2014; pp. 22–53. [CrossRef]
56. Cazón, P.; Velazquez, G.; Ramírez, J.A.; Vázquez, M. Polysaccharide-based films and coatings for food packaging: A review.
Food Hydrocoll. 2017, 68, 136–148. [CrossRef]
57. Duan, C.; Meng, X.; Meng, J.; Khan, M.I.H.; Dai, L.; Khan, A.; An, X.; Zhang, J.; Huq, T.; Ni, Y. Chitosan as a preservative for fruits
and vegetables: A review on chemistry and antimicrobial properties. J. Bioresour. Bioprod. 2019, 4, 11–21. [CrossRef]
58. Teixeira-Costa, B.E.; Silva Pereira, B.C.; Lopes, G.K.; Andrade, C.T. Encapsulation and antioxidant activity of assai pulp oil
(Euterpe oleracea) in chitosan/alginate polyelectrolyte complexes. Food Hydrocoll. 2020, 109, 106097. [CrossRef]
59. Klinmalai, P.; Hagiwara, T.; Sakiyama, T.; Ratanasumawong, S. Chitosan effects on physical properties, texture, and microstructure
of flat rice noodles. LWT Food Sci. Technol. 2017, 76, 117–123. [CrossRef]
60. Han, M.; Clausen, M.P.; Christensen, M.; Vossen, E.; van Hecke, T.; Bertram, H.C. Enhancing the health potential of processed
meat: The effect of chitosan or carboxymethyl cellulose enrichment on inherent microstructure, water mobility and oxidation in a
meat-based food matrix. Food Funct. 2018, 9, 4017–4027. [CrossRef]
61. Pereda, M.; Amica, G.; Marcovich, N.E. Development and characterization of edible chitosan/olive oil emulsion films. Carbo-
hydr. Polym. 2012, 87, 1318–1325. [CrossRef]
62. Morelli, S.; Holdich, R.G.; Dragosavac, M.M. Chitosan and Poly (Vinyl Alcohol) microparticles produced by membrane emulsifi-
cation for encapsulation and pH controlled release. Chem. Eng. J. 2016, 288, 451–460. [CrossRef]
63. Rachtanapun, C.; Tantala, J.; Klinmalai, P.; Ratanasumawong, S. Effect of chitosan on Bacillus cereus inhibition and quality of
cooked rice during storage. Int. J. Food Sci. Technol. 2015, 50, 2419–2426. [CrossRef]
64. Bonilla, J.; Poloni, T.; Lourenço, R.V.; Sobral, P.J.A. Antioxidant potential of eugenol and ginger essential oils with gelatin/chitosan
films. Food Biosci. 2018, 23, 107–114. [CrossRef]
65. Menconi, A.; Hernandez-Velasco, X.; Latorre, J.D.; Kallapura, G.; Pumford, N.R.; Morgan, M.J.; Hargis, B.M.; Tellez, G. Effect of
chitosan as a biological sanitizer for Salmonella typhimurium and aerobic gram negative spoilage bacteria present on chicken skin.
Int. J. Poult. Sci. 2013, 12, 318–321. [CrossRef]
66. Rajaei, A.; Hadian, M.; Mohsenifar, A.; Rahmani-Cherati, T.; Tabatabaei, M. A coating based on clove essential oils encapsulated
by chitosan-myristic acid nanogel efficiently enhanced the shelf-life of beef cutlets. Food Packag. Shelf Life 2017, 14, 137–145.
[CrossRef]
67. Zhou, W.; He, Y.; Liu, F.; Liao, L.; Huang, X.; Li, R.; Zou, Y.; Zhou, L.; Zou, L.; Liu, Y.; et al. Carboxymethyl chitosan-pullulan
edible films enriched with galangal essential oil: Characterization and application in mango preservation. Carbohydr. Polym. 2021,
256, 117579. [CrossRef] [PubMed]
68. Wang, Q.; Zhang, C.; Wu, X.; Long, Y.; Su, Y. Chitosan augments tetramycin against soft rot in kiwifruit and enhances its
improvement for kiwifruit growth, quality and aroma. Biomolecules 2021, 11, 1257. [CrossRef]
69. Hai, L.V.; Zhai, L.; Kim, H.C.; Panicker, P.S.; Pham, D.H.; Kim, J. Chitosan Nanofiber and Cellulose Nanofiber Blended Composite
Applicable for Active Food Packaging. Nanomaterials 2020, 10, 1752. [CrossRef]
70. Wu, T.; Huang, J.; Jiang, Y.; Hu, Y.; Ye, X.; Liu, D.; Chen, J. Formation of hydrogels based on chitosan/alginate for the delivery of
lysozyme and their antibacterial activity. Food Chem. 2018, 240, 361–369. [CrossRef]
71. Yaroslavov, A.A.; Efimova, A.A.; Krasnikov, E.A.; Trosheva, K.S.; Popov, A.S.; Melik-Nubarov, N.S.; Krivtsov, G.G. Chitosan-based
multi-liposomal complexes: Synthesis, biodegradability and cytotoxicity. Int. J. Biol. Macromol. 2021, 177, 455–462. [CrossRef]
72. Muşat, V.; Anghel, E.; Zaharia, A.; Atkinson, I.; Mocioiu, O.; Buşilă, M.; Alexandru, P. A chitosan-agarose polysaccharide-based
hydrogel for biomimetic remineralization of dental enamel. Biomolecules 2021, 11, 1137. [CrossRef]
Biomolecules 2021, 11, 1599 18 of 19
73. Sousa, C.F.V.; Saraiva, C.A.; Correia, T.R.; Pesqueira, T.; Patrício, S.G.; Rial-Hermida, M.I.; Borges, J.; Mano, J.F. Bioinstructive
layer-by-layer-coated customizable 3D printed perfusable microchannels embedded in photocrosslinkable hydrogels for vascular
tissue engineering. Biomolecules 2021, 11, 863. [CrossRef] [PubMed]
74. Pop, N.L.; Nan, A.; Urda-Cimpean, A.E.; Florea, A.; Toma, V.A.; Moldovan, R.; Decea, N.; Mitrea, D.R.; Orasan, R. Chitosan
functionalized magnetic nanoparticles to provide neural regeneration and recovery after experimental model induced peripheral
nerve injury. Biomolecules 2021, 11, 676. [CrossRef]
75. Ladiè, R.; Cosentino, C.; Tagliaro, I.; Antonini, C.; Bianchini, G.; Bertini, S. Supramolecular structuring of hyaluronan-lactose-
modified chitosan matrix: Towards high-performance biopolymers with excellent biodegradation. Biomolecules 2021, 11, 389.
[CrossRef]
76. Marinho, S.; Illanes, M.; Ávila-Román, J.; Motilva, V.; Talero, E. Anti-inflammatory effects of rosmarinic acid-loaded nanovesicles
in acute colitis through modulation of NLRP3 inflammasome. Biomolecules 2021, 11, 162. [CrossRef] [PubMed]
77. Ribeiro-Santos, R.; Andrade, M.; Melo, N.R.; de Sanches-Silva, A. Use of essential oils in active food packaging: Recent advances
and future trends. Trends Food Sci. Technol. 2017, 61, 132–140. [CrossRef]
78. Sohail, M.; Sun, D.-W.; Zhu, Z. Recent developments in intelligent packaging for enhancing food quality and safety. Crit. Rev.
Food Sci. Nutr. 2018, 58, 2650–2662. [CrossRef]
79. Kamdem, D.P.; Shen, Z.; Nabinejad, O. Development of biodegradable composite chitosan-based films incorporated with xylan
and carvacrol for food packaging application. Food Packag. Shelf Life 2019, 21, 100344–100366. [CrossRef]
80. Carina, D.; Sharma, S.; Jaiswal, A.K.; Jaiswal, S. Seaweeds polysaccharides in active food packaging: A review of recent progress.
Trends Food Sci. Technol. 2021, 110, 559–572. [CrossRef]
81. Groh, K.J.; Backhaus, T.; Carney-Almroth, B.; Geueke, B.; Inostroza, P.A.; Lennquist, A.; Leslie, H.A.; Maffini, M.; Slunge, D.;
Trasande, L.; et al. Overview of known plastic packaging-associated chemicals and their hazards. Sci. Total Environ. 2019, 651,
3253–3268. [CrossRef]
82. Kleine Jäger, J.; Piscicelli, L. Collaborations for circular food packaging: The set-up and partner selection process. Sustain. Prod.
Consum. 2021, 26, 733–740. [CrossRef]
83. Soares, J.; Miguel, I.; Venâncio, C.; Lopes, I.; Oliveira, M. Public views on plastic pollution: Knowledge, perceived impacts, and
pro-environmental behaviours. J. Hazard. Mater. 2021, 412, 125227–125235. [CrossRef]
84. Rai, P.; Mehrotra, S.; Priya, S.; Gnansounou, E.; Sharma, S.K. Recent advances in the sustainable design and applications of
biodegradable polymers. Bioresour. Technol. 2021, 325, 124739–124751. [CrossRef] [PubMed]
85. Flury, M.; Narayan, R. Biodegradable plastic as an integral part of the solution to plastic waste pollution of the environment.
Curr. Opin. Green Sustain. Chem. 2021, 30, 100490. [CrossRef]
86. Otoni, C.G.; Avena-Bustillos, R.J.; Azeredo, H.M.C.; Lorevice, M.V.; Moura, M.R.; Mattoso, L.H.C.; McHugh, T.H. Recent
Advances on Edible Films Based on Fruits and Vegetables-A Review. Compr. Rev. Food Sci. Food Saf. 2017, 16, 1151–1169.
[CrossRef] [PubMed]
87. Petkoska, A.T.; Daniloski, D.; D’Cunha, N.M.; Naumovski, N.; Broach, A.T. Edible packaging: Sustainable solutions and novel
trends in food packaging. Food Res. Int. 2021, 140, 109981. [CrossRef]
88. Mkandawire, M.; Aryee, A.N. Resurfacing and modernization of edible packaging material technology. Curr. Opin. Food Sci.
2018, 19, 104–112. [CrossRef]
89. Liang, J.; Yan, H.; Zhang, J.; Dai, W.; Gao, X.; Zhou, Y.; Wan, X.; Puligundla, P. Preparation and characterization of antioxidant
edible chitosan films incorporated with epigallocatechin gallate nanocapsules. Carbohydr. Polym. 2017, 171, 300–306. [CrossRef]
90. Leceta, I.; Guerrero, P.; Cabezudo, S.; de la Caba, K. Environmental assessment of chitosan-based films. J. Clean. Prod. 2013, 41,
312–318. [CrossRef]
91. Oberlintner, A.; Bajić, M.; Kalčíková, G.; Likozar, B.; Novak, U. Biodegradability study of active chitosan biopolymer films
enriched with Quercus polyphenol extract in different soil types. Environ. Technol. Innov. 2021, 21, 101318. [CrossRef]
92. Liu, M.; Zhou, Y.; Zhang, Y.; Yu, C.; Cao, S. Preparation and structural analysis of chitosan films with and without sorbitol.
Food Hydrocoll. 2013, 33, 186–191. [CrossRef]
93. Zakaria, S.; Chia, C.H.; Wan Ahmad, W.H.; Kaco, H.; Chook, S.W.; Chan, C.H. Mechanical and Antibacterial Properties of Paper
Coated with Chitosan. Sains Malays. 2015, 44, 905–911. [CrossRef]
94. Sun, Y.; Liu, Z.; Zhang, L.; Wang, X.; Li, L. Effects of plasticizer type and concentration on rheological, physico-mechanical and
structural properties of chitosan/zein film. Int. J. Biol. Macromol. 2020, 143, 334–340. [CrossRef] [PubMed]
95. Kerch, G.; Korkhov, V. Effect of storage time and temperature on structure, mechanical and barrier properties of chitosan-based
films. Eur. Food Res. Technol. 2011, 232, 17–22. [CrossRef]
96. Zhong, Y.; Li, Y. Effects of storage conditions and acid solvent types on structural, mechanical and physical properties of kudzu
starch (Pueraria lobata)-chitosan composite films. Starch Stärke 2011, 63, 579–586. [CrossRef]
97. Wang, H.; Ding, F.; Ma, L.; Zhang, Y. Edible films from chitosan-gelatin: Physical properties and food packaging application.
Food Biosci. 2021, 40, 100871. [CrossRef]
98. Abugoch, L.E.; Tapia, C.; Villamán, M.C.; Yazdani-Pedram, M.; Díaz-Dosque, M. Characterization of quinoa protein-chitosan
blend edible films. Food Hydrocoll. 2011, 25, 879–886. [CrossRef]
99. Madian, N.G.; Mohamed, N. Enhancement of the dynamic mechanical properties of chitosan thin films by crosslinking with
greenly synthesized silver nanoparticles. J. Mater. Res. Technol. 2020, 9, 12970–12975. [CrossRef]
Biomolecules 2021, 11, 1599 19 of 19
100. Pavinatto, A.; de Almeida Mattos, A.V.; Malpass, A.C.G.; Okura, M.H.; Balogh, D.T.; Sanfelice, R.C. Coating with chitosan-based
edible films for mechanical/biological protection of strawberries. Int. J. Biol. Macromol. 2020, 151, 1004–1011. [CrossRef]
101. Da Costa, J.C.M.; Miki, K.S.L.; da Ramos, A.S.; Teixeira-Costa, B.E. Development of biodegradable films based on purple yam
starch/chitosan for food application. Heliyon 2020, 6, 1–10. [CrossRef]
102. Riaz, A.; Lei, S.; Akhtar, H.M.S.; Wan, P.; Chen, D.; Jabbar, S.; Abid, M.; Hashim, M.M.; Zeng, X. Preparation and characterization
of chitosan-based antimicrobial active food packaging film incorporated with apple peel polyphenols. Int. J. Biol. Macromol. 2018,
114, 547–555. [CrossRef]
103. Giannakas, A.; Patsaoura, A.; Barkoula, N.-M.; Ladavos, A. A novel solution blending method for using olive oil and corn oil as
plasticizers in chitosan based organoclay nanocomposites. Carbohydr. Polym. 2017, 157, 550–557. [CrossRef]
104. Shahbazi, Y. The properties of chitosan and gelatin films incorporated with ethanolic red grape seed extract and Ziziphora clinopodioides
essential oil as biodegradable materials for active food packaging. Int. J. Biol. Macromol. 2017, 99, 746–753. [CrossRef]
105. Ren, L.; Yan, X.; Zhou, J.; Tong, J.; Su, X. Influence of chitosan concentration on mechanical and barrier properties of corn
starch/chitosan films. Int. J. Biol. Macromol. 2017, 105, 1636–1643. [CrossRef] [PubMed]
106. Siripatrawan, U.; Vitchayakitti, W. Improving functional properties of chitosan films as active food packaging by incorporating
with propolis. Food Hydrocoll. 2016, 61, 695–702. [CrossRef]
107. Lekjing, S. A chitosan-based coating with or without clove oil extends the shelf life of cooked pork sausages in refrigerated
storage. Meat Sci. 2016, 111, 192–197. [CrossRef]
108. Cardoso, G.P.; Dutra, M.P.; Fontes, P.R.; Ramos, A.D.L.S.; Gomide, L.A.D.M.; Ramos, E.M. Selection of a chitosan gelatin-based
edible coating for color preservation of beef in retail display. Meat Sci. 2016, 114, 85–94. [CrossRef] [PubMed]
109. Sady, S.; Błaszczyk, A.; Kozak, W.; Boryło, P.; Szindler, M. Quality assessment of innovative chitosan-based biopolymers for
edible food packaging applications. Food Packag. Shelf Life 2021, 30, 100756. [CrossRef]
110. Kalia, A.; Kaur, M.; Shami, A.; Jawandha, S.K.; Alghuthaymi, M.A.; Thakur, A.; Abd-Elsalam, K.A. Nettle-Leaf Extract Derived
ZnO/CuO Nanoparticle-Biopolymer-Based Antioxidant and Antimicrobial Nanocomposite Packaging Films and Their Impact
on Extending the Post-Harvest Shelf Life of Guava Fruit. Biomolecules 2021, 11, 224. [CrossRef] [PubMed]
111. Gubanova, G.N.; Petrova, V.A.; Kononova, S.V.; Popova, E.N.; Smirnova, V.E.; Bugrov, A.N.; Klechkovskaya, V.V.; Skorik, Y.A.
Thermal properties and structural features of multilayer films based on chitosan and anionic polysaccharides. Biomolecules 2021,
11, 762. [CrossRef]
112. Liu, J.; Liu, S.; Wu, Q.; Gu, Y.; Kan, J.; Jin, C. Effect of protocatechuic acid incorporation on the physical, mechanical, structural
and antioxidant properties of chitosan film. Food Hydrocoll. 2017, 73, 90–100. [CrossRef]
113. Abbott, A.P.; Boothby, D.; Capper, G.; Davies, D.L.; Rasheed, R. Deep Eutectic Solvents Formed Between Choline Chloride and
Carboxylic Acids. J. Am. Chem. Soc. 2004, 126, 9142. [CrossRef] [PubMed]
114. Mbous, Y.P.; Hayyan, M.; Wong, W.F.; Looi, C.Y.; Hashim, M.A. Unraveling the cytotoxicity and metabolic pathways of binary
natural deep eutectic solvent systems. Sci. Rep. 2017, 7, 41257. [CrossRef] [PubMed]