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Chitosan Application in Food Technology: A Review of Recent Advances

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ПИЩЕВЫЕ СИСТЕМЫ | Том 3 № 1 | 2020 FOOD SYSTEMS | Volume 3 № 1 | 2020

UDС 664.8/.9.022 DOI: 10.21323/2618–9771–2020–3–1–10–15


Review paper

CHITOSAN APPLICATION IN FOOD TECHNOLOGY:


A REVIEW OF RECENT ADVANCES
Vladimir L. Kabanov*, Lyudmila V. Novinyuk
All-Russia Research Institute for Food Additives —
Branch of V. M. Gorbatov Federal Research Center for Food Systems of RAS, St. Petersburg, Russia
KEY WORDS: A BS T R AC T
chitosan, food additive, The review focused on global trends in the development of scientific research and the practical applications of chitosan
preservative, antioxidant, in food technology in recent years. Chitin and its derivative chitosan obtaining from the crustacean shells and the cell
edible films, biodegradable wall of fungi are among the most common biopolymers in the world. Chitosan is a polysaccharide discerned by a large
polymers, emulsifier, flocculant, number of unsubstituted amino groups. Featured properties of chitosan providing its high chemical and biological
encapsulation activities. Chitosan has various abilities as polycationite, film former, antimicrobial and antioxidant agent. Multifunc-
tional properties open up broad prospects for the chitosan applications in various fields of technology, medicine and
industry. The most attention in the review is paid to the works on extending food products shelf life with chitosan based
primary edible film coatings and biodegradable packaging. At the same time chitosan applications as an emulsifier, a
flocculant, as well as functional food additive, nutrient encapsulating material and dietary supplement are highlighted.

1. Introduction chitosan due to scavenging effect on free radicals. This ability


Chitosan — p
​ oly-β-(1,4)-d-glucosamine is a deacetylated product depends on DD and increases with unsubstituted amino groups
of chitin — ​poly-β-(1,4)-N‑acetyl-d-glucosamine, one of the most amount increased. High MW chitosan exhibits a less pronounced
abundant natural polysaccharide, found in composition of crustacean antioxidant effect, because its structure is more compact due to
shells and fungal cell walls [1]. There is great scientific and practical the formation of strong intramolecular hydrogen bonds [6]. The
interest in chitin and chitosan caused to the unique properties as antioxidant activities of chitosan in lard and rapeseed oil is com-
biocompatibility, safety, biodegradability, sorption performance of parable to ascorbic acid [8]. Also an antioxidant effect of chitosan
heavy metals and radionuclides [2]. Scientific publications amount in semi-finished products from meat, fish and seafood is noted [9].
related to chitin and chitosan is increasing annually and several The antimicrobial and antifungal activity of chitosan caused
scientific papers related to its production and application are pub- by cationite properties appeared in an acidic media. At pH values
lished weekly according to the Web of Science and Google Scholar. below pKa of chitosan protonated amino groups binding negatively
Chitin global production in 2015 was 28 thousand tons, and its charged carboxyl groups of lipopolysaccharides and peptidogly-
still increasing [3]. Due to its properties, chitosan has been widely canes at the bacterial cell wall surface, leading to permeabilization
used in various fields of technology, medicine and food industry. and destruction of external membranes [10]. The mechanism of
Chitosan properties are significantly influenced by its molecular antifungal action of chitosan is similar to antibacterial and ap-
weight (MW), which occurs in a range from 2 to more than 200 kDa. pears to fungi containing a significant amount of polyunsaturated
Deacetylation degree (DD) is other important chitosan property af- fatty acids [11]. Processing with chitosan solutions of fresh or
fecting an acid solubility which differs it from chitin. Chitosan with chopped fruits, berries and vegetables extends their shelf life,
DD more than 55% becomes soluble in a 1% acetic or hydrochloric inhibits the development of microorganisms and molds. Chitosan
acids [4]. Solubility associated with the protonation of the amino addition inhibits bacterial growth in noodle dough, hummus, and
group at the C‑2 position of the d-glucosamine unit converts the cheese [9,12].
polysaccharide to a polyelectrolyte under acidic conditions [5]. Edible film coatings are the most promising chitosan applica-
The purpose of present work is the development progress tion for food shelf life extending. Edible films are defined as the
problem study on food technology chitosan applications and primary packaging designed to protect foods against external
analysis of these trends. impacts, also it can be used as carrier of active ingredients such
as preservatives, flavors and colorants. [13]. Chitosan film coat-
2. Main part ings are prepared as a solution in dilute acids. Depending on DD,
A biological activity of chitosan along with safety for the hu- solution concentration, additional components and the drying
man brings its wide application for food industry. Antioxidant and conditions, there is a wide variety to change physicochemical
antimicrobial activity of chitosan allows to use it for increasing and biological properties of the resulting compound [14]. Edible
the foods shelf life, excellent emulsifying properties gives an coatings reducing weight loss during storage, prevent oxygen
opportunity to replace synthetic surfactants in food technolo- permeability, shows antimicrobial and antioxidant activities to,
gies, also chitosan can be used as a functional ingredient against increase the shelf life of processed foods significantly.
hypercholesterolemia, hypertension and inflammations, and for The tensile strength of chitosan films produced with acetic
the encapsulation of nutrients for a functional food development acid is higher in comparison with citric, lactic, and malic acids
[6]. Polyelectrolyte and flocculant behavior of chitosan allow to and increases during long-term storage [15]. Elasticity of the
use it as an effective clarifying agent for beverages, as well as for coatings could be increased by addition of glycerol or sorbitol as
preliminary purification of drinking water [7]. plasticizer. Chitosan-based film coatings effectively extend the
shelf life of carrots [16, 17], tomatoes [18], cucumbers [19], bell
Chitosan applications for food shelf life prolongation peppers [20], bananas [21], apples [22], pomegranates [23], pears
Most significant factors limiting the shelf life of food products [24], plums [25], strawberries [26], papaya [27], mango [28], fish
are an oxidative and microbial spoilage. Antioxidant activity of [29], meat [30] and minced meat [31, 32].

FOR CITATION: Kabanov  V.  L., Novinyuk  L.  V.  Chitosan application in food technology: a review of recent advances. Food systems. 2020; 3(1): 10–15.
DOI: 10.21323/2618–9771–2020–3–1–10–15

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ПИЩЕВЫЕ СИСТЕМЫ | Том 3 № 1 | 2020 FOOD SYSTEMS | Volume 3 № 1 | 2020

A number of studies concerning coatings composed of chito- antioxidant effect than these components separately [61]. Chito-
san blends with other film-forming biopolymers allowed to keep san coating containing eucalyptus essential oil and α-tocopherol
biodegradability, non-toxicity, compatibility with food products prolongs the shelf life and reduces fat oxidation of fresh silver
and improve functional properties. Chitosan-starch blend films carp, which is more related to the combined presence of chi-
shows good water vapor permeability and a high antioxidant tosan and eucalyptus oil than α-tocopherol used as an regular
activity [33,34]. The addition of cellulose and its derivatives to antioxidant food additive [62]. Cinnamon and clove essential oils
chitosan films increases elasticity, tensile strength, and optical enriched chitosan-arabic gum films enhances moisture resistance
transparency while maintaining high antimicrobial activity [35,36]. as well as antimicrobial activity against Escherichia coli and
Chitosan-alginate multilayer coatings applied to fresh cut fruits Staphylococcus aureus more in comparison with the inclusion
allows to save succulence during a longer while [37,38]. Pectin of these oils by itself [63]. In chitosan-carboxymethylcellulose
and chitosan combination occurring a strong intermolecular elec- edible coating cinnamon oil exhibits better antifungal activity
trostatic interaction, and the films obtained are characterized by add reduces the water vapor permeability by increasing the
high transparency, strength, and elasticity [39]. Compositions of hydrophobicity than ginger oil but in conjunction emerging a
chitosan with proteins, such as casein and gelatin [40,41,42], are significant synergistic antifungal and moisture resistance effect
characterized by good mechanical properties, low vapor perme- [64]. Addition of cinnamon and ginger essential oils slightly
ability, and UV‑protection due to absorption by peptide bonds [43]. reduces the transparency of chitosan films, but allows to obtain
Soy protein or beeswax included to coating composition increasing a thinner coatings. That films effectively prevent caused by fat
film hydrophobicity [44,45]. oxidation and the action of microorganisms fresh pork spoilage
Because of active functional groups chitosan can be used as part [65]. In some cases, essential oils addition to the coating may
of composite materials containing not natural only but synthetic not have any effect or even negatively affecting on the result-
polymer compounds [46]. Opuntia mucilage — a​ complex mixture ing products. The synergistic antifungal effect on Penicillium
of functional polysaccharide residues used as film-forming agent digitatum, the main cause of citrus green mold when cinnamon
with polyvinyl alcohol and chitosan obtaining edible coatings with essential oil incorporated chitosan coating, showed in vitro was
different properties when the composition is varied. These coatings not confirmed when applied to the mandarins [66]. Oregano and
are hydrophilic due to the opuntia mucilage. Inclusion of chitosan basil essential oils reduce tensile strength, while increasing
has technological approach because it is able to stabilize the film- transparency and improving the antimicrobial and antioxidant
forming solution increasing zeta potential and also a functional properties of chitosan-based films [67]. Thyme oil with chitosan
since films with higher content of chitosan became tougher. When coating reduces moisture loss, retains color and inhibits yeast
increasing polyvinyl alcohol amount film flexibility is increased. growth, but does not affect on enterobacteria, mesophilic and
That make those mixtures compatible with different food applica- lactic acid bacteria for ham [68]. Cumin and eucalyptus essential
tions required [47]. Films formed by chitosan and polyvinyl alcohol oils as part of the chitosan coating of chicken breasts reducing
with lignin nanoparticles are characterized by increased strength spoilage caused by various types of microorganisms, extending
compared to films formed by individual components, antibacterial shelf life and enhancing, the taste and aroma of fried chicken
action against gram-negative microorganisms and the synergistic [69]. Lemon oil compared to oregano oil in the chitosan coating
antioxidant effect of chitosan and lignin [48]. composition shows a more pronounced bactericidal effect, both
Natural plant extracts included with the chitosan coating have not adversely affect chilled chicken breast organoleptic [70].
composition has a significant positive effect on the mechanical However, lemon oil added with a strawberry coating despite an
and biological properties of the protective edible films formed. For antifungal resistance increasing negatively changing a typical
example, polyphenols of thyme extract increase tensile strength aroma due to terpenes contained in lemon oil [71].
of chitosan-based films as crosslinkers, and also increase the A promising direction of food quality monitoring is visual ed-
antioxidant activity [49], turmeric extract addition reduces the ible film colorimetric indicators that change color when the pH
UV‑permeability, significantly increases the tensile strength and accompanying spoilage changes. That coatings were developed
antimicrobial activity [50], milk thistle extract reduces films solubil- for fresh fish on the chitosan-starch base containing red cabbage
ity and water vapor permeability, as well as improves antioxidant extract [72], and as polyvinyl alcohol films including chitosan
properties [51]. Barberry seed extract increases the hydrophobic- nanoparticles and mulberry extract [73].
ity of coatings, while whole fruit extract reduces it compared to a Development of biodegradable polymer packaging materials is
control sample. The antimicrobial activity of chitosan films with one of modern trends to extend food shelf life. A microcrystalline
barberry extracts based quorum sence inhibitory property [52]. cellulose-polyvinyl alcohol-chitosan composition showed two or-
Ethanolic extracts of rosemary, cinnamon, guarana and peumus ders of magnitude higher water vapor permeability with comparable
added to chitosan and gelatin based films allows to achieve very strength to polyethylene films and relative elongation exceeds
high antioxidant and antibacterial activities [53], grapefruit seed cellophane because of plasticizing effect of polyvinyl alcohol
extract increases the antifungal activity, elasticity and elongation [74]. Polylactic acid with chitosan nanoparticles using polyvinyl
at break of chitosan films [54]. alcohol as a plasticizer and polyethylene glycol as crosslinking
A significant synergistic antimicrobial effect is observed agent is characterized by a significant increase in tensile strength
for composite coatings based on the chitosan matrix including and antimicrobial activity against aerobic microorganisms [75].
nanoparticles of inorganic antimicrobial agents such as silver Amphiphilic nanoparticles formed by a chitosan grafted polylactic
[55,56,57] and zinc oxide [58,59,60]. acid oligomers used as a filler for polylactic acid makes resulting
Essential oils addition to film-forming composition gives for material more flexible and significantly increase the oxygen bar-
the edible films supplemental functional properties. Essential rier properties [76].
oils increasing antioxidant ability and activity against molds
and microorganisms and also changing physical properties of Chitosan emulsifying applications
the chitosan films, such as strength, moisture resistance and Chitosan is an excellent emulsifier to stabilize heterogeneous
transparency. That coatings can be used for berries, fruits, fish or oil-in-water systems. Chitosan increases viscosity of the continuous
meat. Combined action of essential oils and chitosan may lead to phase, complicating the diffusion of disperced particles and reduc-
synergistic effects. Rosemary oil containing chitosan coating on ing the droplet aggregation rate. In addition, positively charged
rainbow trout fillets exhibits more pronounced antibacterial and amino groups, making chitosan an amphiphilic surfactant polymer.

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ПИЩЕВЫЕ СИСТЕМЫ | Том 3 № 1 | 2020 FOOD SYSTEMS | Volume 3 № 1 | 2020

Chitosan can be used as a single emulsifier, however the emul- A promising direction of nanoencapsulation of biologically
sions obtained are reversible due to the sensitivity to the pH values. active substances is chitosan-based multilayer composite coatings
In an acidic media with pH < pKa protonated chitosan exhibits development. In this way is possible to obtain orally digestible
surface-active properties, interacting with triglycerides carbonyl insulin [106], and keep stable vitamin D3 in food products for up
groups. With pH increasing, the solubility of chitosan decreases, to 60 days [107].
while the emulsion remains stable because of oil phase droplets Whell known that chitosan itself exhibits biological activity.
adsorbed on chitosan particles. If acidity increases back chitosan It binds fats, cholesterol and bile salt due to both hydrophobic
passes into a soluble form desorbing a disperced oil droplets and interactions and the formation of hydrogen bonds, and as a result
the emulsion is reversibly separating [77]. The emulsifying abil- of electrostatic attraction of positively charged amino groups and
ity of chitosan largely depends on the DD and MW and increased negatively charged carboxyl groups of fatty acids.
for low MW chitosan with DD less than 60% or more than 86%, The binding of cholesterol to chitosan was confirmed by
whereas when the values of DD from 65% to 77%, that proper- a number of clinical studies, so chitosan may be used in the
ties are significantly dependent on concentration [78]. Most of hypercholesterolemia treatment [108, 109] and included in the
the practical studies on chitosan applications as an emulsifier formulations of special foods with an anticholesterol effect.
consider it as part of complex compositions containing other sur- The fat binding ability of chitosan can be used in the produc-
factants. Presence both chitosan and protein emulsifiers makes a tion of dietary foods reducing the rate of lipids absorption and
heterogeneous system more stable. Incorporation of chitosan with digestion [110]. Moreover, a composite film coating containing
soybean isolate protein can increase the digestibility and stability chitosan, gelatin and gallic acid can be used to simulate fat in
of emulsified carotenoids [79]. The complex containing chitosan food products, acting as a fat substitute by imparting organoleptic
with modified β-lactoglobulin fibers stabilizes the fish oil emul- surface properties [111].
sion in water [80]. Also, stable Pickering emulsions with corn oil Chitooligosaccharides have antitumor activity. Despite the
are formed as a result of electrostatic interaction of chitosan with large number of clinical studies, antitumor mechanism still not
gelatin [81]. The ability of chitosan to form micelles in aqueous well understood, however, the most important factors in the action
solutions may be used for unstable compounds as carotenoids [82] of chitosan are cancer cells viability reducing associated with the
and anthocyanins [83] sustainability increasing. electrostatic interaction between chitosan and cell wall glycopro-
teins, inhibition of angiogenesis, which is the main reason for the
Applications of chitosan as a flocculant rapid growth of cancer tumors, also a complex immunostimulating
Polycationite chitosan properties can be used for drinks clari- effect is possible [112].
fication from solid suspended particles comprising polyphenols,
proteins, polysaccharides and mineral compounds [5]. Chitosan can 3. Conclusion
be effectively used to clarify fruit juices [84–87], fruit [88] and grape A global trends analysis in the research of chitosan in food tech-
[89] wines, beer [90] and also at the preliminary drinking water puri- nology applications shows that the most attention to this problem
fication since this increases suspended particles sedimentation rate is paid in Asian countries that have an abundant raw material base
and increases the degree of separation of bacteria and viruses [91]. for its production. A large number of developments are currently
proceeded in China, unlike Japan which lost its past leadership
Chitosan application in the functional foods production in this direction. Widespread research is also carries out in India,
Chitosan may be used as a carrier for encapsulating and con- Spain and Iran. It should be noted that in Russia, unlike the 90s,
trolled delivery of probiotic ingredients in functional food products the amount of studies on the issue has significantly decreased.
beacuse of its high biocompatibility, emulsifying ability, polycation- In recent years most intensive researches focused on the use
icity and hypoallergenic properties [92]. Components encapsulation of chitosan applications to extend the shelf life of foods, and also
used to prevent chemical changes during the preparation process as an emulsifier, flocculant and dietary supplement. Today the
or stomach acidic media, for lipophilic components as vitamins explosively developing area of chitosan applying is the edible
or flavonoids with polymer matrix delivery, to control nutraceu- films producing. Edible coatings perform not only the function
ticals release and to mask smell and taste of some substances. of food primary packaging, but also prevent moisture loss and
The most common method of nutraceutics encapsulation is ion oxygen access, have antimicrobial and antioxidant activity due
gelation [6] using polyanionites — ​tripolyphosphate or proteins to the unique properties of chitosan. At the same time is possible
as gelling agents. Particle size depends on chitosan properties to enrich the products with additional functional ingredients as
and increases with a low DD and MW associated with a decrease natural plant extracts, essential oils, vitamins and antimicrobial
in the zeta potential, determined by unsaturated amino groups components. Thoset components enhancing the properties of the
of the macromolecule interacting with polyanionite [93]. Can films obtained up to reach a synergistic effect over prolonging
be obtained nanoparticles containing vitamins C [94,95] and B2 the foods shelf life. The latest trends of chitosan application are
[96], dyes as curcumin [97] and lutein [98], flavonoids, including associated with freshness indicating coatings development, with
catechins [99,100,101] and quercetin [102], bioactive minerals vitamins, nutrients and probiotics encapsulation and delivery, and
selenium [103,104] and zinc [105]. also with the biodegradable packaging engineering.

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AUTНOR INFORMATION
Vladimir L.  Kabanov — ​Junior Researcher, Laboratory of technology and processing of biosynthesis products, Аll-Russian Research Institute for Food Ad-
ditives — ​Branch of V. M. Gorbatov Federal Research Center for Food Systems of RAS, 191014, St.-Petersburg, Liteynу prospekt, 55, Tel: +7–812–273–75–24,
e-mail: kabanof_v@yahoo.com
ORCID: https://orcid.org/0000–0001–6339–7795
* corresponding author
Lyudmila V. Novinyuk — ​candidate of technical sciences, Chief Researcher, Laboratory of technology and processing of biosynthesis products, Аll-Russian
Research Institute for Food Additives — ​Branch of V. M. Gorbatov Federal Research Center for Food Systems of RAS, 191014, St.-Petersburg, Liteynу prospekt,
55, Tel: +7–812–273–75–24, e-mail: novinyuk@yandex.ru
ORCID: https://orcid.org/0000–0002–9577–9330
All authors bear responsibility for the work and presented data.
All authors made an equal contribution to the work.
The authors were equally involved in writing the manuscript and bear the equal responsibility for plagiarism.
The authors declare no conflict of interest.
Received 09.11.2019 Accepted in revised 18.02.2020 Accepted for publication 05.03.2020

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