碳水化合物 壳聚糖综述
碳水化合物 壳聚糖综述
碳水化合物 壳聚糖综述
Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol
Review
A R T I C L E I N F O A B S T R A C T
Keywords: The perishability nature of harvested fruits and vegetables, along with the effect of environmental factors,
Biopolymer storage conditions, and transportation, reduce the products' quality and shelf-life. Considerable efforts have been
Chitosan allocated to alternate conventional coatings based on new edible biopolymers for packaging. Chitosan is an
Nanocomposites
attractive alternative to synthetic plastic polymers due to its biodegradability, antimicrobial activity, and film-
Coating
Packaging
forming properties. However, its conservative properties can be improved by adding active compounds,
Anti-browning limiting microbial agents' growth and biochemical and physical damages, and enhancing the stored products'
Postharvest quality, shelf-life, and consumer acceptability. Most of the research on chitosan-based coatings focuses on
antimicrobial or antioxidant properties. Along with the advancement of polymer science and nanotechnology,
novel chitosan blends with multiple functionalities are required and should be fabricated using numerous
strategies, especially for application during storage. This review discusses recent developments in using chitosan
as a matrix to fabricate bioactive edible coatings and their positive impacts on increasing the quality and shelf-
life of fruits and vegetables.
Abbreviations: UV, Ultraviolet light; CA, Controlled atmosphere; NPs, Nanoparticles; CNPs, Chitosan nanoparticles; PPO, Polyphenol oxidase; ROS, Reactive
oxygen species; PAL, Phenylalanine ammonia-lyase; Ca, Calcium; SA, Salicylic acid; AgNPs, Silver nanoparticles; ZnO NPs, Zinc oxide nanoparticles; SiNPs, Silisium
nanoparticles; TiO2NPs, Titanium dioxide nanoparticles; Fe2O3 NPs, Iron oxide nanoparticles; PNPs, Propolis nanoparticles; CuNPs, Copper nanoparticles; ZnNPs,
Zinc nanoparticles; MSNPs, Mesoporous silica nanoparticles; BC-NT-TT, Chitosan- titanium dioxide nanoparticles- thymol and tween; CCNC, Chitosan clay
nanocomposite.
* Corresponding author.
E-mail addresses: [email protected] (R. Saberi Riseh), [email protected] (J.F. Kennedy).
https://doi.org/10.1016/j.carbpol.2023.120666
Received 29 November 2022; Received in revised form 17 January 2023; Accepted 1 February 2023
Available online 6 February 2023
0144-8617/© 2023 Elsevier Ltd. All rights reserved.
R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
Following the restriction of synthetic fungicides and waxes, exploring Guebitz, & Nyanhongo, 2022). These functionalities and also thermal
novel preservation methods based on renewable, abundant, cost- and mechanical properties of polymer-based coatings and films can be
effective, and biodegradable alternatives for achieving healthy and improved via the fabrication of polymer nanocomposites (Youssef, de
fresh food has intensified (Santosh Kumar, Mukherjee, & Dutta, 2020). Oliveira, Tischer, Hussain, & Roberto, 2019). As a promising technol
Therefore, developing green and eco-friendly alternative strategies for ogy, nanotechnology improves agricultural productivity through man
effectively preserving fruits, vegetables, cereals, roots, and tubers is aging wastewater, regulating soil features, intelligent use of nano
essential. Bio-based materials are considered safe and can play an fertilizers, adequate use of pesticides and herbicides, and detecting
important role in coating and packaging harvested products by phytopathogens (Hassanisaadi et al., 2022; Okey-Onyesolu et al., 2021).
decreasing the rate of respiration and ripening, decreasing ethylene, Nanotechnology increases food production with a high market value,
controlling moisture loss, and eliminating microbial activities (Basu elevates sensing and nutritional characteristics, improves food safety,
matary, Mukherjee, Katiyar, & Kumar, 2022). Recently, much attention and inhibits microbial agents in a better way (Hassanisaadi et al., 2022).
has been paid to biopolymer-based coatings as protector materials to It also protects quantitative and qualitative food product losses via
ensure food safety, maintain food quality and enhance its shelf-life. increasing postharvest product shelf-life with the help of various nano
Additionally, biopolymer-based coatings are mainly edible, abundant, particles (NPs) (Neme, Nafady, Uddin, & Tola, 2021). NPs are used to
non-toxic, biocompatible, biodegradable, and eco-friendly and can act fabricate intelligent and active packaging, maintaining the food quality
as carriers for antioxidant and antimicrobial agents (Basumatary et al., during storage time. NPs possess UV impermeability, oxygen scavenging
2022). Chitosan, alginate, starch, gelatin, cellulose, pectin, soy protein, ability, antimicrobial activity, and many other characteristics, which
dextran, and gums are the most common biopolymers utilized for the make them suitable for nanocomposite preparation. In this vein,
fabrication of food films and coatings to prolong postharvest shelf-life chitosan-based nanocomposites embedded with NPs provide numerous
(Basumatary et al., 2022; Basumatary, Mukherjee, Katiyar, Kumar, & benefits over other packaging and coating systems due to their unique
Dutta, 2021; Davidović et al., 2021; Santosh Kumar et al., 2020; Lazić antimicrobial properties and absorbing mycotoxins (Abd-Elsalam,
et al., 2020). These materials are the best alternatives to petroleum- Hashim, Alghuthaymi, & Said-Galiev, 2017). Fig. 1 schematically de
based and non-biodegradable polymers, including polyvinylchloride, picts the deacetylation of chitosan from chitin and its application in
polyamide, polyethylene, polypropylene, polystyrene, and more others postharvest preserving fruits.
(Song, Murphy, Narayan, & Davies, 2009). Chitosan is gaining consid Chitosan-based nanocomposites are proper alternatives to mitigate
eration due to its innate antimicrobial activity, environmentally-friendly the negative impacts of conventional coatings and films on human and
nature, abundance, and good film-forming ability among the most environmental health. Additionally, natural chitosan coatings and
common bio-polymers (van den Broek, Knoop, Kappen, & Boeriu, 2015). packaging incorporated with functional compounds decrease the post
Although, the high production cost limits the application of chitosan in harvest losses of fruits and vegetables without changing their nutritive
the food packaging industry on a commercial scale (Kumari, Kumar, & and sensorial properties. The main aspect of this review includes the
Muthuswamy, 2022). Chitosan is a deacetylated chitin derivative, ob recent advancement in the use of chitosan as a basis for edible coatings,
tained from the exoskeleton of insects and crustaceans (such as shrimps their application as active films, and their impact on extending the shelf-
and crabs), mollusks, the cell wall of fungi, and some algae (Pellis, life of harvested products.
Fig. 1. The synthesis of chitosan by deacetylation from chitin and its application in postharvest preserving fruits.
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2. Postharvest damage as an effective factor in reducing the respiration rate and extend the development of microorganisms result
marketability of crops ing in serious product damage. In the case of tropical crops, chilling
injury caused by low temperatures is also observed (Yahaya & Mardiyya,
Agricultural products, especially fruits, vegetables, and cereal grains, 2019). Additionally, biochemical (enzymatic) browning is determined
play an essential role in the human food chain. However, approximately by the activity of the polyphenol oxidase enzyme present in fruits and
15 to 70 % of these products are damaged at different postharvest stages, vegetables. Enzymatic browning mostly occurs during harvest, storage,
mainly harvesting, storage, transportation, and marketing (Alghu transportation, and subsequently affects the products' nutritional value
thaymi, Abd-Elsalam, Paraliker, & Rai, 2020). There are many reasons (Moon, Kwon, Lee, & Kim, 2020). Fig. 2 schematically depicts the types
for these losses, including insects, diseases, rodents, mechanical dam of damages to postharvest agricultural products. Considering the fact
ages, lack of proper packaging and marketing systems, inappropriate that consumers prefer fresh, proper mature, and disease-free fruits and
harvesting and storage methods, premature and overmature harvesting, vegetables, to preserve the quality of fruits and vegetables, numerous
and adverse climate changes (Baradar, Saberi-Riseh, Sedaghati, & methods have been applied depending on the aim of preservation, for
Akhgar, 2015; Etefa, Forsido, & Kebede, 2022; Saberi-Riseh, Hajiegh instance, extending shelf-life, preventing browning reactions, deterio
rari, Rouhani, & Sharifi-Tehrani, 2004). Fresh fruits and vegetables are ration, microbial growth, oxidation reactions and nutritional loss
more vulnerable due to the high rate of respiration, high moisture (Panahirad, Naghshiband-Hassani, Ghanbarzadeh, Zaare-Nahandi, &
content, and nutrients which lead to limited storage shelf-life and Mahna, 2019).
postharvest deterioration. Overall, postharvest losses are mainly caused
by physical, mechanical, physiological, pathological, environmental, 3. Polymer nanocomposites
and hygienic factors. However, pathological rots followed by mechani
cal injuries are the most serious among these agents. First, careless Recent advances in nanotechnology have facilitated the use of
handling during harvesting, improper packaging, transportation, and nanofillers as functional groups in the packaging system, which has
storage can cause mechanical damage. Although, some birds and insects resulted in the production of biodegradable polymer-based nano
are responsible for these injuries (Firdous, 2021). Most of the time, composites (Jamróz, Kulawik, & Kopel, 2019). Nanofillers can signifi
horticultural crops with cracks are more vulnerable to organisms, fol cantly improve or adjust the different properties of the materials into
lowed by increasing the rate of water loss and reducing marketability (Li which they are incorporated, such as optical, electrical, mechanical,
& Thomas, 2014). Secondly, microbial losses caused by fungi, bacteria, thermal, barrier properties, and fire-retardant properties. The properties
molds, and yeasts are the main causes of product spoilage (Lorenzo of composite materials can be significantly impacted by the mixture
et al., 2018). The most common postharvest fungi pathogens damaging ratio between the organic matrix and the nanofillers (Othman, 2014).
fruits and vegetables are Fusarium solani, F. oxysporum, Pythium apha These nanofillers/nanostructures are categorized into carbon nano
nidermatum, Alternaria alternata, Botrytis cinerea, Diplodia, Monillinia structures, clays, organic, and inorganic nanofillers. However, due to
fructicola, Phomopsis, Sclerotinia sclerotiorum, Rhizopus stolonifer, Asper their strong tendency for oxidation and agglomeration, quantum dots
gillus flavus, Penicillium viridicatum, Colletotrichum gloeosporioides, Colle are another desired nanofillers capable of improving the stability and
totrichum spp. etc. Among bacteria, Burkholderia seminalis, Erwinia spp., compatibility of biopolymers (Guo et al., 2016). Fullerenes, graphene-
Pseudomonas spp., etc. cause extensive damage (Hassanisaadi et al., based materials, nanofibers, and carbon nanotubes are classified as
2021; Jamali, Sharifi-Tehrani, Okhovvat, Zakeri, & Saberi-Riseh, 2004; carbon nanostructures (Nasrollahzadeh, Issaabadi, Sajjadi, Sajadi, &
Saberi-Riseh, Javan-Nikkhah, Heidarian, Hosseini, & Soleimani, 2004; Atarod, 2019). Natural clays, such as montmorillonite and halloysite,
Saberi Riseh et al., 2022). The third factor that plays an important role in are the most utilized nanoclays (Majeed et al., 2013). On the other hand,
the postharvest loss of fruits and vegetables is environmental factors like inorganic nanofillers are based on metals and metal oxides, whereas
temperature, humidity, and gas composition, such as ethylene, CO2, and organic nanofillers are based on biopolymers, such as chitosan and
O2 around the fruits and vegetables, which adversely impact the respi cellulose (Silva et al., 2019; Sothornvit, 2019). These nanofillers affect
ratory rate and general metabolic rate (Romanazzi, Feliziani, Baños, & the physical, mechanical and antimicrobial properties of polymer-based
Sivakumar, 2017). High temperature and relative humidity increase the films and coatings (Alizadeh-Sani, Khezerlou, & Ehsani, 2018; Cazón,
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R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
Velazquez, Ramírez, & Vázquez, 2017; Jamróz et al., 2019). controlled delivery of active ingridients, owing to its proven non-
toxicity, absorption capability, biodegradability, and biocompatibility
4. Chitosan nanoparticles (Mujtaba et al., 2020). The degradation rate of chitosan-based products
depends on their application. For instance, when using chitosan as a
Chitosan nanoparticles (CNPs) are considered interesting choices as carrier matrix, it should degrade almost quickly but in a controlled
functional agents for biopolymer films because of their film-forming manner to continuously deliver the functional agent to the target. The
ability, nontoxicity, biocompatibility, and high surface area (Olivera biodegrading rate of chitosan depends on molecular weight, degree of
et al., 2016). Additionally, CNPs have unique physiological properties acetylation and the availability of amino groups. Many studies have
and polycationic nature, making them a potent antimicrobial agent proven the in vitro and in vivo biodegrading of chitosan by lysozyme,
against fungi and bacteria (Saberi Riseh, Hassanisaadi, Vatankhah, chitinase, chitin deacetylase and chitosanase enzymes (Matica, Men
Abdani Babaki, & Barka, 2022). CNPs have been studied extensively, ghiu, & Ostafe, 2017; Reay, Jackson, Ferreira, Hilkens, & Novakovic,
and different fabrication methods have been developed considering 2022). Another important feature is chitosan's toxicity, which is fully
diverse factors such as size, stability, loading capacity, and retention discussed by Kean and Thanou (2010) and Zubareva, Shagdarova,
time. Ionic gelation, spray drying, top-down, self-assembly, emulsifica Varlamov, Kashirina, and Svirshchevskaya (2017). Entrapting active
tion and crosslinking, reversed micelles (microemulsion) and precipi ingridients in chitosam matrix not only develop a controlled delivery
tation are basic approaches used to form CNPs (Yanat & Schroën, 2021). system for food protection under storage conditions but also improve the
Although, ionic gelation and spry drying can be termed as the most stability and bioactivity of encapsulated ingredients for application due
appropriate production protocols for the large-scale production of CNPs to its bio-adhesive properties as innovative food preservatives (Das,
(Stevulova, Singovszka, & Demcak, 2021). Molecular weight and the Singh, Chaudhari, Dwivedy, & Dubey, 2021). For instance, using chi
degree of deacetylation of chitosan are two key properties that affect the tosan as a matrix to encapsulate essential oils protected them from
particle size and surface charge of CNPs prepared by these methods oxidation, evaporation, and degradation and maintained their biological
(Mohammed, Syeda, Wasan, & Wasan, 2017). CNPs, either alone or features during storage (Detsi et al., 2020). Biotic or abiotic stresses may
combined with natural active agents to fabricate composite films and stimulate the release of active ingredients from the chitosan matrix.
coatings, have been extensively used to extend the shelf-life of fruits and After responding to the trigger, the release occurs through pore diffu
vegetables (Esyanti, Zaskia, & Amalia, 2019; Odetayo et al., 2022; sion, surface desorption, capsule swelling, and degradation (Camara
Youssef & Roberto, 2021). Many studies also demonstrated that CNPs et al., 2019). Fig. 3 depicts the release mechanism of core materials from
are an efficient coating to preserve harvested crops from postharvest the chitosan matrix. The surface desorption mechanism relies on the
pathogens and decrease damage by inducing plant defense mechanisms active ingredients adsorbed on the matrix surface, while the diffusion
(Divya & Jisha, 2018). For instance, exogenous application of CNPs method refers to the diffusion rate gradient. The diffusion method
effectively triggered strong defense resistance against P. expansum in consists of several steps: first, water penetration and matrix swelling;
apples by promoting the expression of defense-related genes including, second, alteration of a glassy polymer into a plasticized or rubbery
phenylalanine ammonia lyase-1, pathogen-related proteins, chitinase, swollen matrix and third, dissolution and diffusion of active ingredients
β-1,3-glucanase, peroxidase and xyloglucan endotransglycosylase from the matrix (Kashyap, Xiang, & Heiden, 2015). After hydration, the
(Abdel-Rahman et al., 2021). Similarly, the application of edible coat release of active ingredients depends on the swelling of the chitosan
ings and films with chitosan gel nanoparticles on fruits and vegetables capsules. Erosion or degradation of the polymer is related to water up
notably induced the production of chitinase, glucanase, and phenylal take or enzymatic reactions. So, the stimuli-dependent release of active
anine ammonia-lyase (Adiletta et al., 2018). Production of nano agents from the chitosan matrix provides an efficient and effective
composite films using CNPs reduced postharvest losses and provided release of active ingridients at the target site (Maluin & Hussein, 2020).
more maintenance and high safety to eatable products on fruits and The more likely release mechanisms in agricultural systems are pore
vegetables (Santosh Kumar et al., 2020). Eshghi et al. (2014) applied diffusion and degradation. The evaluation of the release behavior of
nano chitosan-based coating on strawberry fruits. Their results indicated linalool from chitosan nanocomposite was done in an alcoholic aqueous
the role of bioactive preservative components based on chitosan in solution at pH 7.4, as the system stimulates similar conditions for most
increasing the shelf-life of strawberry fruits. Chitosan-based nano stored food products. The findings exhibited an initial burst phase of
particles revealed better antifungal and antibacterial efficacy on fresh- release, which may be attributed to the release of linalool molecules
cut apples compared to bulk chitosan coating and control during the absorbed at the chitosan's surface through surface erosion, diffusion,
storage period (Pilon et al., 2015). Hashim, Youssef, and Abd-Elsalam desorption, and decomposition. But, the gradual and sustained release
(2019) observed the reduction of gray mold on table grapes by after 96 h may be due to the release of linalool through pores on the
applying chitosan and silica NPs. Moreover, CNPs extended the storage surface of the hydrocarbon portions of the chitosan matrix and unique
life and kept the quality of banana and grapevine, respectively (Lus intermolecular interactions between chitosan and linalool (Das et al.,
triane, Dwivany, Suendo, & Reza, 2018; Melo et al., 2018). Despite these 2021). Choudhary et al. (2017) found that encapsulation of Cu into
advantages, the important limitations of using CNPs include poor sta CNPs was pH dependent, which increased the release of Cu from 21.5 %
bility and solubility. Although, it's possible to resolve these problems by to 44.1 % when pH changed from three to one. A stimuli-response
altering the structure with some chemical agents (Naskar, Sharma, & release mechanism was observed for CNPs loaded with hexaconazole
Kuotsu, 2019). which demonstrated diffusion-controlled release of the fungicide at pH
5.5 in a sustainable manner with a prolonged release time up to 86 h
5. Chitosan biopolymer as matrixes in a carrier system (Maluin et al., 2019). Moreover, Sandeep Kumar, Chauhan, Gopal,
Kumar, and Dilbaghi (2015), observed the pH-dependent release of
Enhancing the shelf life of stored food commodities without any insecticide acetamiprid from chitosan-alginate nanocapsules, in which
detrimental effect on human health is the essential development of the amount of acetamiprid released after 24 h at pH 10 was equal to the
controlled delivery systems. Choosing a suitable matrix to release active released amount after 36 h at pH 7 and 4. Chitosan in its various forms
ingridients for a long time depends on many factors, including its has also been extensively used as a matrix for the encapsulation of
biodegradability, the matrix's preparation method, the type of core different functional agents including, antioxidants, antimicrobials, anti-
materials, and the experimental condition of the process (Pirzada et al., browning, vitamins, nutrients, biological agents, plant essential oils, and
2020; Saberi-Riseh, Moradi-Pour, Mohammadinejad, & Thakur, 2021; extracts to maintain the storage quality and prolong the shelf-life of post-
Saberi Riseh, Hassanisaadi, Vatankhah, Soroush, & Varma, 2022). harvest fruits and vegetables (Basumatary et al., 2022; Liu et al., 2022).
Among various biopolymers, chitosan is a beneficial carrier for the For example, chitosan-based coatings loaded with essential oils
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R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
diminished physiochemical changes as well as microbial growth on can be preserved by adding different functional agents, such as nutri
strawberries and apple slices during the storage period, resulting in the ents, vitamins, antimicrobials, antioxidants, probiotics, and enzymes,
improvement of post-harvest shelf-life and quality (Popescu et al., into the chitosan as a coating matrix (Dubey & Dubey, 2020; Zeynadini-
2022). Heras-Mozos, Gavara, and Hernández-Muñoz (2021) used chi Riseh et al., 2018). These coating systems preserve products by
tosan to develop a novel device capable of carrying trans-2-hexenal and decreasing microbial contamination, avoiding oxidation reactions,
perillaldehyde covalently inserted into the polymer. This antifungal maintaining sensorial and nutritional characteristics, and delaying
volatiles are released by acid hydrolysis of imine bonds, reducing the senescence and ripening (Arroyo et al., 2020). Different techniques
growth of B. cinerea and P. expansum under in vitro conditions. More could be used to apply edible coatings on fruits and vegetables, as
over, chitosan films grafter by trans-2-hexenal extended the shelf life of
blackberries from 3 to 12 days at 4◦ C and pH 4. Another important
application of chitosan in delivery systems is using chitosan with or
without incorporating different metals as a sustainable alternative to
conventional pesticides against phytopathogens. For instance, the
growth and development of C. gloeosporioides, Penicillium steckii, and
Cladosporium oxysporum under post-harvest conditions was inhibited in
the presence of chitosan-TiO2 NPs (Xing et al., 2021). Additionally,
loading chitosan with linalool as the active agent improved overall
bioefficiency in terms of storage antiaflatoxigenic, antifungal and
untioxidant activity compared to its unencapsulated form, resulting in
high quality and prolonged shelf life of rice (Das et al., 2021).
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R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
depicted in Fig. 4. quinones into their precursor diphenols by suppressing the activity of
PPO (Moon et al., 2020). Basumatary et al. (2021) developed chitosan-
6.1. Coating-based chitosan nanocomposites against microbial damages based coatings in composition with aloe vera gel, as an antioxidant, and
ZnO NPs, as an antimicrobial agent. Their results indicated a 5 %
As most fresh products are sensitive to fungal and bacterial decay, reduction in weight loss, oxidative decay, and delayed ripening
antimicrobials are one of the most common functional compounds compared to uncoated pineapples. Incorporating Zataria multiflora Boiss
among active ingredients (Fathi, Saberi-Riseh, & Khodaygan, 2021; essential oil and grape seed extract in chitosan films increased the
Panahirad et al., 2021; Saberi-Riseh & Moradi-Pour, 2021). These active coatings' phenol content and antioxidant activity (Moradi et al., 2012).
agents improve the shelf-life and health of fruits and vegetables by The prevention of increasing malondialdehyde content, total polyphenol
inhibiting microbial growth and losses. Rapid inactivation and the direct content, peroxidase, phenylalanine ammonia-lyase, and polyphenol
contact of active ingredients with fruit and vegetable bark have been oxidase activity was observed when tomato fruits were coated with
reported as limitations of the application of antimicrobial material in nano‑silicon oxides (SiOx)-chitosan composites (Zhu et al., 2019). In a
free forms (non-coated). The loading of antimicrobial agents into similar study, Lo’ay and Dawood (2017) coated banana fruits with
nanocomposite-based coatings is considered as a practical solution to chitosan-polyvinyl alcohol-oxalic acid composition. They demonstrated
maintain the effective concentration of active ingredients, increase a noteworthy reduction in the activity of browning enzymes, polyphenol
shelf-life longevity during postharvest storage time, and enhance the oxidase (PPO), and phenylalanine ammonia-lyase (PAL). Therefore, the
antimicrobial efficiency of antimicrobial substances (Khodaeimehr, total phenol content was preserved, and less browning incidence was
Peighambardoust, & Peighambardoust, 2018). Different antimicrobial observed on the fruit peel during the shelf-life. Another edible coating
agents, including organic acids (propionic, tartaric, benzoic, sorbic, composed of chitosan, aloe vera gel, and CaCl2 was evaluated on mango
citric, acetic, and lactic acid), polypeptides (lactoferrin, nisin, natamy shelf-life during the storage time at ambient temperatures. This com
cin, lysozyme, and peroxidase), microbial bacteriocins (extracted from posite maintained the quality of mango fruits for 21 days by suppressing
biocontrol bacteria, such as Bacillus spp. and lactic acid bacteria), the activity of PPO (Hajebi Seyed, Rastegar, & Faramarzi, 2021). These
essential oils and plant extracts (capsicum, lemongrass, oregano, studies proved the potential of chitosan-based coatings incorporating
carvacrol, garlic, and cinnamon), metallic nanoparticles (CuNPs, AuNPs, anti-browning agents to preserve fruit and vegetables against oxidative
ZnNPs, and AgNPs), mineral salts (ammonium and sodium bi reactions. Table 2 presents other examples regarding applying active
carbonates), sulphites and parabens are used in the composition of chitosan-based coatings with anti-browning and antioxidant activity.
polymer coatings (Moradi Pour, Saberi-Riseh, Mohammadinejad, & Also, to gain a clearer insight into the anti-browning and antioxidant
Hosseini, 2019; Panahirad et al., 2021; Saberi Riseh et al., 2021). Arroyo effect of these active coatings, Fig. 6 schematically depicts the applying
et al. (2020) coated ZnO-nanoparticles in edible alginate and chitosan, chitosan-based coatings enriched with anti-browning and antioxidant
which increased the shelf-life of Guava fruits during storage time. In agents.
another study, chitosan and methylcellulose were used as a coating
material for citrus essential oils. This product inhibited the activity of 6.3. Coating-based chitosan nanocomposites against physical damages
L. monocytogenes in different fruits (Randazzo et al., 2016). More studies
in chitosan incorporating natural antimicrobial substances for preser Physical damages mainly occur during processing agricultural
ving fruits and vegetables are illustrated in Table 1. Also, Fig. 5 depicts products, such as peeling, slicing, shredding, coring, blanching, canning,
the antimicrobial preserving effects of coating-based chitosan nano etc., contributing to the activity of cell wall modifying enzymes (e.g.,
composites against microbial damage. cellulase, polygalacturonase and pectin methylesterase). As pectolytic
enzymes play an important role in decreasing the firmness of fruit and
6.2. Coating-based chitosan nanocomposites against biochemical vegetable texture, limiting their activity will retain the stiffness. Using
damages edible coatings loaded with active ingredients minimizes tissue soft
ening of the products during storage. These coatings delay poly
Fresh fruits and vegetables are negatively influenced by oxidative galacturonate activity and preserve the membrane's structural integrity,
reactions, such as browning, which notably decrease the products' making them retain firmness (Firdous, 2021). Calcium (Ca) salts,
appearance and customer acceptability during storage and marketing including CaCO3, Ca lactate, CaCl2, Ca pectate, and Ca propionate, are
(Lante, Tinello, & Nicoletto, 2016). For the most part, fruit browning is commonly considered firmness retainers for controlling softening chal
mostly due to the enzymatic oxidation of phenolics to quinones lenges. The interaction between polymer structure and Ca ions could
moderated by polyphenol oxidase (PPO). Various studies exposed the increase mechanical strength by providing cross-linked networks,
inhibitory effect of chitosan-based coatings on PPO action in pineapple, therefore retard senescence and controlled physical damages. Lo’ay and
fig, lemon, grape, guava, longan, loquat, pistachio, mango, sweet apple, Dawood (2017) demonstrated the decreasing cell membrane degrading
lemon, strawberry, sweet cherry, and cherimoya. According to these enzymes, such as cellulase, lipoxygenase, and pectinase in the banana
findings, coating fruits with chitosan-based nanocomposites lower O2 fruits treated with chitosan-polyvinyl alcohol-oxalic acid composition.
accessibility, which is essential for starting browning reactions. Addi Salicylic acid (SA), a phenolic compound, plays an important role in
tionally, these coatings maintain the membrane firmness by balancing fruit quality, such as taste, aroma, color, and firmness (Romanazzi et al.,
the production of reactive oxygen species (ROS) and scavengers, pre 2017). In a recent study, Punjab Beauty pear fruit was coated with a
serving cell compartmentalization, and separating PPO from phenolic compound consisting of chitosan and SA under cold and room temper
substrates (Adiletta et al., 2018). Ascorbic, sorbic, carboxylic acid, thiol- ature conditions. Results indicated that this treatment suppressed the
containing compounds, resorcinol, and phenolic acids are the most electrolyte leakage and malondialdehyde accumulation and prevented
common anti-browning and antioxidants agents used in the composition membrane damage. Also, this compound delayed fruit softening by ac
of coatings (Liu et al., 2016). These anti-browning and antioxidant tivity inhibiting cell wall degradation enzymes, including poly
components have a dual effect on PPO activity by 1) Inactivating the galacturonase, cellulase, and pectin methylesterase (Sinha, Gill,
PPO enzyme through interaction with the deoxy form of PPO and 2) Jawandha, & Grewal, 2022). In another study, the covering of Ginkgo
Acting as an enzyme inhibitor by competing for the catalytic site (Pan biloba seeds with composite coatings of chitosan/TiO2 NPs efficiently
ahirad et al., 2021). Antioxidant agents react with oxygen, suppressing prolonged the firmness (Tian et al., 2019). The results of Xing et al.
the initiation of browning. They can also react with the intermediate (2021) suggested that coating blackcurrant fruit with the composition of
products to break the chain reaction and inhibit melanin formation chitosan/SA/TiO2 NPs significantly maintained the firmness and quality
(Moon et al., 2020). Anti-browning agents inhibit the formation of o- of this fruit during storage at 4 ◦ C. Therefore, applying chitosan-based
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Table 1
Coatings based on chitosan biopolymer incorporating natural antimicrobial substances for the preservation of fruits and vegetables.
Matrix Bioactive Coating Function Effects on the product Fruit/ Reference
component techniques vegetable
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R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
AgNPs, Silver nanoparticles; ZnO NPs, Zinc oxide nanoparticles; SiNPs, Silisium nanoparticles; TiO2NPs, Titanium dioxide nanoparticles; Fe2O3 NPs, Iron oxide
nanoparticles; CNPs, Chitosan nanoparticles; PNPs, Propolis nanoparticles; CuNPs, copper nanoparticles; ZnNPs, Zinc nanoparticles; MSNPs, Mesoporous silica
nanoparticles; BC-NT-TT, Chitosan- titanium dioxide nanoparticles- thymol and tween; CCNC, Chitosan clay nanocomposite.
Fig. 5. The antimicrobial preserving effects of coating-based chitosan nanocomposites against microbial damage.
Table 2
Coatings based on chitosan biopolymer incorporating anti-browning and antioxidant substances for preserving fruits and vegetables.
Matrix Bioactive component Function Fruit/vegetable Reference
Chitosan TiO2 NPs Delaying decay rate and ripening Mango (Xing et al., 2020)
Coated seeds delayed decay rate, shrinkage rate and
Chitosan TiO2/SiO2NPs Ginkgo seeds (Tian et al., 2019)
maintained firmness during storage
Maintaining the physiological and nutritional
Chitosan, pullulan Chitosan, pullulan Papaya (L. Zhang, Huang, & Zhao, 2019)
attributes of papaya and extending the fruit shelf life
Delaying weight loss, softness, senescence, and
Chitosan Nano-SiOx Green tomato (Zhu et al., 2019)
significantly extended shelf life of green tomatoes
Lactic acid, levulinic
Chitosan Extending the shelf life Ginseng root (Jin, Huang, Niemira, & Cheng, 2016)
acid, and acetic acids
Acetylated soy protein,
Stearic acid Increasing sensory quality Apple (B. Wu, Zhu, & Le, 2017)
chitosan
Antimicrobial activity against yeasts, molds and
Chitosan Lemongrass Grape berry (Oh et al., 2017)
mesophilic aerobes antioxidant
(Espinal-Hernández, Colinas-León, Ybarra-
1-Methylcyclopropene (1- Reducing notoriously the respiration and ethylene
Oleic acid Pitaya Moncada, Méndez-Zúñiga, & Corrales-
MCP) and α-pinene production rates, and inhibited loss of skin firmness
García, 2021)
Maintaining the quality and extending its postharvest
Carboxymethyl chitosan Brassinolide Green asparagus (L. Wu & Yang, 2016)
life
Chitosan nanoparticle
Clove essential oil Extending the Pomegranate aril shelf life Pomegranate arils (Hasheminejad & Khodaiyan, 2020)
coatings
Reducing weight loss, total phenolics, enzymatic
(Molamohammadi, Pakkish, Akhavan, &
Chitosan Salicylic acid activities, color, oxidation of lipids, sensory quality, Fresh pistachio
Saffari, 2020)
and microbial growth during storage
Alginate, chitosan ZnO NPs Increased the shelf life of Guava fruits during storage Guava (Arroyo et al., 2020)
ZnO NPs/ Aloe vera Reducing weight loss by about 5 %, delayed ripening
Chitosan Pineapple (Basumatary et al., 2021)
gel and oxidative decay
Chitosan Mentha essential oils Reducing weight light and enzymatic activity Papaya (dos Passos Braga et al., 2020)
Chitosan with high Grape seed essential Increased the postharvest quality and shelf life during Strawberry and
(Popescu et al., 2022)
molecular weight oil, ascorbic acid storage apple slices
ZnO NPs, Zinc oxide nanoparticles; SiNPs, Silisium nanoparticles; TiO2NPs, Titanium dioxide nanoparticles.
coatings enriched with anti-softening agents can be an attractive offer to 6.4. Chitosan nanocomposites for packaging to enhance shelf-life
prolong the shelf-life and improve the marketability of agricultural
products. Some agricultural products, especially fruits and vegetables, are
easily spoiled after harvest due to their constant respiration and tran
spiration, resulting in a loss of quality and short shelf-life (Santosh
Kumar et al., 2020). Physiological and chemical parameters, including
8
R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
Fig. 6. The schematically applying chitosan-based coatings enriched with anti-browning and antioxidant agents.
changes in sugar content, enzymatic cell wall degradation, chlorophyll okra but also inhibited the development of bacterial and fungal patho
content, the rate of respiration, the level of aromatic contents, and gens (Al-Naamani et al., 2018). Alanas, Saefurahman, and Sani (2021)
ethylene production, affect the ripening of fruits and vegetables (Lee & developed a packaging material based on chitosan-containing cellulose
Hwang, 2017). Moreover, the production of ROS during the trans nanocrystals, effectively enhancing the shelf-life and inhibiting chili
portation of electrons in mitochondria is the main cause of quality loss in peppers' spoilage. Using a chitosan-based bag incorporated with gra
fruits and vegetables under stress or over-ripening conditions (Ali et al., phene oxide conserved melon fruits by maintaining the external
2019). Food quality, stability, and shelf-life can be improved using appearance, extending the storage life, and delaying the senescence of
active packaging systems, releasing antioxidant, anti-softening, anti- the fruits (Alanas et al., 2021). The assessment of chitosan-ZnO NC and
browning, and antimicrobial agents into food. In this vein, chitosan- chitosan-CuO NC for the shelf-life prolongation of packaged guava fruits
based composites incorporated with different natural antimicrobials enhanced the quality and shelf-life by one week compared to unpack
and nanomaterials have been considered as efficient formulations to aged fruits (Kalia et al., 2021). A study on the packaging of carrot pieces
improve shelf-life and preserve the quality of postharvest products indicated that the shelf-life of fruit extended for 9 days in the case of the
(Flórez, Guerra-Rodríguez, Cazón, & Vázquez, 2022). Fig. 7 depicts the chitosan- polyurethane- nano ZnO hybrid films (Indumathi, Sarojini, &
application films based on chitosan nanocomposites for packaging fruits Rajarajeswari, 2019). Recently, Liu & Liu, 2022 prepared chitosan-corn
and vegetables. starch films containing TiO2 NPs and graphene for food packaging. They
In this regard, the shelf-life of green chili was extended using flexible found that CTH-CSH-nano-TiO2-Gr nanocomposite efficiently decreased
rectangular pouches made of chitosan films containing glycerol and food spoilage and increased the shelf-life. As mentioned above, active
citric acid as plasticizer and cross-linker, respectively (Priyadarshi, packaging based on chitosan biopolymer change the atmosphere around
Kumar, & Negi, 2018). de Moraes Crizel et al. (2018) packed fresh the packaged product, as a result changing its metabolism and
walnut kernels in bags from chitosan films incorporated with olive increasing preservation followed by improved quality and shelf-life of
pomace microparticles. This packaging increased the shelf-life of the fresh fruits and vegetables.
product by preventing the oxidation of walnut karnel oils. The investi
gation of polyethylene packaging films coated with chitosan-ZnO
nanocomposite on the shelf-life and quality of okra revealed that
chitosan-ZnO nanocomposites not only maintained the quality of packed
9
R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
Fig. 7. The application films based on chitosan nanocomposites for packaging fruits and vegetables.
7. Environmental risk assessment and safety concerns chitosan what's the fate of these elements as a human eat tomato fruits? On the
nanocomposites other hand, nanoparticles can directly enter the human body through
inhaling and damage our lungs, kidney, liver, skin, and blood, causing
Despite the abundant advantages of engineered nanomaterials in various kinds of cancer and respiratory and cardiovascular diseases after
food packaging, antimicrobial coatings, and the reinforcement of chi damaging DNA (Chenthamara et al., 2019). The toxicity rate and in
tosan nanocomposites, public concerns have been increasing about the fluence of nanoparticles on biological systems depend on various fac
safety impact and migration of NPs. Although, some researchers re tors, including particle size, solubility, concentration, stability, and
ported the nontoxicity of chitosan nanocomposites against mammalian biological characteristics (Addo Ntim et al., 2018). Application of
somatic cells and plant cells, one of the most important concerns is the nanomaterials in open field conditions provides their release and accu
migration of NPs from chitosan nanocomposites, as coating and pack mulation to the air, water, and soil, endangering the health of living
aging when in contact with fruits, vegetables and other foodstuffs organisms and the ecosystem. Antimicrobial chitosan, silver, copper,
(Regiel-Futyra et al., 2015; Xu et al., 2017). Various properties possessed and carbon nanotubes nanocomposites exposed hazardous effects on
by the nanomaterials, including reactive surface, small size, dustiness, fish and Algae health (Abu-Elala et al., 2018; Aznar-Mollá, Fito-López, &
and high aspect ratio, could possibly affect human health and the Alvaro, 2021). More importantly, chitosan nanocomposites have a
environment adversely (Azizi-Lalabadi, Garavand, & Jafari, 2021). negative impact on the microbial population at different states (Santosh
Although NPs may show unexpected movements from chitosan nano Kumar et al., 2020). It should be noted that the toxicity of nanoparticles
composites and enter into the plant system or accumulate in the eatable can be controlled via particle size, morphology, surface behavior and
parts of the plants, the application of nontoxic concentrations can pro incorporation in biopolymers. Moreover, controlled release of NPs from
mote plant growth, seed germination, and the development of metabolic chitosan, need of smaller amount of active compounds for the same ef
rate through a broad spectrum of mechanisms (Landa, 2021). Moreover, fect as well as low costs are considered as advantages of nanocomposites
NPs protect plants against abiotic (e.g., drought, salt, toxicity, and and can be intensified by application of a nontoxic and edible
accumulation of heavy metals) and biotic (phytopathogens and pests) biopolymer such as chitosan.
stresses. Some NPs, including zinc, iron, and manganese, serve as a
source of trace elements for plants. NPs can also modulate oxidative 8. Conclusion
stress by stimulating oxidative enzymes like superoxide dismutase and
peroxidase (Goswami & Mathur, 2019). Hassanisaadi, Barani, et al. In a decade, the application of several biopolymers as coatings and
(2022) reported the dual effects of NPs (positive or negative) on the films in food packaging systems has been investigated. Among them,
photosynthetic rate, germination, growth, oxidative stress, and defense chitosan, due to antimicrobial, antioxidant, and inhibiting enzymatic
mechanisms of plants. For instance, some NPs exhibit a stimulative ef activities, has been considered a promising coating. Moreover, chitosan
fect at low concentrations and a phytotoxic effect at high concentrations possesses many other benefits, such as being edible, non-toxic, a barrier
(Dimkpa et al., 2012). Another considerable challenge is the migration to gases and moisture, solid, biodegradable, film-forming properties,
of nanoparticles through food chain and their accumulation at toxic and suitable as a bioactive carrier. Chitosan-based coatings develop the
levels. For example, exposing tomato plants with some metal oxide capability of the active agents by releasing them gradually to the surface
nanomaterials resulted in high concentration of potassium and less of coated horticultural products. Moreover, incorporating certain
concentration of magnesium, sulfur, and phosphorus (Vittori Antisari, bioactive and functional agents into the polymeric matrix improves the
Carbone, Gatti, Vianello, & Nannipieri, 2015). The question is that sensory, nutritional, and safety of coated fruits and vegetables, which is
10
R. Saberi Riseh et al. Carbohydrate Polymers 309 (2023) 120666
more beneficial for human health. Shelf-life and quality of fresh fruits Aparicio-García, P. F., Ventura-Aguilar, R. I., del Río-García, J. C., Hernández-López, M.,
Guillén-Sánchez, D., Salazar-Piña, D. A., & Bautista-Baños, S. (2021). Edible
and vegetables could be maintained or even improved by using new
chitosan/propolis coatings and their effect on ripening, development of aspergillus
edible coatings incorporated with special active ingredients, such as flavus, and sensory quality in fig fruit, during controlled storage. Plants, 10(1), 112.
antioxidants, anti-browning, antimicrobials, tissue modifiers, and nu Arroyo, B. J., Bezerra, A. C., Oliveira, L. L., Arroyo, S. J., de Melo, E. A., &
trients. Chitosan application as a biopolymer for food packaging can be a Santos, A. M. P. (2020). Antimicrobial active edible coating of alginate and chitosan
add ZnO nanoparticles applied in guavas (Psidium guajava L.). Food Chemistry, 309,
desirable alternative to synthetic plastics and promote healthy food and Article 125566.
the environment. Therefore, more research should be needed to expand Azizi-Lalabadi, M., Garavand, F., & Jafari, S. M. (2021). Incorporation of silver
the application of chitosan-based coatings on large scales commercials nanoparticles into active antimicrobial nanocomposites: Release behavior, analyzing
techniques, applications and safety issues. Advances in Colloid and Interface Science,
as the technology continues to develop. 293, Article 102440.
Aznar-Mollá, F., Fito-López, C., & Alvaro, J. A. H. (2021). Insights into the potential
CRediT authorship contribution statement effects of released engineered nanomaterials from polymer nanocomposites:
Environmental issues and future activities for risk assessment and management.
Journal of Nanoparticle Research, 23(4), 1–19.
Roohallah Saberi Riseh: Supervision, Project administration, Cor Baradar, A., Saberi-Riseh, R., Sedaghati, E., & Akhgar, A. (2015). Effect of some bacteria
respondence. Masoumeh Vatankhah: Writing-original draft, Investi and iron chelators on potato colonization by arbuscular mycorrhiza fungi inoculated
by rhizoctonia. Indian Journal of Science and Technology, 8(19), 1.
gation, Review and editing. Mohadeseh Hassanisaadi: Writing- Basumatary, I. B., Mukherjee, A., Katiyar, V., & Kumar, S. (2022). Biopolymer-based
original draft, Review and editing, Investigation, Conceptualization, nanocomposite films and coatings: Recent advances in shelf-life improvement of
Validation, Visualization. John F. Kennedy: Review & editing, Inves fruits and vegetables. Critical Reviews in Food Science and Nutrition, 62(7),
1912–1935.
tigation, Validation, Visualization, Correspondence.
Basumatary, I. B., Mukherjee, A., Katiyar, V., Kumar, S., & Dutta, J. (2021). Chitosan-
based antimicrobial coating for improving postharvest shelf life of pineapple.
Declaration of competing interest Coatings, 11(11), 1366.
Camara, M. C., Campos, E. V. R., Monteiro, R. A., do Espirito Santo Pereira, A., de Freitas
Proença, P. L., & Fraceto, L. F. (2019). Development of stimuli-responsive nano-
The authors declare that they have no known competing financial based pesticides: emerging opportunities for agriculture. Journal of
interests or personal relationships that could have appeared to influence Nanobiotechnology, 17(1), 1–19.
Cazón, P., Velazquez, G., Ramírez, J. A., & Vázquez, M. (2017). Polysaccharide-based
the work reported in this paper. films and coatings for food packaging: A review. Food Hydrocolloids, 68, 136–148.
Chávez-Magdaleno, M. E., González-Estrada, R. R., Ramos-Guerrero, A., Plascencia-
Data availability Jatomea, M., & Gutiérrez-Martínez, P. (2018). Effect of pepper tree (Schinus molle)
essential oil-loaded chitosan bio-nanocomposites on postharvest control of
Colletotrichum gloeosporioides and quality evaluations in avocado (Persea
No data was used for the research described in the article. americana) cv. Hass. Food Science and Biotechnology, 27(6), 1871–1875.
Chenthamara, D., Subramaniam, S., Ramakrishnan, S. G., Krishnaswamy, S., Essa, M. M.,
Lin, F.-H., & Qoronfleh, M. W. (2019). Therapeutic efficacy of nanoparticles and
Acknowledgement routes of administration. Biomaterials research, 23(1), 1–29.
Choudhary, R. C., Kumaraswamy, R., Kumari, S., Sharma, S., Pal, A., Raliya, R., &
No applicable. Saharan, V. (2017). Cu-chitosan nanoparticle boost defense responses and plant
growth in maize (Zea mays L.). Scientific Reports, 7(1), 1–11.
Cindi, M. D., Shittu, T., Sivakumar, D., & Bautista-Baños, S. (2015). Chitosan boehmite-
Funding alumina nanocomposite films and thyme oil vapour control brown rot in peaches
(Prunus persica L.) during postharvest storage. Crop Protection, 72, 127–131.
Correa-Pacheco, Z. N., Bautista-Baños, S., Valle-Marquina, M.Á., & Hernández-López, M.
This review received no extranet funding. (2017). The effect of nanostructured chitosan and chitosan-thyme essential oil
coatings on colletotrichum gloeosporioides growth in vitro and on cv hass avocado
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