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International Journal of Biological Macromolecules 164 (2020) 304–320

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Review

Enhancing the functionality of chitosan- and alginate-based active edible


coatings/films for the preservation of fruits and vegetables: A review
M. Sneha Nair a,1, Maharishi Tomar b,1, Sneh Punia c, Wirginia Kukula-Koch d, Manoj Kumar e,⁎,1
a
Department of Nutrition and Dietetics, Faculty of Applied Health Sciences, Manav Rachna International Institute of Research and Studies, Faridabad, India
b
Division of Seed Technology, ICAR-Indian Grassland and Fodder Research Institute, Jhansi, India
c
Department of Food Science and Technology, Chaudhary Devi Lal University, Sirsa, India
d
Department of Pharmacognosy, Medical University of Lublin, Chodźki 1, 20-093 Lublin, Poland
e
Chemical and Biochemical Processing Division, ICAR-Central Institute for Research on Cotton Technology, Mumbai, India

a r t i c l e i n f o a b s t r a c t

Article history: A number of studies have established the potential of chitosan and alginate-based edible film/coatings for pre-
Received 24 April 2020 serving the quality attributes of fruits and vegetables. Findings demonstrate that these films/coatings act as a bar-
Received in revised form 20 June 2020 rier on the surface of fruits and vegetables which causes higher moisture and water retention, create favourable
Accepted 9 July 2020
micro-environments by optimizing the concentration of gases and delays ripening. Sincere efforts are being fur-
Available online 16 July 2020
ther made to improve the efficiency of edible films using functional additives such as phenolics, essential oils
Keywords:
(EOs) and nano-forms. These additives have unlocked a new dimension for enhancing functional properties of
Chitosan and alginate alginate/chitosan-based films. These functional compounds are now emerging as an important component of ed-
Active packaging ible films/coatings for prolonging shelf-life of fruits and vegetables. The present review comprehensively elabo-
Functional additives rates recent studies on functional additives and their mechanism of action. Here we also establish their
proficiency in extending quality and shelf-life of various fruits including guava, pear, blueberries and vegetables
like cucumber, capsicum and mushroom. Principles behind antimicrobial and antioxidant activities of additives
in preventing the food spoilage are also reviewed. Competency of phenolics, EOs and nano-forms in extending
the shelf-life without affecting the nutritional properties and safety aspects of the fruits and vegetables still re-
quire further attention.
© 2020 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
1.1. Problem of perishability in fruits and vegetables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
1.2. Edible films and coatings for preservation of fruits and vegetables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
1.3. Source and film forming properties of chitosan and alginate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
1.4. Chitosan and alginate-based edible films and coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
1.5. Chitosan and alginate blend based edible films and coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
1.6. Chitosan-based edible films and coatings with other biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
1.7. Alginate-based edible films and coatings with other biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
1.8. Superiority of chitosan and alginate-based edible films and coatings from other biomaterials. . . . . . . . . . . . . . . . . . . . . . . 306
1.9. Functional additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
2. Functional additives in alginate- and chitosan-based edible coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
3. Enhancing the functionality of the chitosan-based edible active coating/films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.1. Enhancing the functionality of chitosan-based edible coating/films using phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.2. Enhancing the functionality of the chitosan-based edible coating/films using essential oils (EOs) . . . . . . . . . . . . . . . . . . . . . 310
3.3. Enhancing the functionality of the chitosan-based edible coating/films using nano-forms and other potential substances . . . . . . . . . . 310
4. Enhancing the functionality of the alginate-based edible active coating/film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311

⁎ Corresponding author.
E-mail addresses: manojkumarpuniya114@gmail.com, manoj.kumar13@icar.gov.in (M. Kumar).
1
Authors contributed equally.

https://doi.org/10.1016/j.ijbiomac.2020.07.083
0141-8130/© 2020 Published by Elsevier B.V.
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 305

4.1. Enhancing the functionality of the alginate-based edible coating/films using phenolics . . . . . . . . . . . . . . . . . . . . . . . . . 311
4.2. Enhancing the functionality of the alginate-based edible coating/films using essential oils (EOs) . . . . . . . . . . . . . . . . . . . . . 312
4.3. Enhancing the functionality of the alginate-based edible coating/films using nano-forms and other potential substances . . . . . . . . . . 312
5. Regulatory and safety of the chitosan and alginate-based edible coatings/films before and after enhancing the functionality . . . . . . . . . . . . 313
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
CRediT author statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

1. Introduction (1 → 4)-linked-β-D-mannuronate moieties. Alginates have the property


to form transparent, uniform, water soluble and high quality films [9].
1.1. Problem of perishability in fruits and vegetables Alginate-based films and coatings have lower permeability for fats,
oils and oxygen. This low permeability can retard the lipid oxidation
Fruits and vegetables are an essential component of a balanced diet of various vegetables and fruits. This can help in reducing weight loss
that affects the overall vigour and health of the body. They facilitate cel- and microflora growth [10]. These films and coatings improve the fruits
lular detoxification, regeneration and in healing many diseases. The per- and vegetable quality by minimizing the shrinkage, moisture loss, oxi-
ishable nature of fruits and vegetables results in short postharvet life. dative rancidity, oil absorption, flavour, and colour loss [11].
They exhibit a steady-state of transpiration and respiration even after
the harvesting process, leading to loss of quality and decrease in shelf- 1.4. Chitosan and alginate-based edible films and coatings
life. Fruit ripening is an intricate process which is characterized by pro-
found variations in biochemical and physiological changes like ethylene Chitosan-based films and coatings can effectively be used for food
production, increase in respiration rate, variation in sugar content, ex- preservation due to their versatility, non-toxicity, antimicrobial activity,
pression of cell wall degrading enzymes, chlorophyll stability and syn- antioxidant activity, biocompatibility and bio-degradability. Chitosan,
thesis of aromatic compounds [1,2]. Also, the reactive oxygen species dissolved in solutions of dilute acids (hydrochloric acid and acetic
(ROS) generated by the mitochondrial electron transport during ripen- acid) can be fabricated into edible films [12–14]. A number of fruits
ing can cause cellular damage and degrade the quality and acceptability and vegetables like wolfberry, papaya, tomato, mango, carrot, pome-
of fruits and vegetables [3]. granate, banana etc., have successfully displayed improved storage sta-
bility and increased shelf-life after being coated with chitosan-based
1.2. Edible films and coatings for preservation of fruits and vegetables films.
A number of studies have indicated the antimicrobial nature of chi-
Nowadays consumers demand high quality vegetables and fruits, tosan yet only a few mechanisms can conceivably be conceptualized.
enriched with health promoting compounds. This increasing demand Molecular interactions between the positively charged amines on the
is now a challenge to the food and horticulture industries to formulate chitosan structure and negative charge of microbial cells disintegrate
pertinent preservation techniques. This has also instigated a sense of ur- their membrane structure and integrity causing the leakage of intracel-
gency for the scientists and food processing industries to evaluate di- lular constituents and electrolytes into the external environment, killing
verse approaches for augmenting the keeping quality, food safety, the microbe [15]. The antimicrobial property of chitosan is also attribut-
freshness and shelf-life through the use of natural, edible and biode- able to its low molecular weight. This enables it to effectively penetrate
gradable polymers [4]. These edible films and coatings reduce the loss the microbe cell membrane, enter the cytosol and hinder the synthesis
in quality attributes by setting up a semipermeable safety barrier and functions of DNA and RNA leading to microbial cell death. While,
around the vegetables and fruits [5]. A number of biopolymers such as the high molecular weight chitosan encapsulates the cell surface and in-
starch, pectin, carrageenan, alginate, chitosan and xanthan gum have hibits the penetration of nutrients into the microbial cell, starving the
been extensively used to create edible films and food coatings. Their cell and causing its death [16]. Chitosan can also selectively bind the
film-forming properties permit the synthesis of membranes (thick- metals cofactors of various vital metabolic and toxin producing enzymes
ness N 30 μm) and coatings (b30 μm) which are successfully used to pre- of microbes, blocking their metabolism and proliferation.
serve food items [6]. Chitosan-based films and coatings increase the shelf-life of fruits and
vegetables and prevent their oxidative deterioration by exhibiting anti-
1.3. Source and film forming properties of chitosan and alginate microbial and antioxidant properties. The antioxidant activity of these
biopolymers is due to their ability to scavenge free radicals and chelate
Chitin, a poly β-(1–4)-2-acetamido-D-glucose is a profusely occur- metal ions [17]. A number of researchers have also reported that their
ring natural biopolymer, present in the crustacean exoskeleton, fungal antioxidant activities increase with an increase in the degree of
walls and many other materials of biological origin. Chitin when deacetylation of chitin [18]. Pure chitosan-based films have proven to
deacetylated in an alkaline medium, forms chitosan. Chitosan is a copol- maintain the nutritional and qualitative characteristics, increase the an-
ymer made from β-(1–4)-2-amino-D-glucose and β-(1–4)-2- tioxidant activity, prevent microbial contamination, and extend the
acetamido-D-glucose [7]. The feasibility of chitosan based films and shelf life of fruits and vegetables.
coatings to act as a natural preservative is widely known. It can be Alginate is an economical, biocompatible, biodegradable, uniform,
used as a high quality film forming macromolecule. Coatings and films transparent, water soluble and non-toxic film/coating forming
made from chitosan are selectively permeable to gases (O2 and CO2) biomacromolecule [19,20]. It can be used to fabricate excellent quality
and have excellent mechanical properties [8]. Since chitosan-based films and coatings due to its adequately fibrous chemical structure
films and coatings have a high permeability to water vapour, which and gelling properties [21]. These films and coatings are used as post-
limits their use in moist environments, as the control of moisture trans- harvest treatment to preserve the quality of fruits like sweet cherry,
fer is a desired trait. peach, tomato. They delay the ripening and prolong the shelf-life of
Another linear copolymer called alginate is extracted from sea- fruits and vegetables [22,23]. They prevent the microbial spoilage by im-
weeds. Structurally it consists of (1 → 4)-linked-α-L-guluronate and peding microbial proliferation and retarding respiration [24].
306 M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320

1.5. Chitosan and alginate blend based edible films and coatings these composite films. The superior mechanical strength of these films
is due to the cohesive forces between the chains and synergistic interac-
Both alginate and chitosan originate from aquatic ecosystems and tions between the film forming polysaccharides [34]. Composite films
thus display a unique physical and chemical compatibility with each were fabricated by using sodium alginate, gelatin and whey protein iso-
other than their blends with other biopolymers like protein or lipids late and exhibited adequate oxygen permeability, vapour permeability,
[16]. The films and coatings made from these polysaccharides alone tear strength, percentage elongation at break point and tensile strength
have various drawbacks such as poor water resistance and inferior me- [36]. The random coiled conformation of gelatin maximizes the number
chanical properties making them unsuitable for their application in and surface area of contact with the oppositely charged sodium alginate
films and coatings when compared to the polymeric films made by groups increasing the tensile strength and elongation at break. Edible
blending these two biopolymers [25]. Alginates form a gel at pH value films and coatings made from carboxymethyl cellulose has good barrier,
which is lower than its pKa via ionotropic gelation. The electrostatic in- thermal, biodegradability, mechanical and good-film forming proper-
teractions between the polyanionic sodium alginate and polycationic ties [37]. Edible films were prepared by integrating epigallocatechin gal-
chitosan make them highly biocompatible for producing stable poly- late with carboxymethyl cellulose and sodium alginate films. These
meric films. This electrostatic interaction is caused by –NH3+ on chito- films had improved tensile strength, flexibility and reduced elongation
san and –COO− on sodium alginate forming a white, insoluble at break due to the intramolecular and intermolecular interactions in
polymer. A sophisticated layer-by-layer technology has been developed the polymer network [38].
in which polyelectrolyte multilayer films are formed with excellent
properties [25]. The film made from these blends possesses superior 1.8. Superiority of chitosan and alginate-based edible films and coatings
water vapour transmission and gas exchange properties which help in from other biomaterials
increasing the shelf-life, maintaining the appearance and also
preventing the off-flavour development in food items [26]. Chitosan and alginate have a number of benefits attributable to their
biodegradability, biocompatibility and their amenability to biochemical
1.6. Chitosan-based edible films and coatings with other biomaterials and chemical modifications [39,40]. Alginate and chitosan-based coat-
ings and films are more promising than the other polysaccharides, lipids
Chitosan can be blended with various naturally occurring biomate- and protein-based coatings and films. Alginate is easily soluble in water
rials like polysaccharides (cellulose, pectin, carrageenan and alginates) while chitosan is soluble in glacial acetic acid. However, cellulose re-
and proteins (caseinate, gelatin and collagen) for making films. Gener- mains insoluble in water and also sparingly soluble in most of the
ally, polysaccharide blends offer a number of benefits compared to pro- polar solvents. Also, alginate and chitosan-based edible coatings and
teins and lipids blends as the developed film is cheap, stable, exhibit films show good barrier and mechanical properties. In contrast,
better water and thermal stability [27,28]. The blending of chitosan starch-based films demonstrate comparatively poor mechanical prop-
with starch from corn, rice and cassava have been studied in detail erties and hydrophilic nature resulting in brittleness. Pectin based
[16]. High amylose starch and chitosan forms highly stable film is due films also brittle and being a carbohydrate may serve as a source of mi-
to the formation of strong hydrogen bonds between these polymers. In- crobial growth [41]. Even, lipid-based films are not preferable due to
creasing the concentration of chitosan in chitosan-coated starch film their poor mechanical properties contributing to brittleness and poor
improves the tensile strength while a higher starch content increases gas barrier properties [42]. Protein based films when compared with al-
the value of elongation at break of the film [29]. Carrageenan an anionic ginate and chitosan-based films are not only brittle in nature but can
polysaccharide is isolated from red seaweed. Similar to alginate it can also be allergic [43].
also associate with chitosan to form a polyelectrolyte complex. The U.S. Food and Drug Administration (US FDA) and European Commis-
films prepared by the blends of carrageenan and chitosan are thermally sion classifies food grade sodium salt of alginate as GRAS (generally rec-
less stable and lack moisture barrier properties, hence are less popular ognized as safe) material and has recommended their use as thickener,
for making films for the preservation of foods [30]. Chitosan and stabilizer, emulsifier, and gelling agent. Similarly, chitosan was also rec-
cellulose-based hybrid films are mechanically strong which is attribut- ognized as GRAS for application in agricultural and medicinal fields
able to the electrostatic interaction between them. These films pos- under different regulation by the US FDA depending on the source of de-
sessed high elasticity, transparency and resistance that are considered rivatives [44–46]. Chitosan shows inherent antimicrobial properties due
important for food packaging. Pectin is another polysaccharide which to its cationic nature which is absent in other polysaccharides, protein
forms uniform composite films with chitosan which are stabilized by in- and lipid-based polymers [31]. Moreover, chitosan and alginate-based
termolecular interaction. These films display desirable attributes which coating and film biomaterials have a high biological capacity to carry
help in maintaining the sensory values and shelf life of fruits and vege- and integrate a number of functional compounds, food additives and
tables [31]. Chitosan-based blended films with protein biopolymers are antimicrobial compounds. Additionally, alginate and chitosan-based
also well documented. The blends developed from chitosan and gelatin films and coatings give an aesthetic appearance, are non-toxic, selective
have excellent affinity and compatibility due to the hydrophilic nature gas barriers, cost-effective and are non-polluting. These films and coat-
of these biopolymers [16]. The resulting films have increased barrier ings can also be used as carriers of antioxidant, antimicrobial and aro-
properties against water vapour and significantly improved elongation matic functional compounds. The modern consumer is more inclined
at break value. Similarly, chitosan also blends with the carboxylic towards green consumerism, which encompasses less artificial ingredi-
groups of casein through electrostatic interactions [32]. These films ents, guaranteeing high-nutritive value, safety, quality and prolonged
have improved impact strength, tensile strength and also act as an effi- post-harvest shelf-life.
cient barrier against moisture loss [33].
1.9. Functional additives
1.7. Alginate-based edible films and coatings with other biomaterials
Integration of functional additives like preservatives, antimicrobials
Alginate can be conceivably blended with pectin to make packaging and antioxidants in films and coatings are used to improve the quality
films. Both pectin and alginate belong to polyuronates group of com- attributes of fruits and vegetables. The quality attributes include in-
pounds, and undergo synergistic chain to chain association to form creased shelf-life due to superior antimicrobial and barrier properties,
hydrogels by adding divalent cations like Ca+2 [34]. These films enhanced appearance and acceptability to the consumer. Phenolics are
displayed enhanced thermal, transparency and mechanical properties omnipresent in the plant system and are a crucial part of human diet
[35]. The unique colloidal nature of pectin increases the thickness of and nutrition, by virtue of their high antioxidant properties [47–49].
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 307

On incorporation into food as functional compounds with the edible components is a promising technique in modern barrier technologies
films, they control rancidity, prolong shelf-life and affirms the nutri- to boost the antimicrobial activity, antioxidant capacity and shelf-life
tional quality. Additives like ascorbic acid decrease the browning of of food products [56]. This also has a positive influence on the distribu-
fruits and vegetables [50]. Nanoparticles made from copper and zinc ox- tion, commercialization and conservation of food products [57].
ides improve the shelf-life due to their antimicrobial properties [51]. EO Use of phenolics as functional compounds in packing films has been
extracts from tea tree, thyme, clove, bergamot etc. are used in coating recently studied due to their high antioxidant and antimicrobial proper-
formulations. They improve anti-microbial activity, control water loss ties [58–60]. Addition of polyphenols derived from tea extracts in algi-
and respiration during cold storage [52,53]. Some oils also have the po- nate based edible films increases their antioxidant and physical
tential to augment the shelf-life of fruits and vegetables [54]. properties [61]. Ruan et al. [38] prepared sodium alginate based edible
The present review focuses on the application of alginate and films containing a polyphenol, epigallocatechin gallate. These films
chitosan-based edible coatings and films and their blends with other had a tensile strength with strong antioxidant activities. These im-
biopolymers for the preservation of fruits and vegetables. Here we ac- proved mechanical properties were due to the increased intramolecular
centuate the recent advancements in the evolution of edible films and and intermolecular interactions. In a similar study, tea polyphenols
coatings and functional additives with respect to their application in were integrated into sodium alginate based films. These films demon-
the preservation of fruits and vegetables. We also focus on various post- strated an enhanced degree of cross-linking, tensile strength and anti-
harvest applications of these films and coatings and functional com- oxidant activity.
pounds to prolong shelf-life, confer antimicrobial potential and Essential oils (EOs) are hydrophobic concentrated liquids, derived
manage physiological disorders of fruits and vegetables. The various from aromatic plants. They contain a multitude of bioactive compounds
components discussed in the current review are presented in Fig. 1. like terpenoids and phenolics. These oils exhibit potent antioxidant and
antimicrobial properties, which can act as feasible preservative com-
2. Functional additives in alginate- and chitosan-based edible pounds for perishable foods [62]. Predominantly alkaloids, isoflavones,
coatings phenolic acids, aldehydes, carotenoids, monoterpenes, and flavonoids
constitute the main components of EOs [63]. EOs are nearly water-
Edible films and coatings made from chitosan and alginate can be insoluble, highly volatile and lipophilic, susceptible to oxidation and
amalgamated with a number of functional compounds that can enhance photothermal effects, limiting their overall application. To reduce their
the mechanical, antimicrobial and maintain nutritional qualities of food volatility, increase biological activity and utilization, they need to be
products. These films and coatings have the ability to be combined with immobilized and encapsulated in polymer matrices like alginate and
bioactive functional components to produce high-quality active packag- chitosan for their effective applications. This increases the stability and
ing materials [55]. Incorporation of these bioactive functional contact area of EOs and helps in their stable dispersion on the surface

Fig. 1. Diagram representing various components discussed in the review i.e. polysaccharide matrix (chitosan and alginate), functional materials (phenolics, essential oils and nano-forms)
and matrix incorporated with functional materials for improving the overall properties of the edible coatings/films. Here m (α-L guluronic acid) and n (β-D mannuronic acid).
308 M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320

of fruits and vegetables where the majority of microbes proliferate [64]. of EOs can be degraded on coming in contact with food components
Oxygenated terpenoids, aldehydes and phenols confer antimicrobial (minerals, lipids and proteins) or its uneven distribution can signifi-
properties to EOs [65]. Hydrophobicity of EOs assists the interaction be- cantly decrease its antimicrobial activity [70]. Various factors of food en-
tween the EOs and the lipid membranes of mitochondria and microbial vironment like pH, water activity, enzymes influence the biological
surface. This interaction deteriorates the structural integrity and mem- activity of EOs [71]. Consequently, the concentration of EOs has to be in-
brane permeability of the microbe and instigates the outflow of ions creased to accomplish their similar effectiveness in the food system [63].
and vital cell constituents leading to cell death [65]. To maintain the biological activity of EOs and decrease their effect on or-
A number of past studies related to the integration of EOs derived ganoleptic properties of food items, the EOs should be encapsulated in a
from Origanum vulgare, Cinnamomum verum, Zataria multiflora, Zingiber food compatible delivery system.
officinale, Cymbopogon, Thymus vulgaris into the matrix of natural poly- Nanoemulsions are made of two immiscible liquids where the
mers for coating the food products are well established ([66–68]. droplet size of one liquid phase is 20–500 nm called the dispersed
Mahcene et al. [9] studied the effects of EOs derived from M. pulegium L, phase which is suspended in another liquid phase called the contin-
A. herba alba Asso, O. basilicum L, R. officinalis L, incorporated into sodium uous phase. The EOs are used as the dispersed phase while chitosan
alginate films. These films were then analyzed for their antioxidant and and alginate are used as continuous phase [11,72]. Small droplet
antimicrobial properties. The antioxidant capacity of these films varied size can augment the transport of EOs through biological membranes
from 4.5% to 23%. These films had improved barrier, thermal and biode- and the increase in surface area/volume ratio enhances diffusion, im-
gradable properties. Similarly, the incorporation of EOs of Cinnamomum proves functionality and antimicrobial activity [64]. Encapsulating
verum into chitosan films enhanced their antioxidant potential, due to EOs in nanoemulsion can help to achieve the desired effect at a sig-
the presence of terpenoids and cinnamyl aldehyde [69]. nificantly lower concentration with higher efficiency and increased
Use of EOs in food packaging is limited due to its instability and precision [73]. Nanoemulsions of lemongrass, thyme and sage,
strong aromatic flavour which influences the organoleptic characteris- when used with sodium alginate films, increased their antimicrobial
tics of food. Using EOs directly is challenging as the reactive compounds activity [72].

Fig. 2. The role and mechanism of action of functional materials in enhancing the shelf-life of fruits and vegetables. (A) The matrix of alginate/chitosan along with functional additives act as
water and oxygen barrier for inhibiting the respiration and eventually ROS generation. The specialised coating also inhibits the spoilage of fruits by microbes and UV-light. (B) Phenolics,
essential oils and nano-particles destabilize the microbial membranes, they then perforate into the cells and block the protein synthesis, cause electrolyte leakage and ultimately cell death.
Nano-metallic forms generate (ROS) like hydroxyl radicals, superoxides and results in organelle damage. They further restrict the synthesis of DNA, RNA and lipids required for the survival
of the microbes. (C) These functional materials mainly phenolics act as antioxidant and prevent the fruits and vegetable from the damage by ROS. (D) The synergistic effect of alginate/
chitosan based coatings with functional additives maintain the appearance, flavour, and extend the shelf-life of fruits and vegetables. Here ROS (reactive oxygen species), TSS (total
soluble solids), TAC (titratable acidity), TAC (total ascorbic acid content).
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 309

Use of nanomaterials as a functional material in the films is a prom- preservation and enhancing the shelf-life of fruits and vegetables are
ising area in food packaging and processing. Since the chemical and discussed in the following sections.
physical properties of nanomaterials can be easily modulated as per
our need at a nanoscale, a diminutive change in shape and structure 3.1. Enhancing the functionality of chitosan-based edible coating/films
can significantly alter the final product. Studies confirm that the using phenolics
nanomaterials can effectively be used with packaging polymers to pro-
long the shelf-life, impart antioxidant and antimicrobial property with- Phenolics are secondary metabolites produced by the plants in re-
out changing the physicochemical properties and taste of the food sponse to stress. They prevent cell damage and oxidation. Plant extracts
materials [74]. Nanoparticles (NPs) made from calcium oxide (CaO) contain polyphenolic compounds such as phenolic acids, flavonoids and
and zinc oxide (ZnO) can improve the barrier and mechanical character- anthocyanins. These extracts contain phenolics and its derivatives
istics of the polymeric films. Alginate films have a high interaction with which serve as effective antioxidant and antimicrobial agents. Phenolics
water molecules, creating an inadequate barrier for water vapour and act as antioxidants by their radical scavenging activity which in turn
increased solubility. Crosslinking the film matrix with zinc and calcium blocks the oxidative chain reactions [92]. The individual phenolic con-
NPs can improve their barrier properties [75,76]. The antimicrobial ac- stituents, exhibit synergy when used in coating formulations and en-
tivity of these NPs is due to the production of reactive oxygen species hance their overall antimicrobial and antioxidant potential. Phenolics
(ROS) like hydroxyl radicals, superoxides and hydrogen peroxide chiefly destabilize the microbial membranes, they then perforate into
under the presence of UV light and moisture. These ROS react with the the cells and block the protein synthesis, ultimately causing cell death
cell surface of microbes and damage the vital intracellular components (Fig. 2) [93]. A study reveals that the efficacy of phenolic extracts in
like lipids, proteins, DNA (Fig. 2). They also increase the porosity of terms of its antimicrobial property is dependent on its concentration
the microbe cells by destroying their membrane integrity. Even though, and the duration of exposure to the test microorganism [94].
the use of NPs for food packaging is a rising field, one of the chief possi- Phenols interact with the polymeric matrix of chitosan-based films
ble concern is the migration of NPs from film matrix into the food [77]. through hydrogen bonds. This enables the slow and regulated release
NPs made from ZnO/CaO and ZnO NPs were integrated into alginate of these phenols in the surrounding medium [95]. A number of studies
based edible films. These films exhibited enhanced mechanical proper- indicate an increase in the antimicrobial efficacy of chitosan films with
ties owing to the large surface area and higher surface energy of these the integration of plant phenol extracts [53,96,97]. Kanetis et al. [98]
NPs. Metal NPs also influence the opacity of the films and edible coat- showed that the addition of 500 mg/L Salvia fruticosa Mill. extract in
ings, which can eventually affect the perception of food by the con- 1% chitosan based coating preserved the physicochemical characteris-
sumer. This behaviour is attributable to the unique light scattering tics of table grapes and inhibited the growth of Botrytis cinerea during
property of NPs, which restricts the light transition across the polymeric their storage at 10 °C for 21 days. Kaya et al. [99] demonstrated the effect
films. This transition depends on particle concentration and size [78]. of 60 mL chitosan-based films containing 1 g Berberis crataegina dried
ZnO NPs fused with chitosan and alginate based films were applied on extract and 1 mL seed oil and found that these films exhibited a high
guava (Psidium guajava L.). These fruits displayed almost no fruit rotting thermal stability, antioxidant property and anti-quorum sensing activ-
due to the antimicrobial nature of these particles along with superior ity as compared to chitosan films without the plant extract. Also, these
barrier properties of the films [79]. chitosan films containing B. crataegina dried extract and seed oil in-
duced resistance against Escherichia coli, Staphylococcus aureus, Proteus
microbilis, Proteus vulgaris, Pseudomonas aeruginosa, Enterobacter
3. Enhancing the functionality of the chitosan-based edible active aerogenes, Bacillus thuringiensis, Salmonella typhimurium and Streptococ-
coating/films cus mutans.
Zhang et al. [100] showed that 2% chitosan films enriched with 4%
Chitosan is known for its antimicrobial, antioxidant, non-toxic, bio- banana peel extract resulted in a smooth and compact structure with
degradable and film forming potential. These properties facilitate their excellent antioxidant activity and high tensile strength, demonstrating
wide use in the development of edible coatings, edible films and enhanced mechanical properties. The higher tensile strength was due
nano-emulsions [80,81]. However, the functional ability of chitosan is to the higher degree of stable cross linkage between the banana peel
based on several factors like the degree of deacetylation, molecular phenolics and chitosan matrix. These phenolics integrated chitosan
weight, pH, concentration and source of its origin [82]. It is well docu- films also serve as efficient barriers against gaseous exchange due to
mented that the effectiveness of chitosan as an antimicrobial agent in- their densely packed microstructure. These films also showed reduced
creases with the degree of deacetylation and its concentration moisture and water vapour permeability which was due to the binding
[83–85]. Chitin is deacetylated to produce chitosan with soluble amine of -OH and -CHO groups of phenolic compounds on to the chitosan ma-
groups. The presence of these soluble amine groups in chitosan deter- trix, thereby, reducing its interaction with water molecules. In addition,
mines its degree of solubility which increases with the degree of the interaction of -OH and -CHO groups with the -NH2 and -CHO groups
deacetylation [86]. in chitosan molecule reduces the water solubility of these films. Applica-
Chitosan exhibits strong antimicrobial properties against a number tion of chitosan films containing banana peel extract on apple fruit de-
of Gram-negative and Gram-positive bacteria, yeast and fungi [82]. In creased the respiration rate and delayed change in fruit weight,
spite of these antimicrobial properties, there is still a need to boost increased firmness, retained total soluble solids (TSS), titratable acidity
and diversify their antimicrobial potential which can be boosted by in- (TA) and ascorbic acid content at storage and under room temperature.
tegrating them with essential oils [87], plant extracts [88], NPs [89], Nguyen et al. [94] investigated the application of 1% chitosan-based
gamma-irradiation and high hydrostatic pressure [90,91]. The role of coating enriched with 1–3% Sonneratia caseolaris (L.) Engl. leaf extract
these functional additives in maintaining the overall quality of fruits on Areca banana fruit. The enrichment of S. caseolaris (L.) Engl. leaf ex-
and vegetable is displayed in Fig. 2. Further, the use of the nano-metal tract made the films more compact and smoother with an improved
oxides such as TiO2, ZnO, silica NPs when used in nano-emulsions and barrier property against moisture and decreased light transmittance.
applied on fruits and vegetables aid in the extension of their shelf-life. The enhanced structural properties of the S. caseolaris (L.) Engl. leaf ex-
These nano-metal oxides function as anti-microbials and prevent the tract enriched chitosan films may be attributed to the formation of hy-
spoilage of the food materials. Integration of functional compounds in drogen bonds between the polyphenol components of the extract and
chitosan improves their functionality, thereby aiding the preservation chitosan. Also, the chitosan films with the incorporation of (1%, 3%)
of nutritive and sensory attributes of fruits and vegetables and delaying S. caseolaris (L.) Engl. leaf extract proved to be effective against
their senescence. Some of the most widely used functional materials for P. aeruginosa infestation. The increased concentration of the extract
310 M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320

consisting of high levels of flavonoids- luteolin and luteolin 7-o-α- Huds in cherry tomato fruits (Solanum lycopersicum L.). These films ef-
glucoside was responsible for the antibacterial activity. Chitosan-based fectively controlled infection causing molds like Penicillium expansum,
coating films were amalgamated with olive pomace and leaf extracts Botrytis cinerea, Rhizopus stolonifera and Aspergillus niger. Rotundifolone
and applied over apple. The coated fruits displayed a higher retention and menthol are the chief antimicrobial compounds in these EOs. They
of antioxidants, flavonoids, total phenols, fruit weight, increasing the are chemically monoterpenes and have the ability to disorganize the
overall nutritional quality of fruits [102]. Edible coatings made from chi- membrane structure, resulting in depolarization and morphological al-
tosan and locust bean gum integrated with phenolics rich water pome- terations, interfering with fungal metabolism. These films also have ef-
granate peel extract and a biocontrol agent (Wickerhamomyces ficient barrier properties due to the strong hydrophobic nature of EOs.
anomalus). These films reduced the postharvest decomposition of or- However, (7.5, 10 mg/mL) chitosan alone caused the highest inhibition
anges by inhibiting the growth of Penicillium digitatum by the synergis- against C. gloeosporioides isolates. This may be due to the interaction be-
tic effect of bioactive phenolic compounds and biocontrol agents [103]. tween the positive charge on chitosan molecule and the negative charge
Interestingly, the flavonoids in this study demonstrated antibacterial on the fungal membrane, causing destabilization of the membrane com-
activity against P. aeruginosa (gram negative bacteria) and were not ponents, loss of electrolytes and eventually fungal cell death [110]. The
very effective against S. aureus (gram positive bacteria). Further, the in- authors found an improved inhibitory effect of (5 and 7.5 mg/mL)
teractions between the phenolic components with the bacterial mem- chitosan-based coatings containing (0.15, 0.3, 0.6 and 1.25 μL/mL)
brane induce the permeability of these membranes for these M. piperita L. or Mentha × villosa Huds EOs against different test strains
compounds resulting in an imbalance in the structural integrity of of C. gloesporioides and C. brevisporum. In addition, coating formulations
these membranes and inhibiting their vital cellular processes. These consisting of 5 mg/mL chitosan and 0.6 or 1.25 μL/mL of M. piperita L. or
studies establish the use of phenolic compounds as a potential additive Mentha × villosa Huds retarded the development of anthracnose in the
in the chitosan-based edible coatings and films and serve as an antimi- coated papayas stored for 10 days at 25 °C. These coatings displayed a
crobial and antioxidant agent for preventing the spoilage of fruits and slow diffusion of the EO constituents onto the surface of the cantaloupe,
vegetables. which increased their antifungal activity [111]. Chitosan nanoparticles
loaded with Illicium verum EO exhibited enhanced antioxidant, anti-
3.2. Enhancing the functionality of the chitosan-based edible coating/films aflatoxigenic and antifungal activities. These films were useful against
using essential oils (EOs) a number of food borne molds and aflatoxigen producing strain of As-
pergillus flavus by reducing their ergosterol content and leakage of
EOs are volatile secondary metabolites that are chiefly extracted ions like Mg2+, K+ and Ca2+ [112].
from aromatic plants and exhibit strong aroma, antioxidant and antimi- Nanoemulsions and conventional emulsions of lemongrass EO were
crobial properties [104,105]. Essential oils consist of major and minor amalgamated with chitosan-based films and applied on grape berries.
structural components. The major structural components contribute to The berries coated with nanoemulsions displayed increased microbial
the antimicrobial activity of EOs whereas the minor components syner- activity against Salmonella typhimurium, extended shelf life, higher anti-
gistically expedite and diversify their antimicrobial action [16,106]. oxidant activity, retention of colour and total soluble solid content [113].
While, the EOs exhibit synergism, they are more effective when used Modified chitosan based films integrated with nanoemulsion of lemon
as a whole rather than as their individual constituents [107]. A number EOs, when applied on rucola leaf increased its shelf life to 7 days in com-
of studies demonstrate an increase in the effectiveness of chitosan when parison to control samples. The effectiveness of nanoemulsion based
incorporated with EOs. films in extending the shelf-life was more than chitosan or oil coatings
Ma et al. [108] found that cantaloupes (melon) displayed strong an- alone [114]. Hence, it is well established by these studies that integra-
timicrobial properties when coated with 1% chitosan and 0.1% lauric tion of EOs with chitosan-based edible coatings/films can be efficient
arginate based coatings, integrated with 1% cinnamon oil and 0.1% eth- and effective for the preservation of fresh fruits and vegetables.
ylenediaminetetraacetic acid as functional compounds. These coatings
could inhibit the growth of food borne pathogens like E. coli, Listeria 3.3. Enhancing the functionality of the chitosan-based edible coating/films
monocytogenes, Salmonella enterica, a number of several yeast and using nano-forms and other potential substances
mold species. They also ensured consistency in firmness and colour dur-
ing 14 days storage at 2 °C. Delay in the respiration rate with less ethyl- Currently, the use of nano-coatings and films is gaining popularity in
ene production and enzyme activity could be a possible reason for the area of fruits and vegetable preservation. Several studies suggested
retained firmness and colour of the coated cantaloupes. The coated the beneficial effect of using nano-coatings in maintaining the quality
fruits also retained their weight due to the high hygroscopic property of avocado, tomato and bell pepper [115–117]. These nanoforms en-
of the polymeric film. The integrated EOs have strong antioxidant activ- hance the antimicrobial property and retard decay and senescence. Chi-
ities and can also inhibit the enzyme activities of fruits and vegetables tosan exhibits a high capacity to chelate various metal ions like iron,
which govern their physiological deterioration and ripening. silver, copper, therefore, demonstrating their higher feasibility of inte-
Similarly, Shahbazi [109] demonstrated that 1% chitosan integrated grating metal NPs [118]. Youssef et al. [119] indicated the use of 1% chi-
with 0.2% Mentha spicata EOs effectively exhibited strong antimicrobial tosan and silica nanocomposites completely inhibits the growth of
properties against Listeria monocytogenes, psychrotrophic bacteria, Botrytis cinerea thereby preventing the development of grey mold in
yeasts and molds. The major compounds-carvone, limonene and β- table grapes. The decay incidence at the end of post-harvest storage
bourbonene in Mentha spicata EOs are capable of forming hydrogen was significantly reduced to 50 and 67%, for cv. ‘Italia’ and ‘Benitaka’ re-
bonds with the bacterial cell membrane, causing porosity of plasma spectively, thus extending their shelf-life by one week at 1 °C. Saral
membrane and disrupting the amino acid and ionic balance which re- Sarojini et al. [120] studied the effect of mahua oil-based polyurethane
sults in cell death. The strawberries coated with these films displayed and chitosan films incorporated with 1–3% ZnO NPs on fresh cut carrots.
delayed respiration, thereby prolonging their shelf-life by 12 days at These composite films extended their shelf-life by 9 days. Similarly,
4 °C. Antimicrobial activities of these EOs are attributed to limonene, when 1–3% of ZnO NPs were added in mahua oil-based polyurethane
β-bourbonene and carvone which forms hydrogen bonds with the bac- and chitosan composite films, a homogenous surface was observed.
terial membrane. This interaction forms transient membrane pores However, increasing the concentration of ZnO NPs to 5% caused the ag-
leading to depletion of ATP, essential metabolites, disturbance of ionic glomeration of these NPs. The films also exhibited high thermal stability,
gradient causing cell death. tensile strength, hydrophobicity, biodegradability, transparency, anti-
Guerra et al. [105] evaluated the effectiveness of chitosan-based microbial activity and non-cytotoxic properties. The structural proper-
films integrated with the EOs from Mentha piperita L. or Mentha × villosa ties of the ZnO NPs enriched chitosan-based films improved with an
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 311

increase in the amounts of ZnO NPs. This was due to the molecular inter- improved physical and biological properties for preservation of fruits
actions of ZnO NPs with the polymeric matrix, formation of hydrogen and vegetables [130]. Thus, the utilization of nano-forms of chitosan
bonds and blocking of the surface pores of the films. These NPs can dis- or certain NPs such as TiO2, ZnO etc. in edible coating formulations are
rupt the bacterial membrane and induce oxidative stress inside the mi- beneficial in boosting the functional properties of chitosan and preserve
crobe through ROS production (Fig. 2). the overall quality of fruits and vegetables.
Ortiz-Duarte et al. [121] used silver-chitosan nanocomposite films
on fresh cut melons and demonstrated a decrease in respiration rate, in- 4. Enhancing the functionality of the alginate-based edible active
crease in vitamin C, retention of firmness, improved sensory attributes coating/film
and increased microbicidal activities during storage at 5 °C for
13 days. Xing et al. [122] indicated that chitosan incorporated with Sodium alginate is a popular polysaccharide with excellent colloidal
nano-(titanium dioxide) TiO2 composite coatings preserved the overall properties and its high reactivity to polyvalent metal cations, resulting
quality of mangoes stored at 13 °C. The authors also found that these in the formation of gels or insoluble polymers [131]. Due to its potential
coatings could retain optimum TSS, firmness, total phenolic and flavo- to form a semi-permeable membrane when applied on fruits and vege-
noid content, reduced the respiration rate, increased activities of perox- tables, it has extensively been used as an edible coating for preserving
idase (POD) and polyphenol oxidase (PPO). POD is the chief enzyme apples, peaches, mushroom and broccoli [131–134]. Recently, the effi-
that detoxifies oxyradicals, which helps to protect the fruits and vegeta- ciency of sodium alginate based edible coatings and films integrated
bles from oxidative damage by regenerating glutathione and ascorbate. with plant extracts like grapefruit seed extract [135], essential oils
The radical scavenging activity of nano-TiO2 destroys the bacterial cell such as eugenol [136] and antimicrobial compounds like bacteriocin
membranes by ROS production and further inhibit the synthesis of [137] have been investigated for enhancing the shelf-life of fruits and
DNA, RNA and lipids, necessary for the survival of the bacterial cells. In vegetables.
addition, incorporation of TiO2 NPs in chitosan coatings improved
their moisture retention ability. Isturiz-Zapata et al. [123] stated that 4.1. Enhancing the functionality of the alginate-based edible coating/films
when coatings made from nano structured chitosan along with chitosan using phenolics
integrated with cinnamon essential oil or trans-cinnamaldehyde were
applied on cucumber, they significantly improve their postharvest qual- Binding of polyphenols to polysaccharides depends on the pH, tem-
ity. They effectively resisted the growth of Fusarium solani, reduced res- perature, ionic strength, structure and native charge of the polysaccha-
piration and ethylene production, retained weight, total chlorophyll rides. Some major structural properties determine the binding between
content and extended its shelf-life up to 2 days when stored at 12 °C the phenols and polysaccharides including the availability of hydroxyl
and 85% relative humidity for a period of 16 days. and hydrogen bonding groups on polyphenols, with their respective
Apart from phenolics, essential oils and nano-forms there are few binding sites on the polysaccharides, their molecular flexibility and
other novel ways to enhance the functionality of the chitosan-based ed- the extent of steric hindrance due to presence of side chains in polysac-
ible coatings. Song et al. [124] incorporated (64 μg/mL) nisin and charides [138]. Chen et al. [59] demonstrated that when Nanfeng man-
(250 μg/mL) ε-polylysine in 1% chitosan based coatings and studied darin was coated with 1.5% alginate enriched with Ficus hirta fruit
their effect on the maintenance of quality and growth of microbes like extracts, inhibited the growth of pathogenic fungi, Penicillium italicum
S. aureus, Pseudomonas spp., yeasts and molds. Nisin has the ability to during the storage at 6 °C for 100 days. They also exhibited enhanced
promote ε-polylysine uptake by the microbial cells, this consequently synthesis of phenolic compounds and enzymatic activities of superox-
facilitates the interaction between ε-polylysine and nucleic acids of mi- ide dismutase (SOD), catalase (CAT), POD, CHI, GLU and PAL in the
crobes, interfering with their replication. These coatings also restricted fruit and decrease the decay rate, respiration rate and malonaldehyde
the gene expression and catalytic activities of cinnamate-4- content (MDC).
hydroxylase and 4-coumarate-CoA ligase resulting in reduced lignin Nair et al. [56] showed that the application of 2% alginate based coat-
production and white blush formation on fresh cut carrots. ings incorporated with 1% pomegranate peel extract on capsicum could
According to Shen and Yang [125], coatings made from chitosan and effectively protect and maintain the chlorophyll, ascorbic acid, firmness
salicylic acid, induced the activities of phenylalanine ammonia lyase and colour while inhibiting the growth of fungal pathogen
(PAL), chitinase (CHI), β-1, 3-glucanase (GLU) and reduced the decay Colletotrichum gloeosporioides at 10 °C storage. The growth of the fungal
of table grapes by inhibiting the growth of microbes like Botrytis cinerea. strain C. gloeosporioides was inhibited by the presence of punicalagin, a
1% chitosan-salicylic acid composite coating formulation successfully major phenolic present in the pomegranate peel extract. A synergy be-
decreased the respiration rate and delayed changes in weight loss, tween the phenolic compounds in pomegranate peel extract and chito-
TSS, TA and sensory attributes of table grapes during storage. The san retarded the respiration rate and the enzymatic activity of
amino group of chitosan interacts with the carbonyl group of salicylic chlorophyllase in the coated guavas. The process aided in preventing
acid to form a conjugate molecule. Similar findings were reported by the degradation of the chlorophyll molecule, thereby, reducing changes
Zhang et al. [126] on the application of chitosan and salicylic acid coat- in the colour during storage.
ing in cucumber. Integrating essential oils or phenolic extracts in edible Fabra et al. [139] investigated the effect of novel films based on algi-
coatings and edible films has been beneficial in extending the shelf-life nate enriched with (0.75 g extract/g alginate) green tea and a (0.75 g ex-
of food materials as discussed in the previous sections. However, these tract/g alginate) grape seed extracts. The alginate films integrated with
EOs and phenolics sometimes diffuse into the food products imparting green tea extract displayed better inhibitory action against murine
undesirable flavour and aroma owing to the presence of a mixture of norovirus and hepatitis A virus. They displayed higher antioxidant activ-
volatile and non-volatile components in them. Due to the sensitivity of ity and improved water barrier properties than the films containing
these components to light, oxygen, pressure and high temperature, grape seed extract. The increased antiviral activity of the alginate-
the active compounds present in EOs or phenolics could be alternatively based films containing the extracts (green tea, grapeseed) can be attrib-
utilized by microencapsulation or nanoencapsulation techniques [127]. uted to the slow release of these active components from the film [140].
Encapsulation is also referred to as ‘Delivery systems’ [128]. These deliv- The water barrier properties of these films were improved by the addi-
ery systems not only ensure the controlled release of these active com- tion of oleic acid and soybean oil. Also, the addition of lipid compounds
ponents from the coating formulations but also, protects them from produced a heterogeneous surface in the alginate-based films, which
oxidation. Further, they eliminate the undesirable taste and prolong further increased with the addition of green tea and grape seed extracts.
the shelf-life of the food products that contain them [129]. Droplet This might be due to the formation of hydrogen bonds between pheno-
size below 100 nm constitutes the nano-emulsions, contributing to lic compounds and the lipid components present in the alginate films,
312 M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320

causing limited interactions of free -OH groups with water [141]. The alginate. These coatings extended the shelf life of refrigerated cut apples
transparency of these films also reduced as a result of the heteroge- by inactivating E. coli [143,144].
neous surface, causing scattering of light. In addition, absorption of
light at low wavelength by the phenolic compounds causes a further re- 4.3. Enhancing the functionality of the alginate-based edible coating/films
duction in the light transmittance by these films [140]. Tea polyphenols using nano-forms and other potential substances
were integrated into alginate-based edible coatings and applied on ju-
jube fruits. The coated fruits displayed reduced malonaldehyde content, Sodium alginate, a non-toxic, biodegradable and abundantly avail-
electrolyte leakage, respiration rate and retained antioxidant activity, able inexpensive biopolymer can effectively be used for micro- or
total phenolic content, ascorbic acid content and juice quality under nano-encapsulation. It can function efficiently in the presence of diva-
normal temperature [142]. Therefore, phenolic compounds can play lent ions and result in gel formations [153]. The encapsulation efficiency
an important role in the preservation of fruits and vegetables when increases with the use of multiple polymers or the formation of multiple
used as an additive in the alginate-based edible coatings. layers as it enhances the physical properties of the microcapsules. The
nano-coatings based on sodium alginate have also been used in fruit
4.2. Enhancing the functionality of the alginate-based edible coating/films and vegetable preservation. Studies have shown to extend the shelf-
using essential oils (EOs) life of fresh-cut carrots and shiitake mushroom with the help of nano-
based formulations [131,154]. Emamifar and Bavaisi [155] demon-
EOs are the secondary metabolites derived from aromatic plants, strated that the addition of ZnO NPs in sodium alginate-based nano-
which are capable of interacting with the bacterial membranes and coatings enhanced the shelf-life of strawberries stored at 1 °C by
hence serve as antimicrobial agents [143,144]. Addition of EOs into chi- preventing the weight loss, texture quality, ascorbic acid, total phenols
tosan based edible coatings resulted in synergistic action of chitosan and and total anthocyanins content. 1.5% sodium alginate with (1.25 g/L)
EOs as discussed in the previous sections. However, sodium alginate nano-ZnO proved to be the most effective nano-coating against micro-
does not have an inherent antimicrobial activity, and the addition of bial load and possessed high antioxidant activity and sensory attributes,
EOs into alginate-based coatings or films enhanced its antimicrobial ac- and low peroxidase activity. Similarly, nano-emulsion (b500 nm) made
tivity and was confirmed by several studies [135,145,146]. from 2% sodium alginate and 2% citral or 1.2% lemongrass essential oil
Chiabrando and Giacalone [147] investigated the combined effect of demonstrated uniform particle size and high stability. Both the nano-
2% alginate coating integrated with 1% calcium ascorbate, 0.3% cinna- emulsions had antimicrobial action, prevented internal browning, re-
mon bark essential oil and 0.3% rosemary essential oil in preserving stored colour and firmness which resulted in high sensory scores in
the quality of fresh-cut apples. The authors found that the addition of pear stored at 0 °C for six months [156]. ZnO NPs demonstrated a high
cinnamon essential oil into alginate based coatings was more effective optical clarity to the nano-emulsions, which is important in maintaining
than rosemary oil in controlling the weight loss, browning, respiration colour by retarding hue values in the coated pear. The firmness was
rate, and enzymatic activities of PPO and POD. de S. Gomes et al. [148] highest in case of lemongrass enriched sodium alginate-ZnO NPs
showed the inhibitory effect of alginate based antimicrobial coating for- based coated fruits. Integration of highly concentrated citral EOs caused
mulations integrated with 0.2% lemon EOs and 0.1% orange EOs against softening of the fruits which may be due to a reduction in the moisture
bacterial, yeast and mold growth in red raspberries. They also did not loss properties and also penetration of citral EO into the cell membranes
observe any change in the inherent odour or flavour of the fruits. Rasp- [146].
berries coated with 2% alginate coating solution enriched with 0.15% cit- Arroyo et al. [79] showed that the presence of 1% ZnO NPs in alginate
ral and 0.1% eugenol remained fresh when stored at 5 °C for 7 days. and chitosan composite coatings inhibited the growth of Phyllosticta
These coatings preserved the quality of raspberries such as TSS, weight psidicola, a causative agent of rot in guavas and retarded the ripening
and antioxidant properties by reducing microbial spoilage due to yeasts, process and extended the shelf-life of up to 20 days. The coatings con-
mold and aerobic mesophiles. Moreover, these coatings did not alter the taining 90% alginate, 10% chitosan and 1% ZnO NPs did not allow inter-
sensory characteristics of raspberries. action between alginate and ZnO NPs as the alginate polymer shows
Zhu et al. [149] reported an improvement in the physico-chemical an ordered sequence in the presence of divalent metals [157]. In con-
attributes of Pholiota nameko mushroom coated with 5% alginate trast, 100% chitosan-1% ZnO NPs; 90% chitosan-10% alginate-1% ZnO
based coating enriched with 1% thyme oil and 0.04% nisin during a stor- NPs showed the lowest weight loss in guavas during storage due to syn-
age period of 9 days at 20 °C. The application of EOs resulted in a consid- ergistic action of chitosan and ZnO NPs. In another study, the authors re-
erable reduction in browning, malondialdehyde content, enzymatic ported, improved performance of 1% alginate based nano-emulsions
activities of PPO, POD and cellulase and maintained the TSS and protein consisting of 1% lemongrass oil through ultrasound treatment. The
content, ascorbic acid and high bacteriostatic activity. Hence, it can be study revealed a decrease in the viscosity and increase in the stability
stated that sodium alginate coatings or films exhibit poor antimicrobial of the nano-emulsions with the ultrasonic treatment of 100 nm for
activities, but they demonstrate superior antimicrobial activities when 180 s by forming small droplet size (4.3 ± 0.18 nm) and also improved
integrated with EOs. Superior quality film forming potential of sodium transparency of lemongrass oil in the nano-emulsion [158]. Different
alginate can be exploited with the additions of such EOs, which would combinations of EOs (cinnamaldehyde) and bacteriophages (obligate
be more resourceful and cost effective when compared to the other bacterial parasites) were integrated into food coating films made by so-
polysaccharide-based coatings. Alginate-based coatings were incorpo- dium alginate emulsion to impart antimicrobial activity to these films
rated with EOs (citral and eugenol) and applied on raspberries. The against Escherichia coli and Salmonella enterica to prevent food contam-
coated berries displayed enhanced shelf-life, sensory attributes and re- ination [159]. These films exhibited superior bactericidal activities due
duced microbial growth [151]. Fresh-cut cantaloupe was coated with to the synergistic effect of EOs and bacteriophages and also displayed
thyme oil enriched alginate-based edible coating. The coated fruits lower values of moisture content due to the blockage of water
retained their colour and weight, delayed respiration rate and reduced interacting groups on alginate coatings by cinnamaldehyde. A similar
growth of food spoiling microbes like Escherichia coli, Salmonella study was conducted to integrate bacteriophage ϕIBB-PF7A into films
Typhimurium, Staphylococcus aureus and Listeria monocytogenes [152]. made by sodium alginate crosslinked with calcium chloride to impede
Edible films made from sodium alginate integrated with lemongrass, the poultry meat spoiling bacteria Pseudomonas fluorescens. These
thyme, sage EO nanoemulsion. These films displayed superior antimi- films had strong antibacterial activities which increased the shelf-life
crobial activity, mechanical flexibility, resistance to water vapour and of meat by preventing the bacterial growth [160].
increased transparency [72]. In another study nanoemulsion of lemon- Apart from phenolics, essential oils and nano-forms, a number of
grass EO was amalgamated with edible coatings made of sodium other ways for enhancing the functionality of the alginate-based edible
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 313

coatings are extensively studied by a number of researchers. Xu et al. concluded that not only utilizing phenolics, EOs and nano-forms into so-
[10] reported that incorporation of cyclolipopeptides (0–3%) produced dium alginate based coating formulations bear an impact on its func-
by Bacillus subtilis into 3% sodium alginate coating solutions proved to tional properties, but also, using other bioactive additives such as
be an effective antifungal agent against Aspergillus niger besides main- cyclolipopeptides also show similar positive effects in extending the
taining the physical attributes such as firmness, colour and the respira- shelf-life of fruits and vegetables.
tion rate of berries. Peretto et al. [161] demonstrated the use of An overview of the mechanism of synergistic effect of alginate/chito-
electronic spraying technique using 2% alginate coating enriched with san matrix and functional additives (phenolics, essential oils, nano-
1% carvacrol and 1.4% methyl cinnamate to extend the shelf-life of forms) can be seen in Fig. 3.
strawberries up to 13 days. The authors reported retention of physical
parameters such as weight loss, firmness and colour of strawberries. 5. Regulatory and safety of the chitosan and alginate-based edible
Further, it has been reported that using 20 mL oxidized ferulic acid as coatings/films before and after enhancing the functionality
a crosslinking agent in developing an active bilayer composed of
(0–2 g in 80 mL of acetic acid) chitosan and (0–2 g in 100 mL) sodium Any substance is considered edible if they are of food-grade, non-
alginate produced films with a smoother, more uniform appearance, poisonous and made under high hygienic standards [162]. The safe
better thermal stability, mechanical and optical properties. Also, cherry use of edible coatings and films materials is nowadays critical, consider-
tomatoes coated with this cross-linked bilayer of chitosan-alginate film ing their impact on the health of consumers. In view of this, to maintain
enriched with citric acid successfully regulated the ascorbate- the safety and acceptability, regulatory guidelines for the use of biopoly-
glutathione cycle and improved the antioxidant levels contributing to mers and functional additives have been formulated [162]. GRAS mate-
extended postharvest life of cherry tomatoes [150]. Thus, it can be rials can be used in the formulation of edible films/coatings within the

Fig. 3. An overview of the mechanism of the synergistic effect of alginate/chitosan matrix and functional additives (phenolics, essential oils, nano-forms). (A) Acting as an oxygen barrier.
(B) Acting as an antioxidant. (C) Acting as anti-microbial. The overall action of (A), (B), and (C) results in prolonged shelf-life of fruits and vegetables.
314 M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320

Table 1
Enhancing the functionality of chitosan-based edible coatings/films using phenolics, nano-forms and other potential substances.

Chitosan Fruit or Functional material used and its concentration Type of Potential advantages and key findings of study Reference
based edible vegetable functionality
coating/film preserved introduced
composition

Enhancing functionality of chitosan-based edible coatings/films using phenolics


CH (2%) Apple Olive wastes extract (olive leaves extract (1%), olive Antioxidant ↔ Weight loss, TPC, TFC, TANC, TCAC, TCC, & TAC [102]
pomace extracts (2%))
CH (1%) Orange WPPE, MPPE & BCA-Wickerhamomyces anomalus Antifungal × Penicillium digitatum, W. anomalus BS91 (MPPE- [103]
(108 cells/mL) modified coatings)
↓ Disease incidence by 49% at 0.361 g dry
WPPE/mL
CH-peony extract Strawberries – Antimicrobial ↔ Weight loss & AOC [163]
(0.25%) + AG ↑ TAC & TPC
(1%) × Pichia kluyvery, Candida pulcherrima & Candida
valida
CHN (44.6% of Bell pepper Byrsonima crassifolia extract (55%) Antimicrobial, ↓ Alternaria alternate & microbial activity [117]
0.05%) antifungal ↑ AOC
↔ Weight loss, colour, phenolic & carotenoids
content.
CH (2%) Blueberries Blueberry leaf extracts (8% or 12%) Antimicrobial, ↔ Weight loss, retained firmness, TPC [88]
antioxidant ↓ Decay rate
↑ RSA
× E. coli, S. Typhimurium, L. monocytogene, S.
aureus and fungi
CH (2%) Apple Banana peels extract (4%) Antioxidant, ↓ Respiration rate [100]
cross-linking ↔ Weight loss, firmness, TSS & TAC

Enhancing functionality of chitosan-based edible coatings/films using essential oils


CH (2.5, 5, 7.5 and Papaya Mentha essential oils (0.15–2.5 μL/mL) Antifungal × C. gloeosporioides and C. brevisporum at 7.5 and [186]
10 mg/mL) 10 mg/mL chitosan
↓ Development of anthracnose
CH-IvEO (1:0.8) – Illicium verum Hook essential oil Antifungal, × Aspergillus flavus, aflatoxin B1 [112]
anti-aflatoxigenic,
antioxidant
CH (2%), SA (2%) Apple fruit Cinnamon essential oil (1%) Antifungal, × Penicillium expansion [101]
antibacterial
CH Mangaba Myrcia ovata Antimicrobial ↓ Total aerobic mesophilic bacteria, mold & yeast [15]
(0.5%) + cassava Cambessedes essential oil (1.25%) counts
starch (0.5%) × B. cereus, B. subtilis, P. aeruginosa and S. aureus

Enhancing the functionality of the chitosan-based edible coating/films using nano-forms and other potential substances
CH (2%) Fresh-cut Trans-cinnamaldehyde (500 mg/L) Free radical ↑ Firmness, colour, TSS, VCC & TCAC [164]
melons scavenger & ↓ Antioxidant enzyme activity, cell wall hydrolytic
enzyme inhibitor enzyme activity (GPOD, PPO), lipid peroxidation
degree, electrolyte leakage levels, respiration rate,
O2-dependent processes, hydrogen peroxide
radical levels
Shelf life up to 15 days
CH (1.5%) Strawberries PE (1%), GE (1%), NS (1%), NT (1%) Antimicrobial ↓ O2 consumption, water activity, mesophilic [165]
bacteria, yeast & mold & microbial load
↔ pH, TSS, texture
↑ Shelf life up to 30 days
CH (1%) Sugar snap Gibberellic acid (1 mmol/L) Antioxidant ↓ TA, chilling injury, POD activity, pod decay [166]
peas ↑ TCAC
↔ TCC, VCC, TPC, protein, weight loss
CHN (0.05%) Cucumber Cinnamon essential oil (0.1%), Antifungal × Fusarium solani, yeasts & fungi [123]
trans-cinnamaldehyde (0.05%) ↔ TCC, weight loss.
CH (1%) Tomato BW (0.1%) + LO (0.1%); OA (1%) + LO (1%) Antibacterial, × R. stolonifer and E. coli DH5a (CH + BW + LEO) [57]
BW (0.1%) + TO (1%) antifungal × R. stolonifer growth (CH + OA + LEO)
× E. coli DH5α (CH + BW + TO)
CH (1%), CMCH & Cucumber, MLT (25, 50 & 100 mg/L chitosan solution) Antioxidant, ↑ Antioxidant activity in CH films and in [167]
CMC (2.5%) broccoli antimicrobial CMCH-CMC assembly
melon Antimicrobial activities of CMLLA against
microorganisms was: E. Coli b L.
monocytogenes b S. Enteritidis
↑ Sensory attributes
CH/PVA (1 g of CH ‘Superior Ascorbic acid (8.2 mM) Antioxidant ↓ Water loss, berry [168]
in a 2% acetic seedless’ Shattering, rate of deterioration, membrane
acid; 1% PVA) grapes damage, cell wall degrading enzymatic activity
(CEL, PG & XLN) & rachis browning
↔ Colour, TSS, TA, TPC, TFC & SSC/TA ratio content.
CH/PVP (1% CH, 1% Guava Salicylic acid (2 mM) Antioxidant ↓ Browning, cell wall degradation enzymes [169]
PVP) activities CEL, LOX, and PT, water loss, hue value,
TSS/TA ratio
↔ TSS, TA, TCC, TAC, firmness
CH (1.5%) Navel Cinnamaldehyde (1.5%) Antioxidant ↓ Decay & senescence [170]
orange ↔ Weight loss, TSS, TA, VCC
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 315

Table 1 (continued)

Chitosan Fruit or Functional material used and its concentration Type of Potential advantages and key findings of study Reference
based edible vegetable functionality
coating/film preserved introduced
composition

↑ Activities of antioxidant enzymes –POD, PPO,


CAT, SOD
CH (1%) Grape CH-g- salicylic acid (1.03%) (ratio of CH to salicylic Antifungal, ↑ PAL, chitinase, & β-1, 3-glucanase activities [125]
acid of 1–0.35) antioxidant ↔ TPC, TSS, TA & sensory attributes
× Botrytis cinerea
↓ Decay incidence, respiration rate & weight loss
CH (1.5%) Tangerine Montmorillonite (1%) Antioxidant, ↓ Decay rate & weight loss [171]
fruits antimicrobial ↔ TSS & TA
CH (0.01% in 1% Mango Sodium laurate modified nano-TiO2 (0.01 g, 0.03 g Antioxidant ↓ Decay & respiration rate [122]
aqueous acetic in 1 g glycerin, followed by the sequential addition ↔ Firmness, TSS, TPC & TFC
acid solution) of 100 mL 1% aqueous acetic acid solution, after ↑ Activities of antioxidant enzymes – POD, PPO
which 1 g chitosan powder was added)
CH (1.5 g/ L) Fresh-cut Ag-chitosan nanocomposites (Ratio 1:40) (100 mg Antimicrobial, ↑ Sensory attributes [121]
melon CH, 37.5 mg of AgNO3) antioxidant ↓ Respiration, ethylene production & microbial
load
↔ VCC
CH (1%) + SA Chinese Nano-silica (0.05%) Antioxidant ↓ PPO activity & ↓ browning reaction [172]
(0.5%) coating winter ↑ Antioxidant enzyme activities (SOD, POD, PAL)
jujube ↔ Weight loss, TSS, TAC, TCC, TANC
↑ Shelf life up to one month
Nanoalminate (0.2% Tomato Flourensia cernua extract (5000 mg/ L) Antioxidant, ↔ Weight loss, firmness & colour [116]
SA, 0.6% CH) Antimicrobial ↓ Microbial growth, gas exchange & ethylene
production.

PPO - polyphenol oxidase, SOD – superoxide dismutase, POD - peroxidase, PAL - phenylalanine ammonia lyase, TSS - total soluble solids, TAC - total ascorbic content, TCC - total chlorophyll
content, TANC - total anthocyanin content, AOC - antioxidant content/capacity, TCAC - total carotenoids content, RSA - radical scavenging activity, CH - chitosan, SA - sodium alginate, CHN
- nano-chitosan, AG - agar, WPPE - water pomegranate peel extract, MPPE - methanol pomegranate peel extract, BCA - biocontrol agent, VCC - vitamin C content, GPOD - guaiacol perox-
idase, CMCH - carboxymethyl chitosan, CMC - carboxymethylcellulose, MLT - melatonin, BW - bee wax, LEO - lime essential oil, OA - oleic acid, TO - thyme essential oil, CH/PVA – active
chitosan & polyvinyl alcohol blend, TSS/TA - ripening index, CEL - cellulase, PG – polygalacturonase, XLN - xylanase, LOX - lipoxygenase, PT - pectinase, PVP - poly-vinyl-pyrrolidine, PE -
pomegranate extract, GE - grape seed extract, NS - nisin, NT - natamycin, × - inhibition, ↔ - retention, ↑ - increase, ↓ - decrease.

limits specified by the FDA [185]. Alginate is considered as GRAS and can to commercialize these innovative films and coatings at the industrial
be used as a safe biomaterial for preparation of the coatings/films for the level.
preservation of fruits and vegetables. On the other hand, chitosan also
comes under GRAS for its application in agriculture and medical field, 6. Conclusion
but it has not yet been approved as an antimicrobial food additive [46].
The addition of functional compounds such as phenolics and EOs are The current review presents an extensive investigation of functional
also regarded as GRAS and can be used for enhancing the functionality additives such as phenolic compounds, EOs, nano-forms and also other
of chitosan and alginate-based films/coatings as per the FDA regulation, functional compounds which are added into the polysaccharide-based
2019. The fabricated films and coatings have higher antimicrobial and edible coatings i.e. chitosan and alginate. It is well demonstrated by
antioxidant properties without affecting the safety. Other category of the researchers that these additives play an important role in extending
aforementioned functional additives are inorganic NPs which have the shelf-life and also maintaining the nutrient profile of numerous
been vastly studied for their application in active coating and films but fruits and vegetables. These functional molecules play a synergistic
there are very few studies in real food systems [46]. Currently, there is role along with the chitosan and alginate-based edible coating and re-
a relatively poor understanding of the fate of NPs in the gastrointestinal tain the moisture, antioxidant potential, enhance the activity of antiox-
tract and also the toxicity of a majority of NPs is unknown. Hence, it is idant enzymes, reduces the activity of browning enzymes and imparts
not possible to make a generalised statement about the safety aspects antimicrobial properties in fresh fruits and vegetables. All these proper-
NPs in the edible films and coating system. ties help in sustaining the appearance, lowering the senescence and ex-
EOs and phenolic compounds have been extensively researched for tends the life of the coated fruits and vegetables. Besides having a
their possible application in the development of the functionalised edi- number of advantages these additives, EOs and phenolics sometimes
ble films and coatings. Many studies have also demonstrated the use of diffuse into the food products imparting undesirable flavour and
these functional additives in edible films and coatings for the preserva- aroma owing to the presence of a mixture of volatile and non-volatile
tion of various fruits and vegetables at laboratory level (Tables 1 and 2) components in them, limiting their application. Recent developments
without any real application and commercialization at industrial level. in the field of edible films/coatings utilizing micro- and nano-
Modification in the organoleptic profile, physio-chemical properties encapsulation techniques can enhance the compatibility of functional
and effectiveness of functionalised films and coatings in a real situation additives and assist in overcoming such issues. Promotion of these edi-
are the various concerns which limit the application of EOs and phenolic ble coatings/films needs to be increased among the consumers so to
compounds. To overcome this problem, EOs and phenolic compounds broaden and diversify their use in fruits and vegetable preservation.
can be selectively used with the compatible food matrices with respect
to taste and flavour. Further, tasteless and odourless derivatives can be CRediT author statement
developed so is to make the final product sensorially inert. The concen-
tration of functional additives must be optimized as they may act as pro- M. Sneha Nair, Maharishi Tomar, Manoj Kumar: Writing - original
oxidant, which can ultimately result in DNA damage and mutagenesis. draft. Manoj Kumar, Maharishi Tomar, Sneh Punia, Wirginia Kukula-
Further, the study of the potential toxicity of food-grade NPs in living Kuch: Writing - review & editing; Revision of the manuscript. All au-
model needs to be explored and confirmed with standardized methods thors discussed the review and contributed to the final manuscript.
316 M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320

Table 2
Enhancing the functionality of alginate-based edible coatings/films using phenolics, nano-forms and other potential substances.

Alginate based edible Fruit or Functional material used Type of Potential advantages and key findings Reference
coating/film composition vegetable and its concentration functionality of study
preserved introduced

Enhancing functionality of alginate-based edible coatings/films using phenolics


SA (2%) Table grapes Vanillin (1%) Antifungal, ↔ TSS, TA, sensory quality, LAC, TPC & AOA [173]
antioxidant
activity
SA (1%) Peaches Rhubarb extract (50 mL Antifungal, ↓ Respiration rate & MDC [27]
in 1% coating solution) antioxidant ↔ Weight loss, firmness, TSS and sensory
activity attributes
↓ PPO activity
× Penicillium expansum
SA (1%) Chinese 0.25 g/L of sunflower oil, 1 g/L tea Antioxidant ↓ Respiration rate, electrolyte leakage & MDC [142]
winter jujube polyphenols ↔ TAC, TCC & TPC
↑ Antioxidant enzyme activity (SOD, POD & CAT)
SFA/CaCl2 (SFA-2.5%) – Black chokeberry Antioxidant ↑ TPC & AOA [174]
extract (1%) ↑ Elongation break
↓ Tensile strength
SA + Konjae glucomannan and Goji Lotus leaf extract (0.2%) Antioxidant ↓ Decay rate & MDC [175]
starch (ratio 2:3:3) ↔ TSS, TA, TAC, antioxidant enzyme
activity (SOD, POD, CAT), weight loss
↑ Shelf life up to 4 days
CH-SA-LDPE + cold plasma – Summer savory extract Antioxidant ↑ Tensile strength [55]
treatment ↓ Physical and mechanical properties
↑ Antioxidant properties
G-SA (G-4%, SA-3%) – Tea polyphenol (2%) Antioxidant ↑ TPC, AOA, mechanical & physical properties (TS, [61]
contact
angle, and cross-linking degree, smooth and
continuous surface, dense internal structure)
↓ EB & WVP, light transmittance
SA-PE (1:1) (3%) – Carvacrol (1 mL/100 mL of SA-PE Antioxidant, ↑ Encapsulation efficiency & stability, AOA [176]
blend solution) antimicrobial × E. coli at 0.25 mg/mL
SA (1%) – Green tea extract (1:0.5) & grape Antiviral × Murine norovirus & hepatitis A virus [139]
seed extract (1:0.75) ↑ Water barrier efficiency
↑ Efficiency of green tea extracts added SA than
grape seed extract added SA
SA (2%) – Acacia lignin/SA (10:90, 20:80 & Antioxidant, ↓ WS & TS, cytotoxicity [177]
30:70) antimicrobial ↑ Light barrier, antimicrobial properties
Optimum physico-chemical properties

Enhancing functionality of alginate-based edible coatings/films using essential oils


SA (2%) Raspberry Eugenol (0.1%) & citral (0.15%) Antimicrobial ↑ Sensory attributes [151]
↓ Microbial spoilage
↑ Shelf life by 7 days at 0.5 °C
SA (1.29%) Fresh-cut Thyme oil (0.05, 0.65%) Antibacterial × Listeria monocytogenes, Staphylococcus aureus, [152]
cantaloupe Salmonella Typhimurium, & Escherichia coli
O157:H7 at 0.65%
↔ Colour & weight loss,
↓ Delayed respiration at 0.05%
SA (2%) Fresh-cut 1% thyme & oregano essential oils Antimicrobial ↔ Weight loss, pH & sensory attributes [178]
papaya ↓ Respiration rate & microbial load
SA (2%) Cantaloupes Soybean oil (0.5%) & Cinnamon Antibacterial, × S. enterica, E. coli O157:H7 and L. [126]
bark oil (2%) antimicrobial, Monocytogenes, yeasts & molds
fungicidal ↔ Firmness & colour
SA (3%) Apple & pear Cinnamon oil (0.3 & 0.9%) Antifungal ↓ Aspergillus carbonarius growth & ochratoxin A [179]
production
SA (1%) – Lemongrass essential oil (0.5%) Antioxidant, ↑ Physical properties & AOA with large droplet size [180]
antimicrobial × B. cinerea at 75% & 11% RH, 4 °C; E. coli at 11%
RH, 20 °C
AGA-SA-CAR (each polymer – Zataria essential oil (100 mg/g of Antioxidant ↓ pH, conductivity, zeta-potential & particle size, [179]
1 g/80 mL distilled water) polymer) TS, EM
↑ Viscosity, AOA, EB & thermal stability

Enhancing the functionality of the alginate-based edible coating/films using nano-forms and other potential substances
SA (1%) Strawberries D-limonene (50 μM) liposomes Antioxidant ↓ pH, respiration rates [181]
↑ TANC
SA (3%) – TH-EO, SG-EO, LG-EO Antimicrobial ↑ Transparency, water vapour resistance & [72]
Nano-emulsion & films (1% each) flexibility
(SG-EO nanoemulsions)
× E. coli by TH-EO
Nano-emulsion Okra ATNE & ASNE (0.4%) Antifungal ↔ Physiological weight loss, firmness, & green [182]
colour
× Penicillium chrysogenum & Aspergillus flavus
SA-gelatin nanocomposite beads Potato Pseudomonas fluorescens (VUPF5 Antimicrobial ↓ Fusarium solani disease incidence [183]
(SA-2%; gelatin-1.5%) and T17-4)
SA-CL (SA-3%) Berries CL (3%) from Bacillus Antifungal ↓ Total fungal count, respiration [10]
subtilis ↓ Mechanical properties (TS and ES), WVP, high
M.S. Nair et al. / International Journal of Biological Macromolecules 164 (2020) 304–320 317

Table 2 (continued)

Alginate based edible Fruit or Functional material used Type of Potential advantages and key findings Reference
coating/film composition vegetable and its concentration functionality of study
preserved introduced

WS
↔ Firmness
× Aspergillus niger
SA-MMT (SA-1%, MMT-3%) – Origanum majorana Antimicrobial ↓ WS & TS [184]
essential oil (1.5%) ↑ WVP, surface hydrophobicity
× E. coli, L. monocytogenes, Bacillus cereus, & S.
aureus

TSS - total soluble solids, TA - titratable acidity, sensory quality, LAC - lactic acid content, TPC - total phenolic content, AOA - antioxidant activity, MDC - malonaldehyde content, PPO -
polyphenol oxidase, PPO - polyphenol oxidase, SOD – superoxide dismutase, POD - peroxidase, CAT - catalase, TAC - total ascorbic content, TCC - total chlorophyll content, ATNE - alginate
Tween-20 nano-emulsion, alginate Sapindus nano-emulsion, SA - sodium alginate, TANC - total anthocyanin content, SFA - alginate extracted from Sargassum fulvellum, CH-SA-LDPE - chi-
tosan, alginate low-density polyethylene bilayer films, SA-CL - sodium alginate-cyclolipopeptides composite, WVP - water vapour permeability, WS - water solubility, TS - tensile strength,
ES - elongation strength, EM - elastic modulus, EB - elongation at break, AGA-SA-CAR – agar, sodium alginate & carageenan dispersion, TH-EO - thyme essential oil, SG-EO - sage essential
oil, LG-EO - lemongrass essential oil, G-SA - gelatin & sodium alginate films, SA-PE - sodium alginate & pectin, SA-MMT - sodium alginate-montmorillonite composite films, × - Inhibition,
↔ - retention, ↑ - Increase, ↓ - decrease.

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