Review of Chitosan Coating

Materials Science and Engineering C 33 (2013) 18191841
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Materials Science and Engineering C

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Review
Chitosan based edible lms and coatings: A review

Maher Z. Elsabee a,, Entsar S. Abdou b, c
a b c
Chemistry Department, Faculty of Science, Cairo University, Giza 12613, Egypt Food Packaging and Engineering Department, Food Technology Research Institute, Agriculture Research Center, Giza 12613, Egypt Chemistry Department, Faculty of Science and Humanities, Salman bin Abdulaziz University, Hotet Bany Tamim 11941, Saudi Arabia
a r t i c l e
i n f o
a b s t r a c t
Chitosan is a biodegradable biocompatible polymer derived from natural renewable resources with numerous applications in various elds, and one of which is the area of edible lms and coatings. Chitosan has antibacterial and antifungal properties which qualify it for food protection, however, its weak mechanical properties, gas and water vapor permeability limit its uses. This review discusses the application of chitosan and its blends with other natural polymers such as starch and other ingredients for example essential oils, and clay in the eld of edible lms for food protection. The mechanical behavior and the gas and water vapor permeability of the lms are also discussed. References dealing with the antimicrobial behavior of these lms and their impact on food protection are explored. 2013 Elsevier B.V. All rights reserved.
Article history: Received 9 August 2012 Received in revised form 11 December 2012 Accepted 9 January 2013 Available online 18 January 2013 Keywords: Chitosan Blends Essential oils Nanoclay Water vapor and gas permeability Antibacterial and antifungal properties
Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . Chitin and chitosan . . . . . . . . . . . . . . . . . 2.1. Blending . . . . . . . . . . . . . . . . . . . 2.1.1. Blending of chitosan with starch . . . 2.1.2. Chitosan and gelatin based edible lms 2.1.3. Chitosan with alginate and carageenan 3. Chitosan/essential oil lms . . . . . . . . . . . . . . 4. Chitosan and clay . . . . . . . . . . . . . . . . . . 5. Gas permeation properties of edible coatings . . . . . 6. Effect of electric eld on lm formation . . . . . . . . 7. Antibacterial activity of chitosan and chitosan blends . 8. Increasing the shelf life of foods . . . . . . . . . . . 9. Conclusion . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1820 1820 1820 1821 1826 1827 1827 1830 1831 1833 1833 1837 1839 1839
Abbreviations: DD, degrees of deacetylation; EMC%, Equilibrium moisture content; CH, high molecular weight chitosan; CM, medium molecular weight chitosan; CL, low molecular weight chitosan; MD, machine direction; TD, transverse direction; TS, tensile strength; CS, chitosan; Ec, elastic modulus; E, Elongation at the break; BCC, bacterial cellulosechitosan; BC, bacterial cellulose; FS, Film solubility; MW, molecular weight; WVP, water vapor permeability; M, (1 4)-linked--D-mannuronate; G, (1 4)-linked--L-guluronate; CEO, cinnamon essential oil; TVC, total viable counts; BO, Bergamot essential oil; FFD, Film-forming dispersions; TTO, tea tree oil; PCL, poly-caprolactone; PBS, poly(butylene succinate); PLA, poly(lactic acid); PBTA, poly(butylene terephthalate adipate); PBSA, poly(butylene succinate adipate); WVT, Water vapor transmission rate; MC, methylcellulose; AFM, Atomic force microscopy; GO, Garlic oil; PS, potassium sorbate; N, nisin; AM, antimicrobial; LPSSD, low-pressure superheated steam drying; PDA, potato dextrose agar; CWC, Chinese water chestnut; ACS, acid-soluble chitosan; WCS, water-soluble chitosan; PVDC, polyvinyl dichloride; TVC, total viable counts; MAP, modied atmosphere packaging; CMC, carboxymethyl-cellulose. Corresponding author. Tel.: +20 26352316, +20 1006680474 (mobile). E-mail address: mzelsabee@yahoo.com (M.Z. Elsabee). 0928-4931/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.msec.2013.01.010
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M.Z. Elsabee, E.S. Abdou / Materials Science and Engineering C 33 (2013) 18191841
1. Introduction Recently, considerable research has been conducted to develop and apply bio-based polymers made from a variety of agricultural commodities and/or of food waste products [1]. This increased interest was intensied due to concerns about limited natural resources of the fossil fuel reserve and the environmental impact caused by the use of nonbiodegradable plastic-based packaging materials [2]. Such biopolymers include starches, cellulose derivatives, chitosan/chitin, gums, proteins (animal or plant-based) and lipids [3]. These materials offer the possibility of obtaining thin lms and coatings to cover fresh or processed foods to extend their shelf life. Edible lms and coatings offer extra advantages such as edibility, biocompatibility, esthetic appearance, barrier to gasses properties, non-toxicity, non-polluting and its low cost [4]. In addition, biolms and coatings, by themselves or acting as carriers of foods additives (i.e.: antioxidants, antimicrobials), have been particularly considered in food preservation due to their ability to extend the shelf life [5]. Seafood products are more perishable than chicken or red meat as they contain relatively large quantities of free amino acids and volatile nitrogenous bases compared with other meats [5]. During storage, sh quality is quickly reduced as chemical and enzymatic reactions lead to the initial loss of freshness, while microbial spoilage produces the end of the shelf life. The increasing demand for high quality fresh seafood has intensied the search for new methods and technologies for better sh preservation. One of the possibilities, not much explored, is the application of an edible lm or coating, in combination with other microbial stress factors, on the fresh sh muscle. Gomez-Estaca et al. [6] reported that a gelatinchitosan-based edible lm together with refrigeration and high pressure have lowered the microbial growth of cold-smoked sardine in comparison to uncoated samples. Over the past several decades, several biopolymers have received increased attention for their applications in chemical, biomedical, and food industries, [7]. For example, chitin suture is resorbable in human tissues from which chitosancollagen composites for an articial skin are commercially produced [8]. These polymers are not only biodegradable, but also edible. Another area of growing interest is the preparation of antimicrobial edible lms and coatings [2,9] where chitosan plays an important role due to its well-documented antimicrobial properties [10]. 2. Chitin and chitosan Chitin is an abundant naturally occurring biopolymer and is found in the exoskeleton of crustaceans, in fungal cell walls and in other biological materials. It is mainly poly(-(14)-2-acetamido-D-glucose), which is structurally identical to cellulose except that a secondary hydroxyl on the second carbon atom of the hexose repeat unit is replaced by an acetamide group. Chitosan is derived from chitin by deacetylation in an alkaline media [11]. Actually, chitosan is a copolymer consisting of -(14)-2-acetamido-D-glucose and -(14)-2-amino-D-glucose units with the latter usually exceeding 60%. Chitosan is described in terms of degree of deacetylation and average molecular weight and its importance resides in its antimicrobial properties in conjunction with its cationicity and lm-forming properties. The potential of chitosan to act as a food preservative of natural origin has been widely reported on the basis of in vitro trials as well as through direct application on real complex matrix foods [1217]. Chitosan is also an excellent lm forming material [18]. Chitosan lms have a selective permeability to gasses (CO2 and O2) and good mechanical properties. However, the fact that chitosan lms are highly permeable to water vapor limits their use as being an important drawback since an effective control of moisture transfer is a desirable property for most foods, especially in moist environments. Therefore, several strategies have been used to improve the physical properties of biopolymer based lms.
Among them, promising results in increasing the hydrophobicity have been obtained by addition of neutral lipids, fatty acids waxes [19,20] and clay [21] although often compromising their mechanical and chemical stability and/or of their organoleptic attributes. Moreover, various chemical and physical means have been demonstrated as good strategies to improve their mechanical properties, such as the addition of cross-linking agents, irradiation and ultrasonic treatments [22]. The antifungal and antimicrobial activities of chitosan are believed to originate from its polycationic nature [23]. The antimicrobial action of chitosan is hypothesized to be mediated by the electrostatic forces between the protonated amino group (NH2) in chitosan and the negative residues at cell surfaces [24]. The number of protonated amino groups (NH2) present in chitosan increases with increased degrees of deacetylation (DD) which inuences the antimicrobial activity [25]. Liu et al. (2004) [25] state that the bactericidal activity of chitosan is caused + by the electrostatic interaction between NH3 groups of chitosan and the phosphoryl groups of the phospholipid component of the cell membrane. However, it was found that water-soluble chitosan promoted the growth of Candida albicans even in acidic media whereas waterinsoluble chitosan exhibited inhibitory effect [26]. In addition, a strong interaction between microbial proteins and chitosan at very acidic pH values is low and adsorption of chitosan to Escherichia coli cells increased + strongly with increasing pH. This means that the protonated NH3 is not the predominant factor in the antibacterial capacity of chitosan. Park et al. suggested that the antimicrobial activity of chitosan is not proportional to its DD value [27]. As the water soluble chitosan was not efcient as antibacterial agent it is thus conceivable that chitosan molecules have the ability to interact with bacterial surface compounds, and is absorbed on surface of the cells. However, physiological pH in the cell is around neutral, so water-insoluble chitosan molecules can precipitate, and stack on the microbial cell surface, thereby forming an impervious layer around the cell and blocking the channels, which are crucial for living cells. Such a layer can be expected to prevent the transport of essential solutes and may also destabilize the cell wall beyond repair thereby causing severe leakage of cell constituents and ultimately cell death [26]. In support of this last idea, it was found that the cell membranes of Gram-negative and Gram-positive bacteria showed signicant morphological changes and shrinking after contact with chitosan treated cotton fabrics [28]. 2.1. Blending The functional properties of chitosan-based lms can be improved by combining them with other hydrocolloids [2931]. Chitosan/pectin laminated lms have been developed by the interaction of the cationic groups of chitosan with the anionic groups of pectin. A decrease in water vapor transmission rates (WVTRs) by combining chitosan with two thermally gelatinized corn starches has been observed [31]. An alternative way to improve the mechanical and physical properties of these biolms is by combining proteins (e.g. milk proteins, soy protein, collagen and gelatin) with polysaccharides (e.g. starches, alginates, cellulose and chitosan). Chitosangelatin blend lms have been shown to be homogeneous due to the good miscibility between both biopolymers [3234] leading to improved material properties of the blend lms as compared to those obtained from the pure polymers. This is explained by the formation of electrostatic interactions between the ammonium groups of the chitosan and the carboxylate groups of the gelatin. On the other hand, chitosan/soy protein blended membranes [33], are not completely miscible. The blended membranes became more brittle with increasing soy protein content, and showed a rougher surface morphology, this is probably related to phase separation among blend components. Chitosan/sodium caseinate lms have also been studied; in this case no phase separation was observed due to the complexation of the two polymers within the blend lm matrix [34]. Some polysaccharidewhey protein lms have also been prepared and characterized [35]. Also, the addition of Pullulan to a whey protein
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lm has shown to decrease water vapor and oxygen permeability, although these barrier properties got worse as the amount of polysaccharide increased [36]. Chitosanwhey protein lms have been prepared at pH 6 with different protein concentrations, in the absence or presence of transglutaminase as a cross-linking agent [37]. The chitosan was the main lm component and its amount was kept constant, the protein was from a spray dried whey product still rich in lactose and the amount of whey protein did not exceed the proportion of 1:9 (protein:chitosan) in the nal lms. In more recent work [2], lms of chitosanwhey protein blend with a high amount of protein has been prepared in order to obtain a blend with new functionality out of the interaction of the cationic polyelectrolyte chitosan with protein. The study was aimed also to prepare edible lm-forming material with anti-microbial properties. 2.1.1. Blending of chitosan with starch The main differences between starch and chitosan are the glucoside linkage: (1, 4) for starch and (1, 4) for chitosan and, the hydroxyl group of the second carbon is replaced by the amine group which appears acetylated in the case of the natural polymer chitin. Fernandez et al. [38] studied the physical stability and moisture sorption of aqueous chitosanamylase starch lms plasticized with polyols. They used high, medium and low molecular weight chitosan with amylose-rich corn starch as a co-lm former in the presence of glycerol and i-erythritol. In comparison to regular corn starch which contains approximately 28% amylose, Hylon VII is a corn hybrid containing approximately 70% amylose. Since amylose is a linear polymer, it can closely align or associate through hydrogen bonding. This characteristic of amylose is primarily responsible for the gelling and lm-forming ability of starches. Since Hylon VII contains more than twice as much amylose as regular corn starch it can form more rigid gels and contribute to the formation of stronger and tougher lms. ChitosanHylon VII solutions plasticized with glycerol or erythritol were prepared in a high-pressure reactor equipped with a blade mixer. The steady-state moisture in the starting materials was measured after 9 days of storage of the samples at different relative humidity. As seen in Fig. 1A, the moisture increase of low molecular weight chitosan was lower than that of high and medium molecular weight chitosan at a relative humidity of 95%. The moisture increase of Hylon VII was lower than that of other starting materials from relative humidity of 5295%. The storage of the erythritol at a high humidity resulted in a signicant increase in water uptake, causing a liquefaction of the substance even higher than that of the chitosan. Starch and chitosan are hydrophilic and retain a considerable amount of water which depends on the relative humidity. At least in chitosan, there exist three predominant absorption sites such as the hydroxyl group, the amino group, and the polymer chain end. The polymer chain end is supposed to be composed of a hydroxyl or an aldehydic group [39]. Usually, the amine content increases with increasing molecular weight. In the case of chitosan, the water is bound to the hydroxyl group more strongly than to the amine group. Therefore, the release of water molecules could preferentially occur via the amine group. The crystallinity of various lm samples plasticized with erythritol started to increase after 2 months. The crystallinity of the lms stored at 25 C/60% RH was higher than those of the respective lms stored at 40 C/75% RH. The diffraction pattern of the 40 C/75% RH sample after 2 months has a strong amorphous background and only two reections of crystalline erythritol at about 24.6 and 28.3 (2). Until 3 months, the diffraction pattern has a strong amorphous background and three reections at about 19.6, 20.3, and 37.58 (2), while the diffraction patterns of the 25 C/60% RH samples after 2 and 3 months showed a slightly amorphous background and almost all of reections of crystalline erythritol. Bangyekan et al. [40] prepared chitosan-coated starch lm by coating chitosan solution on cassava starch lm containing glycerol as a plasticizer. A mixture of cassava starch dispersion (6% w/v in water) and glycerol used as a plasticizer was heated at the starch gelatinization temperature
Fig. 1. Equilibrium moisture content (EMC%) of high molecular weight chitosan (CH), medium molecular weight chitosan (CM), low molecular weight chitosan (CL), amylose corn starch (Hylon VII) starting materials (A), and chitosanHylon VII lms (B) stored at different relative humidity for 9 days [38].
of 70 C under stirring until viscous and transparent solution was observed. After homogeneously mixing for 10 min this solution was poured into 5 mm thickness acrylic mold with removable edge strips and allowed to dry freely at room temperature. After air drying, the edges of the mold were removed and four sides of the lm were sealed with adhesive tape to prevent the underneath of starch lm from getting contact with chitosan coating solution in the next step. Chitosan (varied from 1 to 4% (w/v)) was dissolved in 2% (v/v) acetic acid solution then ltered and poured onto the starch lm and the coating was carried out by an automatic lm coater with wire bar coating rod. After coating, the acrylic mold support containing chitosan-coated starch lm was taken out from the automatic lm coater and stored at room temperature, allowing the coated lm to dry for at least 72 h. Three surface properties of the obtained lms were studied; gloss, transparency and hydrophobicity. Gloss is one of the esthetic factors enhancing general appearance as well as consumer acceptance. The gloss values of chitosan-coated starch lms including free starch lm and free chitosan lm are graphically shown in Fig. 2. The gloss values of free chitosan lms are found in the range of 132.5145.6 units, indicating a highly glossy lm probably due to a smooth surface. On the other hand, the gloss values of free starch lms are between 52.4 and 60.1 units, reecting the likelihood of uneven lm surface. For the coated lms, it can be seen that the gloss values increase with an increase in the chitosan coating solution content. From the results, only 1 wt.% chitosan coating solution brings about a signicant increase in gloss values of lm compared with those of free starch lm. The optimum gloss value is achieved when applying
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Fig. 2. The relationship between gloss and chitosan coating content of coated lms containing 2, 3, 4, 5, and 6 wt.% glycerol [40]. Fig. 4. Effect of chitosan coating contents on contact angles of coated lms containing 2, 3, 4, 5, and 6 wt.% glycerol [40].
4 wt.% chitosan coating solution indicating a complete coverage by chitosan layer with an increase in chitosan coating concentration. It could be concluded that the smoother surface of chitosan lm enhanced the regularity of coated lm surface leading to increasing in the gloss value. Transparency may be affected by various factors including lm thickness. The percent transmittance values of coated lms including starch and chitosan free lms are presented in Fig. 3. The transmittance of chitosan lm is slightly higher than that of starch lm. The smoother surface combined with relatively more amorphous structure of chitosan lm (from X-ray evidence) may be responsible for this transparency change. The surface hydrophilicity of the chitosan-coated starch lm was evaluated by means of contact angle determination. The contact angles of coated lms including starch and chitosan free lms are shown in Fig. 4. When considering the particular glycerol content, the free starch lm exhibits the smallest contact angle. It can be clearly seen that an increase in concentration of chitosan coating solution brought about a signicant increase in contact angle values of the coated lms. These results indicate that the wettability of the coated lms decreased with an increase in the chitosan coating concentration. This phenomenon was attributed to the higher hydrophobicity of chitosan surface layer, which was attributed to the role of available
Fig. 3. The relationship between % transmittance and chitosan coating content of coated lms containing 2, 3, 4, 5, and 6 wt.% glycerol [40].
residual hydrophobic acetyl groups present in chitosan chain. This nding suggests that chitosan lm, with this particular degree of deacetylation, was more hydrophobic than starch lm. Mechanical properties are very important for edible lms and coating to improve mechanical handling of foods [41] or pharmaceutical products [42]. The effect of CS coating contents on the tensile properties of CS-coated cassava starch lms in both machine direction (MD) and transverse direction (TD) has been investigated [40]. As shown in Fig. 5, it was found that, at individual glycerol content in the coated lm, there is a signicant change of the tensile stress at maximum load and tensile modulus in both the MD and TD upon increasing the amount of CS coating. The tensile stress and tensile modulus values in MD were higher than those values in TD. This is probably because polymer chain of chitosan aligned along the MD of automatic lm applicator during applying force to wire bar coater. The % elongation at break values in both directions tended to be lower than that of the uncoated or free starch lms. In addition, % elongation at break in MD was found to be lower than in TD. Therefore chitosan improves the tensile stress at maximum load and tensile modulus, of coated starch lms, whereas % elongation at break tends to decrease. In addition, with increasing CS coating concentration, a remarkable decrease in % elongation at break compared to coated lms containing 3, 4, 5, and 6 wt.% glycerol may be attributed to the less plasticizing effect due to the minimized concentration of plasticizer in starch base lm, including the effect of brittleness of chitosan lm. It is observed that there is a little effect on tensile strength of the coated lm containing 5 and 6 wt.% glycerol upon increasing CS coating concentration. Fig. 6 presents the effect of CS coating contents on tensile properties of coated lm containing 5 wt.% glycerol in both directions. At 6 wt.% glycerol, although the improved tensile properties of coated lms in MD and TD are attributed to an increase in CS coating concentration, the greatest tensile strength values obtained from 4 wt.% CS coating are relatively low, i.e., in MD, the tensile stress at maximum load and tensile modulus are about 1.2 and 11.7 MPa, respectively. The % elongation at break in both directions of coated lms containing high glycerol content, especially in TD, tended to increase with increasing the amount of chitosan coating. Mathew and Abraham [43] modied starchchitosan blend lms by incorporating ferulic acid, to nd possible application as an edible lm or coating. Ferulic acid ((E)-3-(4-hydroxy-3-methoxy-phenyl)prop-2-enoic acid) is an abundant phenolic phyto-chemical found in plant cell wall
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Fig. 5. Effect of chitosan coating contents on tensile properties of coated lms containing 5 wt.% glycerol. (A) Tensile stress at maximum load and % elongation at break. (B) Tensile modulus [40].
components, like many phenols, it is an antioxidant in the sense that it is reactive toward free radicals such as reactive oxygen species, it also may have pro-apoptotic effects in cancer cells, thereby leading to their destruction and may be effective at preventing cancer induced by exposure to the carcinogenic compounds. The starchchitosan blend lms were fabricated by means of a casting/solvent evaporation method. Ferulic acid was oxidized by adding different concentrations of ferulic acid (25, 50, 75, and 100) to hydrogen peroxide solution (0.1%, v/v) and kept at room temperature for 1 h under stirring. Thermal analysis of the prepared lms was conducted to investigate the effect of ferulic acid on the stability of the lms since this is a vital property to be considered for their application in food and pharmaceutical industry as the edible lms may be subjected to heat processes during their preparation, processing or consumption [43]. The TGA curves of starchchitosan control lm, ferulic acid and ferulic acid incorporated blend lms are shown in Figs. 7 and 8. It can be seen from these gures that incorporation of up to 100 mg of ferulic acid did not affect the thermal stability. The surface of the control blend lms and ferulic acid incorporated starchchitosan lms were found to be relatively smooth and homogenous. The tensile strength (TS) values of ferulic acid incorporated starch chitosan composite lms have also been investigated [43]. Compared to the control lm, the TS values of the blend lms increased to a value of 62.71 MPa with the incorporation of ferulic acid at a concentration of 75 mg as shown in Fig. 9. However, there was a slight reduction
in strength as the ferulic acid concentration reached 100 mg. Increase in TS could be due to the formation of a stable network on account of the cross linkages introduced by ferulic acid. Ferulic acid can enhance the cross linking between polysaccharides through several mechanisms; through free radical mediated cross linking, by esterication with the hydroxyl groups of chitosan and starch or by quinone-mediated reactions [44]. There has been reports on the cross linking property of ferulic acid in the preparation of edible lms from soy protein isolate [44] and gelatin [45]. The TS increased with the increase in the level of crosslinking agent until the ratio of the ferulic acid/carbohydrate moiety became too high. This may be attributed to the redundant hydroxyl groups which may interact with similar hydroxyl groups and reduce the attractive force. The exibility of the lm is indicated by the percentage elongation (E) value and it was found to be inuenced by the ferulic acid content. The average E values of the lms decreased from 29.3% for the control lm to a minimum of 21.6% and 22.9% for the blend lms containing 75 and 100 mg of ferulic acid (Fig. 9). The reduction in percentage elongation with increase in ferulic acid content might be due to the increase in the number of intermolecular crosslinks and decrease in the intermolecular distance. Starch from two sources, tapioca and rice, has been used with chitosan to make blends with better qualities than from the individual polymers. Tapioca is a signicant crop in South America, [46]. Its edible lms exhibit appropriate physical characteristics, since they are odorless, tasteless, colorless and impermeable to oxygen. However, lms show
Fig. 6. Effect of chitosan coating contents on tensile properties of coated lm containing 6 wt.%glycerol in MD and TD [40].
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Fig. 9. Effect of ferulic acid concentration on the tensile strength and percentage elongation of the blend lms [43].
Fig. 7. Thermogravimetric curves of (a) blend lm; (bd) ferulic acid incorporated lms (50, 75 and 100 mg); (e) ferulic acid and (f) potato starch [43].
brittleness with inadequate mechanical properties. Chillo et al. [47] have blended chitosan (CS) with tapioca starch and glycerol as a plasticizing agent. The apparent viscosity of the lm-forming solution, mechanical and dynamic-mechanical properties, water vapor permeability (WVP) and color of the blend lms have been investigated. The mechanical measurements and viscoelastic properties of the chitosan/tapioca starch-based edible lms have been measured using a stress-controlled Dynamic-Mechanical Analyzer equipped with a tension clamp. Mechanical tests under static, transient and dynamic conditions were performed, i.e. uniaxial tension, stress relaxation and oscillatory stress, respectively. The inuence of CS and glycerol concentrations on the properties of tapioca starch-based edible lm was analyzed. The obtained data inferred that, the elastic modulus (Ec) values were positively affected by the linear and quadratic terms of CS and glycerol contents, respectively, while negatively inuenced by glycerol and CSglycerol interaction. In addition, the tensile strength values were inuenced by the individual positive term of the CS and by the negative inuence of the CSglycerol interaction. Previous studies have shown that the starchchitosan blend lms to exhibit signicantly higher elongation values compared to lms made from starch or chitosan alone [48]. Xu et al. [31] observed a dependence of the elongation at break by starch to CS ratio with a maximum value corresponding to a ratio of
Fig. 8. Derivative thermogravimetric curves of (a) blend lm; (bd) ferulic acid incorporated lms (50, 75 and 100 mg); (e) ferulic acid and (f) potato starch [43].
1.5:1. Probably, in this study, the higher ratio starch to CS was responsible for a negligible effect of the CS on the elongation at break. A biodegradable or edible lm must withstand the normal stress encountered during its application and subsequent shipping and handling of the food to maintain its integrity and barrier properties [49]. High tensile strength is generally required, but deformation values must be adjusted according to the intended application of the lms. That is, whether it is undeformable material to provide structural integrity or reinforce structure of the food. The TS of biodegradable blend lms from rice starch/chitosan with different chitosan ratios is shown in Fig. 10A. The TS of biodegradable blend lms was affected by the chitosan ratios. The results demonstrated that the TS of biodegradable blend lms increased with the addition of chitosan, and the maximum occurred at the rice starch and chitosan ratio of 1:1 and 0.5:1.0. The increasing TS values of the biodegradable blend lms, with the increase of rice starch and chitosan ratios from 2:1 to 0.5:1, are attributable to a high formation of intermolecular hydrogen bonding between NH2 of the chitosan backbone and OH of the rice starch. The amino groups + (NH2) of chitosan were protonated to NH3 in the acetic acid solution, whereas the ordered crystalline structures of starch molecules were destroyed with the gelatinization process, resulting in the OH groups + being exposed to readily form hydrogen bonds with NH3 of the chitosan. However, the TS of biodegradable blend lm prepared at the starch to chitosan ratio of 1:1 and 0.5:1 was not signicantly different. This phenomenon indicated the critical ratios of the greatest miscibility of the two main lm-forming components. Elongation at the break (E) is an indication of the lms exibility and stretchability (extensibility), which is determined at the point when the lm breaks under tensile testing. The value of E was affected by the chitosan ratios (Fig. 10B). The average E values of the biodegradable blend lm behaved inversely to the TS value, decreasing from 12.99% to a minimum 8.06% when the rice starch and chitosan ratio was 0.5:1 (Fig. 10B). E was reduced in the presence of chitosan, probably due to the increased crystallinity of starch in the blend lm. Liu et al. [50] studied the mechanical properties of starch/chitosan blending membrane. Elongation-at-break (E), values of chitosan/starch blend membranes with the different starch masses are shown in Fig. 11. The E membranes' values were affected by the starch contents. This phenomenon has also been reported by Xu et al. [31]. With the mass of starch increasing, the E value of obtained membrane increased in the initial stage until reaching a maximum after which the curve started bending downwards. The data in Fig. 11 could be explained as follows: with the addition of starch, the E value of blend membrane increases + due to the formation of hydrogen bonds between NH3 of the protonat ed chitosan and OH of the starch. However, when the addition of starch was too high, the exibility of obtained membrane was lowered
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Fig. 12. Tensile strength (TS) and elongation at break (E) of sweet potato starch lms as a function of potassium sorbate (K) and chitosan (C) addition. Different lowercase letters in the same curve indicate signicant differences (p b 0.05). Data shown in mean standard deviation (n = 5) [52].
Fig. 10. Tensile strength (MPa) (A), and elongation at break (%) (B) as a function of starch:chitosan ratio [49].
and the E value also decreased for the brittle nature of starch membrane [51]. Thus, it is comparatively difcult to form homogeneous starch/chitosan membrane with higher content of starch. Effects of potassium sorbate (KS) and chitosan incorporation on the tensile strength (TS) and elongation at break (E) of sweet potato starch lm was studied by Shen et al. [52] as seen in Fig. 12. It has been observed that the E values of the lms signicantly decreased when (KS) was added, and the higher the addition of potassium sorbate, the lower the E of the lms. Flores et al. [53] also veried the fact that (KS) could decrease the TS of tapioca-starch edible lms. This was attributed to the interaction between potassium sorbate and the starch molecules resulting in a modication of the starch network in the lms. It is a well-known fact that the mechanical behavior of starch lms is affected by the presence of crystalline phases. Fama, et al. showed that the control lms have higher degree of crystallinity than those with potassium sorbate (KS),
Fig. 11. Elongation-at-break (E) values of chitosan/starch blend membranes with the different chitosan masses [50].
which contributed to the better mechanical behavior of the control starch lm [54]. This was also proved by FT-IR spectra analysis. The addition of chitosan signicantly improved both TS and E of sweet potato starch lms. The TS of lms with 5% and 10% chitosan was lower than those of lms with 15% chitosan, but no signicant difference was observed between TS of lms with 5% and 10% chitosan. Films containing 10% and 15% chitosan had higher values of E than those with 5% chitosan. Gallstedt and Hedenqvist [55] studied the mechanical and barrier properties of pulpberchitosan sheets. They used ve methods to prepare pulpberchitosan sheets, optical micrographs representing the produced sheets are shown in Fig. 13. The results of their work show that, the fracture strain and the fracture stress decreased with increasing chitosan solution content. At chitosan solution contents above 50 wt.%, the shrinkage during the buffer treatment could be reduced effectively by the presence of pulp bers. The buffered sheets also had the highest Young's modulus. Considering that chitosan is a disintegrating polysaccharide with a similar structure to that of cellulose Phisalaphong and Jatupaiboon [56] studied the supplement of chitosan during Acetobacter xylinum cultivation of cellulose. The aim of their study was to develop a new nanostructure lm composed of chitosan and cellulose. Microstructure and mechanical properties of the developed lms are then characterized to provide indications for the modication of bacterial cellulosechitosan (BCC) lm. The blank sample of the bacterial cellulose (BC) lm is the sample with 0% of chitosan content. In comparison to that of the BC lm, the tensile strength of BCC lms (samples containing chitosan) increased with an increase of chitosan content Fig. 14. The tendency of tensile strength of the re-swollen (wet) lms rather corresponded to the dry lms but in a lower range. Fig. 15 shows that the Young's modulus increased with the increase of chitosan supplement correspondingly to the effect on tensile strength. Fig. 16 shows that in contrast to the effect on tensile strength, the percentage of elongation at break decreased with increasing chitosan concentration. Rice is the most widely consumed basic food in the world [49]. Each year over 500 million tons of rice are harvested, providing sustenance to many countries and people throughout the world. The unique properties of rice starches are found in its many varieties. Due to different climates, soil characteristics and cultures, over 240,000 registered varieties of rice exist in the world. These varieties lead to a wide range of rice starches with many different characteristics including: different starting gelatinization temperatures, textures, processing stabilities and viscosities. Rice starch and its major components, amylose and amylopectin, are biopolymers, which are attractive raw materials for use as barriers in packaging materials. They have been used to produce biodegradable lms to partially or entirely replace plastic polymers because of its low
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Fig. 13. Optical micrographs representing sheets produced according to (1) Method 1 (10 wt.% chitosan solution), (2) Method 2 with 20 wt.% chitosan solution and pressure (3) Method 4 with 90% chitosan solution and pressure. The sides of the micrographs correspond to 16.5 cm (A) and (B) and 8.25 cm (C) [55].
cost and renewability, as well as good mechanical properties [31]. However, wide application of starch lm is limited by its mechanical properties and efcient barrier against low polarity compounds [57]. This constraint has led to the development of the improved properties of rice-based lms by modifying its starch properties and/or incorporating other materials. Starch was blended with different proteins to decrease the water vapor permeability of the lms and to increase their tensile strength [58]. Bourtoom and Chinnan [49] prepared biodegradable lms using chitosan with starch. A series of lms was prepared by mixing 100 ml of the starch solutions (1, 2, 3 and 4 g/100 ml) with 100 ml of the chitosan solution (2 g/100 ml). Sorbitol was added as 40% (w/w) of the total solid weight in solution. The mixtures were cast onto at, leveled, non-stick trays to set. Film solubility (FS) is a very important property where water resistance is an important property of biodegradable or edible lms for applications as food protection where water activity is high, or when the lm must be in contact with water during processing of the coated food (e.g. to avoid exudation of fresh or frozen products). However, a high solubility may be an advantage for some applications. Film solubility is advantageous in situations when the lms will be consumed with a product that is heated prior to consumption and may also be an important factor that determines biodegradability of lms when used as packaging wrap. Biodegradable blend lm produced from rice and chitosan maintain their integrity (i.e., did not dissolve or break apart) even after 24 h of incubation with gentle motion. This indicates that the rice starch and chitosan intra and/or intermolecular network remained intact and only the monomers, small peptides, and non-protein material were soluble [49].
Color of the packaging is also an important factor in terms of general appearance and consumer acceptance [59]. The results of the measurements performed on the blend lm's color were expressed in accordance with CIELAB system and the rectangular coordinates; the main difference observed was that biodegradable blend lms with higher content of chitosan had lighter color [49]. 2.1.2. Chitosan and gelatin based edible lms Composite edible lms and coatings can be formulated to combine the advantages of each component. Whereas biopolymers, such as proteins and polysaccharides, provide the supporting matrix, lipids provide a good barrier to water vapor [60]. Since gelatin and chitosan are hydrophilic biopolymers with good afnity and compatibility, they are expected to form composite lms with good properties [61]. Gelatin/ chitosan blends have been used extensively for the production of scaffolds and bi-layers for biomedical applications [62,63]. Rivero et al. [64] developed composite, bi-layer and laminated biodegradable lms based on gelatin and chitosan, to determine lm barrier and mechanical properties and to characterize their microstructure. The gelatin blends with chitosan and chitosan gel to form wound healing materials [65]. The blend has a smooth and homogeneous surface as revealed by SEM and X-ray measurements [66]. The effect of chitosan molecular weight (MW) and degree of deacetylation (DD) on the physicochemical properties of gelatinbased lms were studied [67]. Determination of the dynamic
Fig. 14. The tensile strength of BCC lms in re-swollen (wet) form: (a) BCC-MW 30,000 and (b) BCC-MW 80,000 and in dry form (c) BCC-MW 30,000 and (d) BCC-MW 80,000 as a function of chitosan content (% w/v) in culture medium [56].
Fig. 15. The Young's modulus of BCC lms in re-swollen (wet) form: (a) BCC-MW 30,000 and (b) BCC-MW 80,000 and in dry form (c) BCC-MW 30,000 and (d) BCC-MW 80,000 as a function of chitosan content (% w/v) in culture medium [56].
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properties, suitable for packages of many kinds of food products with different acidities and contents of moisture. More research should be directed to the exploitation of these blends with potential applications for food protection. 2.1.3. Chitosan with alginate and carageenan Alginate is a linear copolymer extracted from brown seaweeds known as Phaeophyceae and composed of (1 4)-linked--D-mannuronate (M) and (1 4)-linked--L-guluronate (G) units. These units are arranged in G-blocks, M-blocks and alternating sequences of GM-blocks forming the polymeric structure, where the sequential arrangement depends on different factors such as the specie, age or parts of the seaweeds from which this material was obtained [71]. It has been well characterized in both the liquid and gel state, making this biopolymer unique compared to other gelling polysaccharides. Alginates possess good lm-forming property, producing uniform, transparent, and water soluble lms. Alginate-based lms are impervious to oils and fats but, as other hydrophilic polysaccharides, have high WVP. However, alginate gel coating can act as a sacricing agent, where moisture is lost from the coating before the food signicantly dehydrates. The coating can also improve the adhesion of batter to the surface of fruits and vegetables [72]. Alginate coatings are good oxygen barriers that can retard lipid oxidation in various fruits and vegetables, and have been found to reduce weight loss and natural micro ora counts in minimally processed carrots [73]. Calcium alginate coatings were found to improve the quality of fruits and vegetables, such as reducing shrinkage, oxidative rancidity, moisture migration, oil absorption, and sealing-in volatile avors, improving appearance and color, and reducing weight loss of fresh mushrooms in comparison with uncoated ones [74]. Carrageenans are anionic linear polysaccharides extracted from red seaweed (Rhodophyceae), consisting of alternating -1, 4 and -1, 3 linked anhydrogalactose residues. There are three major fractions ( kappa, iota and lambda) with varying number and position of sulfate groups on the galactose dimer. Carrageenan-based coatings have been applied to fresh fruits and vegetables such as fresh apples for reducing moisture loss, oxidation, or disintegration of the apples [72,75]. In combination with anti-browning agents such as ascorbic acid, carrageenan-based coatings resulted in positive sensory results and reduction of microbial levels on minimally processed apple slices. By acting as a sacricial moisture layer, carrageenan coating was able to protect moisture loss of grapefruits. In addition, -carrageenan lms can effectively carry food-grade antimicrobials such as lysozyme, nisin, grape fruit seed extract, and EDTA for a wide range of applications as a food package material [76]. Both the alginates and the carrageenans can interact with chitosan forming polyelectrolyte complexes [77] which were used to obtain microcapsules for cell encapsulation and devices for the controlled release of drugs or other substances. It seems there is good potential to investigate this interaction to produce edible lms from these materials which could be of great value, however not yet explored. 3. Chitosan/essential oil lms Many spices and herbs and their extracts possess antimicrobial activity. The composition, structure as well as functional groups of the oils play an important role in determining their antimicrobial activity [78]. Usually compounds with phenolic groups are most effective [79]. Among these, the oils of clove, thyme, cinnamon, rosemary, sage and vanillin have been found to be most consistently effective against microorganisms. Besides antibacterial properties [80,81] essential oils, Eos, or their components have been shown to exhibit antimycotic [82], antitoxigenic [83] and antiparasitic [84] properties. These characteristics are possibly related to the function of these compounds in plants [85]. A comprehensive review dealing with the more common synthetic and natural antimicrobial agents derived from essential oils incorporated into or coated onto synthetic packaging lms for
Fig. 16. The elongation at break of BCC lms in re-swollen (wet) form: (a) BCC-MW 30,000 and (b) BCC-MW 80,000 and in dry form (c) BCC-MW 30,000 and (d) BCC-MW 80,000 as a function of chitosan content (% w/v) in culture medium [56].
viscoelastic properties (elastic modulus G and viscous modulus G) of the lm-forming solutions revealed that the interactions between gelatin and chitosan were stronger in the blends made with chitosan of higher molecular weights or higher degrees of deacetylation than the blends made with lower molecular weights or degrees of deacetylation. Fish gelatin lms modied with chitosan of higher molecular weights or higher degrees of deacetylation had higher tensile strengths. Films of chitosan and gelatin were prepared by casting their aqueous solutions (pH b 4.0) at 60 C and evaporating at 22 or 60 C (lowand high-temperature methods, respectively). The physical (thermal, mechanical and gas/water permeation) properties of these composite lms, plasticized with water or polyols, were studied [68]. An increase in the total plasticizer content resulted in a considerable decrease of elasticity modulus and tensile strength (up to 50% of the original values when 30% plasticizer was added), whereas the elongation percentage increased (up to 150% compared to the original values). The low-temperature preparation method led to the development of a higher percentage crystallinity of gelatin which resulted in a decrease, by one or two orders of magnitude, of CO2 and O2 permeability in the chitosan/gelatin blends. An increase in the total plasticizer content (water and polyols) of these blends was found to be proportional to an increase in their gas permeability. This blend should be a promising candidate for good edible biodegradable lms. It has been found that gelatin origin plays a role in improving the physical characteristics of lms with chitosan [69]. The data revealed that the interactions between gelatin and chitosan were stronger in the blends made with tuna-skin gelatin than in the blends made with bovine-hide gelatin. As a result, the sh gelatin chitosan lms were more water resistant (w18% water solubility for tuna vs. 30% for bovine) and more deformable (w68% breaking deformation for tuna vs. 11% for bovine) than the bovine gelatin chitosan lms. The breaking strength of gelatin chitosan lms, whatever the gelatin origin, was higher than that of plain gelatin lms. Bovine gelatin chitosan lms showed a signicant lower water vapor permeability (WVP) than the corresponding plain lms, whereas tuna gelatin chitosan ones were only signicantly less permeable than plain chitosan lm. Complex gelatin chitosan lms behaved at room temperature as rubbery semi-crystalline materials. In spite of gelatin chitosan interactions, all the chitosan-containing lms exhibited antimicrobial activity against Staphylococcus aureus, a relevant food poisoning. Mixing gelatin and chitosan may be a means to improve the physico-chemical performance of gelatin and chitosan plain lms, especially when using sh gelatin, without altering the antimicrobial properties. The effect of glycerol on the mechanical and water barrier properties, as well as on the water solubility, of sh gelatinchitosan lms was studied by Koodziejska and Piotrowska [70]. The nal goal of their study was to design biodegradable material with good mechanical and barrier
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antimicrobial packaging applications has been published by Kuorwel et al. [86]. The focus is on the widely studied herb varieties including basil, oregano, and thyme and their essential oils (EOs). Because of the effect of direct addition of essential oils to food incorporation of essential oils to lms may have supplementary applications in food packaging [87,88]. Combining antimicrobial agents such as plant essential oils directly into a food packaging is a form of active packaging. Rosemary, a good source of antioxidant compounds, is widely used in the food industry to prevent oxidative degradation of foods [8991]. The antioxidant activity of rosemary extracts is associated with the presence of several phenolic diterpenes, which break free radical chain reactions by hydrogen donation. Oxygen pretreatment and chitosan coating 0.03% rosemary extracts have improved the quality of fresh-cut pears and extend the shelf-life [92]. The chitosan lm was prepared by dispersing chitosan in an aqueous solution of 1% glacial acetic acid (v/v) at 4 C, 1.5% glycerol (w/v) and 0.2% Tween-80 (v/v) were added to the mixture and the mixture was homogenized at 1000 rpm for 10 min. The pH value was adjusted to 5.6 with 1 M NaOH. The solution was strained through layers of cheesecloth and degassed under vacuum at room temperature 0.03% rosemary extract was added to the nal chitosan solution. The chitosan lm solutions were stored in a refrigeration condition (4 C) for 12 days [92]. In spite of the extensive use of chitosan as edible lms for coating, it still suffers from high water vapor permeation which lowers its protective action, therefore trials were made to add oils to increase its hydrophobicity and improve its water vapor permeation. Chitosan was mixed with increasing concentration of olive oils to prepare homogeneous lms with decreasing moisture sorption, lower water vapor permeation through the lms and smaller effective diffusion coefcients of the lms as the oil concentration increases [93]. All the tensile properties (Young modulus, strength and maximum elongation) increased with olive oil concentration and were explained considering the interactions developed between lipid and carbohydrate phases in addition to the lubricant characteristics of the oil [93]. Ojagh et al. [94] studied the effect of adding cinnamon essential oil (CEO) into chitosan-based lms. It was found that CEO increased the antimicrobial activity, while decreased the moisture content, the solubility in water, the WVP and elongation at break of the chitosan
lms. Incorporating CEO at level of 0.4%, 0.8%, 1.5% and 2% (v/v) into chitosan lms increased the tensile strength values signicantly. The authors claimed that a strong interaction between the polymer and the CEO produced a cross-linker effect, which decreases the free volume and the molecular mobility of the polymer. This phenomenon led to a sheet like structure as seen in (Fig. 17C). Arrangement of stacking layers of CEO added chitosan sheets (Fig. 17D) means that in these lms a compact structure has formed leading to a decrease in elongation at break and increasing of the tensile strength. There are also possibilities that such structure enhances the decrease in moisture content of the lms incorporated with CEO. The active component of CEO is cinnamaldehyde (~ 60%) [95]. Chitosan control lms did not show inhibitory zone in bacterial strains tested. Despite antimicrobial activity of chitosan because of its innate characteristic, this effect of chitosan occurred without migration of active agents. Chitosan does not diffuse through the adjacent agar media in agar diffusion test method; so that only organisms in direct contact with the active sites of chitosan are inhibited [13]. Cinnamon oil has also been used by the same authors to blend with chitosan for the preservation of trout sh let [87]. This treatment could maintain trout let shelf life till the end of the storage period (16 days) without any signicant loss of texture, odor, color or overall acceptability and without signicant microbial growth. Variations in the value of total viable counts (TVC) on the sh surface during the refrigerated storage are presented in Fig. 18. The initial TVC (log CFU/g) in trout let ranged from 3.51 in Ch +C-coated samples to 3.86 in controls. In the meantime, the control samples had a shelf life of only 12 days. Therefore, chitosan coating together with cinnamon oil proved to be an efcient method of protecting the sh under refrigerated storage for a longer period f time. Bergamot essential oil (BO) is citrus oil (from Citrus bergamia), whose major chemical compounds are limonene (3245%) and linalool (around 10.23%) [9698]. The antimicrobial efciency of BO, and its components, linaool and citral, have been found to be effective against Campylobacter jejuni, E. coli O157, Listeria monocytogenes, Bacillus cereus, S. aureus, Arcobacter butzleri and Penicillium digitatum [99], among others, both when oil is applied directly and when in contact with the oil vapor. Chitosan-based lms containing BO (CSBO) at 0.5, 1.2 and
Fig. 17. Scanning electronic microscopic images of chitosan control lm (A) and (B), and lm containing CEO at level of 1.5% (C) and (D) surfaces and cross sections, respectively [95].
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Fig. 18. Changes in total viable counts (TVC) of sh samples during refrigerated storage [87].
3% w/w were prepared to evaluate their physical and antifungal properties. Film-forming dispersions (FFD) were also characterized in terms of rheological properties, particle size distribution and -potential. Furthermore, the antifungal effectiveness of CSBO composite lms against Penicillium italicum was studied. Results showed that incorporation of BO provoked a decrease in the water vapor permeability, this reduction being around 50% when using a BOCS ratio of 3:1. Concerning mechanical and optical properties, CSBO composite lms were less resistant to break, less deformable and less glossy. The load parameters (TS and EM) decreased more than 50% and the percentage of elongation at break was also dramatically reduced from 22% to 5%, as compared with the pure chitosan lms. CSBO composite lms showed a signicant inhibitory effect on the growth of P. italicum, which depended on the BO concentration. Chitosan lms with the maximum bergamot oil content (3:1 BOCS ratio) led to a total inhibition of the fungus growth during the rst 5 days at 20 C. Although the antifungal effectiveness of the lms decreased throughout the storage time, a signicant reduction of 2 log units as compared with the control remained possible, after 12 days at 20 C, using the highest BO content. The mechanisms by which essential oils bring about their antimicrobial effect are not clear, Holley and Patel [78] had suggested that terpenes have the ability to disrupt and penetrate the lipid structure of the cell membrane, as well as the mitochondrial membrane, leading to the denaturation of proteins and the destruction of cell membrane, cytoplasmatic leakage, cell lysis and eventually, cell death. The essential oil of Melaleuca alternifolia, also named as tea tree oil (TTO), is a complex mixture of terpen hydrocarbons and tertiary alcohols [100]. The main compounds responsible for the antimicrobial activity are terpinen-4-ol and 1, 8-cineole, TTO has been used successfully in the management of oral candidiasis in AIDS patients [101] and other oral fungal infections in patients suffering from advanced cancer [102]. Sanchez-Gonzalez et al. [100] incorporated TTO into chitosan matrix and investigated the physical and antibacterial behavior of the obtained composite. The CS lms were rough and a reduction of its gloss occurred after the incorporation of TTO. Water vapor permeability was also reduced by 40% when the CS/TTO ratio was 1:2. Likewise, the lms' resistance to break was notably reduced by TTO incorporation due to the presence of discontinuities in the lm matrix that affect its mechanical response. The poor mechanical properties obtained by the addition of TTO may be related with the structural arrangement of the lipid phase into the chitosan matrix. Thus, the structural discontinuities provoked by the incorporation of the oil could explain the lowest resistance to fracture of the composite lms. Some of these results are in line with those reported by other authors when adding oils to a chitosan matrix [103,29] but differ in some aspects due to the great inuence of several, widely studied factors related to CS preparation. Only the composite
lms with TTO:CS ratios higher than 1 showed a limited antifungal effectiveness against Penicillium, which was notably reduced after 3 days of storage. Nevertheless, CS lms presented a signicant antimicrobial activity against L. monocytogenes and the incorporation of TTO in the CS/ TTO ratio of 1:2 improved the antibacterial properties of these lms, showing a complete inhibition of the microbial growth during the fth day at 10 C. Synergism and antagonism between components of EOs and food constituents require more study before these substances can be reliably used in commercial applications [104]. Biodegradable coatings based on chitosan (CS) with and without bergamot essential oil were applied to table grapes, cv. Muscatel investigated by Snchez-Gonzlez et al. [105] in order to nd environmentally friendly, and healthy treatments with which to better preserve fresh fruit quality and safety during postharvest cold storage. Physicochemical properties (weight loss, Brix, total phenols, antioxidant activity, color and texture), respiration rates and microbial counts of samples were determined throughout cold storage when using CS. CS coatings containing bergamot oil produced the most effective antimicrobial activity, and showed the greatest inhibition of the respiration rates in terms of both O2 consumption and CO2 generation. Although the coatings did not seem to reduce the rate of grape browning during storage, they inhibited color development, thus improving the product appearance. Taking into account the overall results obtained, the most recommended coating for Muscatel table grape is the CS containing bergamot oil. An intensive study has been conducted by Gmez-Estaca et al. [106] in which chitosangelatin lms, containing sorbitol and glycerol as plasticizers were incorporated with several different essential oils and tested for their antibacterial behavior against 18 different bacterial strains which included some important food pathogen and spoilage bacteria. Clove essential oil showed the highest inhibitory effect, followed by rosemary and lavender. Clove and thyme essential oils were the most effective food preservatives, when tested on an extract made of sh. The gelatin/chitosan-based edible lms incorporated with clove essential oil were tested against six selected microorganisms: Pseudomonas uorescens, Shewanella putrefaciens, Photobacterium phosphoreum, Listeria innocua, E. coli and Lactobacillus acidophilus. The clovecontaining lms inhibited all these microorganisms irrespectively of the lm matrix or type of microorganism. When the complex gelatin chitosan lm incorporating clove essential oil was applied to sh during chilled storage, the growth of microorganisms was drastically reduced in Gram-negative bacteria, especially enterobacteria, while lactic acid bacteria remained practically constant for much of the storage period [106]. Mayachiew et al. [107] studied the effect of drying methods and conditions (i.e., ambient drying, hot air drying at 40 C, vacuum drying and low-pressure superheated steam drying (LPSSD) within the temperature range of 7090 C at an absolute pressure of 10 kPa) as well as the concentration of galangal extract on the antimicrobial activity of edible chitosan lms against S. aureus. Galangal extract was added to the lm forming solution as a natural antimicrobial agent in the concentration range of 0.30.9 g/100 g. Galangal similar to ginger and turmeric is a member of the rhizome family. Rhizomes are knobby underground stems that are known for their pungent and avorful esh, it is a traditional spice used extensively for avoring and medicinal purposes. Galangal extract has also proved to be an effective natural antimicrobial agent against some food poisoning bacteria, e.g., S. aureus [108]. The main compounds of galangal extract are the terpenes, which have potential antimicrobial activity [78,106,109]. Chitosan lms containing galangal extract at 0.6% and 0.9% (w/w) were effective in inhibiting the growth of S. aureus. No inhibition zone was observed when the extract concentration of 0.3% (w/w) was used. This could be ascribed to a limited galangal extract release probably due to interaction between the extract and chitosan. Another possible reason could be the limit of detection of antimicrobial activity when
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using the disk diffusion method [13,110]. It was noted that drying methods and conditions had signicant effects on the antimicrobial activity of chitosan lms incorporated with galangal extract. The results showed that ambient dried lm had the highest antimicrobial activity; this was followed by LPSSD lms and vacuum dried lms. This may be due to the fact that the lm temperature increased more rapidly and stayed at higher levels in the case of vacuum drying than in the case of LPSSD, thus inducing more thermal degradation of the antimicrobial compound [104,111]. In addition, different intermolecular interactions also contributed to the observed results. The decrease in bacteria inhibition might be due to lower diffusion of the active agent into the agar medium as a result of higher interaction between chitosan and galangal extract. The antimicrobial lms prepared at higher drying temperatures had lower antimicrobial activity, both in the cases of vacuum drying and LPSSD. The antimicrobial lms prepared by LPSSD at 70 C had the highest antimicrobial activity compared with lms prepared at other conditions of vacuum drying. The results showed that the antimicrobial activity of the lms increased with an increase in the extract concentration, as expected. Chitosan lm incorporated with 0.9% (w/w) galangal extract and prepared by ambient drying could reduce the number of S. aureus by about 3.6 log cycle within the contact time of 24 h. On the other hand, ambient dried lm incorporated with 0.3% (w/w) galangal extract exhibited lower cell reduction number of around 2.0 log cycle. Sanchez-Gonzalez et al. [112] prepared antimicrobial lms by incorporating different concentrations of tea tree essential oil (TTO) into chitosan (CS) lms. These lms have been tested against L. monocytogenes and P. italicum. The possible antifungal effect against P. italicum at 20 C of CS and composite lms was determined on potato dextrose agar (PDA) medium and shown in Figs. 19 and 20. This effectiveness was evaluated through the analysis of the growth (or survival) of a determined infection level of P. italicum (105 spores/ml), the growth of fungus was followed by counts immediately after the inoculation and periodically during the storage period of (PDA) plates. CS lms did not show antifungal effect for the assayed times. Previous studies have demonstrated that the antimicrobial effect of chitosan depends on the type of microorganism, being mainly effective against bacteria and also against some molds and yeast [113]. The TTO composite lms delayed the fungal growth of P. italicum (in comparison to the control), which was dependent on the TTO concentration. At low TTO levels, no antimicrobial effect was observed. Only when TTOCS ratio was higher than 1, a moderate inhibition of fungus
Fig. 20. Effect of CS and CSTTO composite lms on the growth and survival of Listeria monocytogenes on TSA NaCl medium stored at 10 C. Mean values and 95% LSD intervals for each sample time [112].
growth was detected. The level of reduction of the Penicillium population in CS2TTO lms observed during the rst 3 days of storage was especially remarkable, reaching a fungal reduction of 3 logs in comparison with the control plates. Nevertheless, the inhibition level of the composite lms decreased throughout storage time. Considering that the antimicrobial activity of TTO has been probed with very low concentrations in the liquid phase, the observed behavior could be explained by the availability level of active antimicrobial compounds against the fungi agent. Numerous studies have demonstrated that these compounds are more effective in reducing microbial growth when incorporated into a lm or gel and applied to the product surface than when applied on the surface via spray solution or directly added to the product [114117] because of the active substances ability to evaporate or diffuse into the medium. 4. Chitosan and clay Natural polymers suffer from lower mechanical strength compared to synthetic polymers and high moister barrier because of their hydrophilic nature. Many strategies have been explored to improve these problems of chitosan based biodegradable packaging lms. These include the addition of plasticizers such as glycerol which increases the exibility of the nal product [103]. The addition of other biodegradable aliphatic polyesters, such as poly-caprolactone (PCL), poly(butylene succinate) (PBS), poly(lactic acid) (PLA), poly(butylene terephthalate adipate) (PBTA), and poly(butylene succinate adipate) (PBSA), has also been investigated to produce materials with properties intermediate between the two components [118]. Other methods included the addition of layered silicates nanoparticles (e.g. sodium montmorillonite) to chitosan to improve its end-use properties such as barrier and mechanical properties [119]. Montmorillonite (MMT) is the most studied nanoscale clays. It is hydrated aluminasilicate layered clay made up of two silica tetrahedral sheets fused to an edge-shared octahedral sheet of aluminum hydroxide. Its advantages of high surface area and platelet thickness of 10 make it suitable for reinforcement purposes. When nanoclay is mixed with a polymer, three types of composites (tactoids, intercalation, and exfoliation) can be obtained. In the case of tactoids, complete clay particles are dispersed within the polymer matrix and the layers do not separate. Mixing a polymer and organoclay forms a micro-scale composite, with the clay serving only as a conventional ller. Intercalation and exfoliation are two ideal nano-scale composites. Intercalation occurs when a small amount of polymer is inserted between the layers of the clay, thus expanding the interlayer spacing and forming a
Fig. 19. Effect of CS and CSTTO composite lms on the growth and survival of Penicillium italicum on PDA medium stored at 20 C. Mean values and 95% LSD intervals for each sample time [112].
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and MMT, hindering the occulation and leaves the MMT stacks randomly orientated in space. A higher reduction of permeability (50%) is obtained in chitosan lms not containing glycerol due to the alignment and occulation of MMT stacks. This system could have potential applications in the packaging eld. 5. Gas permeation properties of edible coatings Permeability is a steady-state property that describes the extent to which a permeating substance dissolves and then the rate at which it diffuses through a lm, with a driving force related to the difference in concentration of that substance between the two sides of the lm [128]. Gas permeability of edible lms and coatings depend on several factors such as the integrity of the lm, the ratio between crystalline and amorphous zones, the hydrophilichydrophobic ratio and the polymeric chain mobility; the interaction between the lm-forming polymer and the presence of a plasticizer or other additives are also important factors in lm permeability [129]. The measurement of permeability of oxygen and carbon dioxide of the edible lms provides important information for their further development. Oxygen is the key factor that might cause oxidation, inducing several unwanted food changes such as odor, color and avor, as well as nutrients deterioration. Therefore, lms providing a proper oxygen barrier can help in improving food quality and extending food shelf life [130]. Carbon dioxide that is formed in some foods due to deterioration and respiration reactions should be removed from the package to avoid further food deterioration and/or package destruction [131]. Such lms can maintain food quality and improve stability and shelf life by retarding unwanted mass transfer (O2 and CO2) in food products migration of moisture for dried and intermediate moisture foods, and migration of solutes for frozen foods. There are several possible edible coatings for fruits, such as cellulose, casein, zein, soy protein, and chitosan. These were chosen since they have the desirable characteristics of generally being odorless, tasteless and transparent. It is not easy to measure the gas permeation properties of the coatings after being placed on fruits. Therefore, separate at lms need to be prepared and tested.
Fig. 21. Inuence of medium pH on the effects of chitosan, without chitosan, 0.005% chitosan, and 0.01% chitosan. Open symbols are pH 4 and closed symbols are pH 6 (T = 7 C). The lines represent the tted Baranyi-model [154].
well-ordered multilayer structure. In exfoliation, the layers of the clay are separated completely and the individual layers are distributed throughout the polymer matrix. The formation of intercalation or exfoliation depends on the types and amounts of nanoclay used [119]. Several reports deal with the preparation characterization of MMT/ chitosan composites and lms [120126]. It has been shown that chitosan interact with MMT and forms a homogenous lm. Chitosan/MMT nanocomposites were prepared by an ion exchange reaction between water soluble oligomeric chitosan and Na MMT. Chitosan showed high afnity to MMT clay host. According to thermogravimetric analysis (TG) and powder X-ray diffraction analysis the thermal stability of chitosan was remarkably improved due to the strong electrostatic interaction of cationic chitosan molecules with anionic silicate layers. It was also found that the nanocomposites showed a synergistic effect in the antimicrobial activity against to E. coli and S. aureus [127]. Delaminated MMT were found to be enriched on the surface of the nanocomposites when the amount of MMT was >103 ppm. This was accompanied by a decrease of the contact angle [121]. The proliferation of broblasts on MMT/CS 103 ppm was signicantly greater than on other materials. The antimicrobial activity was enhanced markedly with the increased amount of MMT. The inammatory responses of MMT in vitro and in subcutaneous rats were not obvious until the concentration of MMT was >103 ppm. The biocompatibility of MMT/CS at 103 ppm was even better than that of CS. The biodegradation rate of CS of the MMT/ CS nanocomposite was much faster than that of the pure CS polymer. These results suggested potential antimicrobial applications for MMT/ CS nanocomposites, especially for those containing 10 3 ppm (0.1%) of MMT [121]. Montmorillonite (MMT) nanoclay and rosemary essential oil (REO) were incorporated into chitosan lm [120]. The MMT weight percent relative to chitosan was varied from 1 to 5 and was activated by three REO levels (0.5%, 1%, and 1.5% v/v), and their impact on physical, mechanical, and barrier properties of the chitosan was investigated. The results of these investigation showed that the combined effect of adding MMT and REO improved the tensile strength and the antibacterial properties of the chitosan composites (lms). It was also found that the MMT/chitosan biocomposite particles exhibited a higher thermal decomposition temperature compared to pure chitosan particles. The dual effect of adding glycerol and MMT to chitosan has been investigated by Lavorgna et al. [124]. The authors found that the mechanical properties of nanocomposite containing glycerol are improved as clay loading increases. This is due to a combined effect of clays and plasticizer. Glycerol modies the hydrogen-bonding network within the material and allows better interaction between ller and matrix, thus facilitating the stress transfer to the reinforcement phase and improving its mechanical properties. The addition of glycerol lowers the water permeability by (30%). Glycerol reduces the hydrogen interactions between chitosan
Fig. 22. The inuence of soluble starch on the antimicrobial activity of chitosan. Lag phase (A) and growth rate (B) of Candida lambica with different chitosan and starch concentrations (T = 7 C and pH = 5). , 0% starch; , 1% starch; , 30% starch [154].
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Fig. 23. The change of antibacterial activities of starch/chitosan blend lms with radiation dose (80% starch, 20% chitosan) [155].
Formulations based on polysaccharides and proteins have proved their excellent selective permeability to O2 and CO2. However, because of their hydrophilic nature they exhibit poor moisture barrier properties, which can be improved by adding hydrophobic materials such as natural waxes, acetylated monoglycerides and surfactants through emulsion or lamination technology. That is why edible lms usually are heterogeneous in nature. Literature data indicate that O2, CO2 and water vapor permeability of edible coatings are lower than the conventional plastic lms. Starch lms ability for food protection is by controlling and reducing oxygen transport, thus extending the shelf life of the food. However, the incorporation of antimicrobial agents to starch lms increases O2 gas permeability thus incorporation of potassium sorbate to sweet potato starch lms, led to higher oxygen permeability [52]. The mass transfer of oxygen in a semi-crystalline polymer is primarily a function of the amorphous phase, because the crystalline phase is usually assumed to be impermeable. Fama et al. [53,55] showed that the incorporation of potassium sorbate decreased the crystallinity of tapioca-starch edible lms causing an increase in oxygen permeation (OP) of the starch lms. The incorporation of potassium sorbate weakened inter-molecular forces between adjacent starch polymeric chains, facilitated chain mobility and increased the free volume between starch molecules, which promoted oxygen permeability [132]. However, a better oxygen transportation barrier property was obtained with the starch lms when chitosan was incorporated. With 15% of chitosan, sweet potato starch lm had a signicantly lower OP (1.940.9510 6 cm3 m/(m2 dkPa)) than that of the control starch lm. Chitosan could form inter-molecular hydrogen bonds with starch, which limited the inter-molecular chain mobility and decreased its free volume, contributing to the decrease of OP. Moreover, Xu et al. [31] reported that chitosan lm possessed low permeability to oxygen. Mathew and Abraham [43] determined the water vapor transmission (WVT) of lms gravimetrically. The lms were xed on to the circular opening of permeation cell-containing anhydrous calcium chloride (0% RH) using melted parafn. The cups were then weighed and placed at 92% relative humidity and 37 C in a humidity chamber. The cups were weighed at 1-h intervals until the change in weight became constant. The water vapor transferred through the lms at different time intervals were determined from the weight gain of the cups. Changes in the weight of the permeation cell were recorded and plotted as a function of time. The slope of each line was calculated by linear regression and WVT rate was calculated from the slope of the straight line (g/h) divided by the transfer area (m 2). Oxidized ferulic acid incorporated lms were found to signicantly decrease the WVT compared to the control blend lms, probably due
to the higher degree of cross linking that results from the formation of quinones and free radicals which tend to promote the cross linking [133]. However, the permeability of the ferulic acid incorporated lm at a concentration of 100 mg increased slightly in comparison to the blend lm containing 75 mg of ferulic acid, but was lower than that of the control lm indicating 75 mg of ferulic acid as the optimal concentration of the cross-linking agent. Blend lms with higher TS had lower WVT rates probably owing to the better degree of organization of the polysaccharide network up to the optimum concentration of ferulic acid. They also studied oxygen transmission rates of chitosan/starch lms with different amount of ferulic acid. In general, polysaccharide lms are expected to be good oxygen barriers, due to their tightly packed and ordered hydrogen-bonded network structure and low solubility. The results showed that the oxygen transmission rate reduced with the increase in the level of cross-linking agent. Kucuk and Caner [134] have reported better stability and quality for sunower oil samples stored under packaging conditions free of air. High levels of oxygen in food packages have been reported to cause the development of off-avors, off-odors and nutritional loss in food stuffs [135]. Since a main function of a food packaging is often to avoid or at least to decrease moisture transfer between the food and the surrounding atmosphere, or between two components of a heterogeneous food product, WVP should be as low as possible. Shen et al. [52] showed that the WVP of sweet potato starch lms decreased signicantly with the addition of over 10% chitosan. This was also the case for tapioca-starch-based edible lm examined by Chillo et al. [47]. They explained the decreasing WVP transmission rate at higher concentrations of chitosan as a result of reducing the available hydrophilic group [31,47]. In addition the hydrogen bonding interaction between chitosan and starch decreased the free sorption sites for water, which is responsible for decreasing the WVP of the lm [136]. WVP of chitosan lms (CS) contain different concentrations of tea tree essential oil (TTO) had been studied by Sanchez-Gonzalez et al. [100]. The room temperature conditions used for measuring the WVP (100/54.4) of the lms were established to simulate the environmental conditions when the lms are applied as a coating for vegetables. WVP values were in the range of those reported by other authors working with lms based on chitosan [29]. The WVP values showed a signicant decrease in line with the increase in TTO concentration, reaching a maximum WVP reduction of about 40% with incorporation of 2% TTO in the lm-forming dispersions. This behavior is expected as an increase in the hydrophobic compound fraction usually leads to an improvement in the water barrier properties of lms, as was previously reported for essential oils addition in CS lms [96].
Fig. 24. The change of antibacterial activities of starch/chitosan blend lms with the content of chitosan (50 kGy) [155].
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Fig. 25. Inhibition area of (A) control lm and (B) AM incorporated lm [167].
6. Effect of electric eld on lm formation Preliminary works have shown that the presence of a moderate electric eld during the preparation of chitosan coating solutions may inuence their transport properties. If such effect is conrmed, moderate electric elds could be used to tailor edible lms and coatings for specific applications. Ohmic heating is based on the passage of electrical current through a sample where the electrical energy is directly converted to heat and instant heating occurs. The use of electric elds in the food area has gained a new interest [137,138]. The application of electric elds has also been an important instrument among researchers in the area of edible lms and coatings, and there are works showing that the application of electric elds promotes a signicant improvement of several properties. Garcia et al. [139] analyzed the effect of an electrical eld applied during drying on the microstructure and macroscopic properties of lms obtained with different mixtures of chitosan (CS) and methylcellulose (MC). The analysis indicated that CS electrically treated lm exhibited a more ordered structure lower WVP and higher Young's modulus values leading to stronger lms. The authors concluded that electrical eld treatment would be a good alternative to improve lm exibility and water vapor barrier properties. Lei et al. [140] reported that using ohmic heating for the production of proteinlipid lms, improves the yield, of the lm formation rate and the rehydration capacity of the lms. Souza et al. [141] determined the effect of eld strength on the functional properties of chitosan coatings. Four different eld strengths were tested, for each electric eld treatment, the water vapor, oxygen and carbon dioxide permeability of the lms formed were determined, together with their color, opacity and solubility in water. Chitosan lms formed from solutions subjected to electric elds at 100 V cm 1 or higher were found to have lower values of O2P and CO2P (oxygen and CO2 permeability). Atomic force microscopy AFM observation of chitosan lms surface treated at 100 V cm 1 or above (conrmed by the Ra values) showed smoother surface as opposed to a rougher surface of untreated lms. AFM imaging modes can potentially provide structural information for a sample in its more natural state (without dehydration or coatings). Nanoscale measurements by AFM allow the inuence of different factors on the hardness, elasticity and permeability of the lm surface to be quantied, which is extremely useful for the design of high performance edible food packaging systems [142]. 7. Antibacterial activity of chitosan and chitosan blends The greatest losses in food are due to microbiological alterations. Many chemical and physical processes have been developed to preserve
food quality. Among such processes, adequate packaging is a fundamental factor in the conservation and marketing phases. Thus, packaging plays a prominent role in maintaining food quality. Antimicrobial lms and coatings have vitalized the concept of active packaging and have been developed to reduce, inhibit or delay the growth of microorganisms on the surface of foods in contact with the packaged product [143,144]. In most fresh or processed foods, microbial contamination occurs at a higher intensity on the food surface, thus requiring an effective microbial growth control. Traditionally, antimicrobial agents are added directly to the foods, but their activity may be inhibited by many substances in the food itself, diminishing their efciency. In such cases, the use of antimicrobial lms or coatings can be more efcient than adding antimicrobial agents directly to the food since these may selectively and gradually migrate from the package onto the surface of the food, thereby high concentrations being maintained when most necessary [114]. L. monocytogenes, a Gram-positive rod, is a bacterium that can cause illness in a variety of food products [145]. One food product of great concern is the refrigerated, ready-to-eat (RTE) foods contaminated with L. monocytogenes [146]. Eating foods contaminated with L. monocytogenes normally causes the disease listeriosis which is more serious for elderly adults and adults with compromised immune systems and can cause meningitis [147]. In pregnant women, the disease may cause spontaneous abortions or stillborn babies. Greenwood [147] has studied the antimicrobial effect of chitosan, as an edible lm, that was dissolved in lactic acid or acetic acid against L. monocytogenes on RTE roast beef. Chitosan with low and high molecular weight (MW) of (4.7 10 5 g/mol) and (1.1 10 6 g/mol) were used to test the molecular weight effect on the antimicrobial capacity. This study showed that the acetic acid chitosan coating was more effective in reducing L. monocytogenes counts than the lactic acid chitosan coating. The study indicated also that chitosan coatings could be used to control L. monocytogenes on the surface of RTE roast beef. However, it has been found that L. monocytogenes was able to grow on the surface of the RTE roast beef regardless of the chitosan treatments used. Coma et al. [13] also observed the ability of L. monocytogenes to grow on the surface of cheese regardless of chitosan treatments. This could be due to the decreased antimicrobial activity of chitosan lms over time as a consequence of the decreased availability of amino groups on chitosan [147]. The L. monocytogenes strain used during this study was able to grow on the surface of the RTE roast beef product. The initial level of 6.50 log CFU/g increased to over 10 log CFU/g on the control samples at day 21 while samples dipped in chitosan have a count of 7.47.9 for high and low molecular weight chitosan respectively. The data indicated an improvement of
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Fig. 26. Tomato fruit at zero time, (A) similar fruit kept for 13 days into a polypropylene bag fabricated from PP lm covered by 12 alternating chitosan/pectin layers in comparison to similar fruit kept for the same period of time in untreated PP bag (B), and another one kept in open air (C).
the antibacterial capacity of the roast beef when treated with chitosan coating and also that higher molecular weight polymers have slightly lower antibacterial properties. The molecular weight and amino group of chitosan have strong inuence on its antibacterial activity [148,149]. In the Gram-positive bacteria, the major constituent of its cell wall is peptidoglycan and very little protein. The cell wall of Gram-negative bacteria on the other hand is thinner but more complex and contains various polysaccharides, proteins and lipids beside peptidoglycan. It has been found that chitosan activity against fungus to be less efcient as compared with its activity against bacteria [110,150]. On the other hand, results from Bautista-Banos et al. [151] were much different than those of Guo-Jane et al. [152] who emphasized on the efciency of
Fig. 27. Effects of chitosan coating on browning (A), eating quality (B) and disease incidence (C) of fresh-cut Chinese water chestnut during storage at 4 C. Each value is the means for three replicates, and the vertical bars indicated the standard errors. , 0 g (control); 0.5 g/100 ml; , 1 g/100 ml; , 2 g/100 ml [173].
chitosan against fungi. Nevertheless, all these studies indicated that the polycationic nature of chitosan is the key to its antifungal properties in addition to the possible effect that chitosan might have on the synthesis of certain fungal enzymes and that the length of the polymer chain enhances that activity. Bautista-Banos et al. [151] have shown that not only chitosan is effective in stopping the growth of the pathogen, but it also induces marked morphological changes, structural alterations and molecular disorganization of the fungal cells. No et al. [153] studied the antibacterial activities of six chitosan samples and six chitosan oligomers with different molecular weights (Mws) against four Gram-negative (E. coli, P. uorescens, Salmonella typhimurium, and Vibrio parahaemolyticus) and seven Gram-positive bacteria (L. monocytogenes, Bacillus megaterium, B. cereus, S. aureus, Lactobacillus plantarum, Lactobacillus brevis, and Lactobacillus bulgaricus). They found that chitosan markedly inhibited growth of most bacteria tested; however, the inhibitory effects differed with regard to the molecular weight of chitosan and the type of bacterium. Chitosan oligomers also inhibited bacterial growth by 15 log cycles at a 1.0% concentration; however, effects were more limited than those of the chitosan. Chitosan generally showed stronger bactericidal effects for Gram-positive bacteria than Gram-negative bacteria. Devlieghere and Debevere [154] investigated the antimicrobial effect of chitosan, with high deacetylation degree and low molecular weight against several psychrotrophic food-borne pathogens and spoilage micro-organisms and compared to those known from the literature. They found that Gram-negative bacteria were more susceptible, while the sensitivity of the Gram-positive bacteria was highly variable: Brochotrix thermosphacta and B. cereus were very sensitive to the applied chitosan while L. monocytogenes and different lactic acid bacteria were less susceptible. Yeasts, represented by Candida lambica and Cryptococcus humicolus, showed an intermediate sensitivity, the effect of pH on the antimicrobial activity of chitosan on C. lambica is illustrated in Fig. 21. The growth of C. lambica in Sabouraud medium (Oxoid, CM147) was not inuenced by the pH in the absence of chitosan. In a medium containing 0.005% (w/v) chitosan the growth was completely inhibited at pH 4.0, while at pH 6.0, the same chitosan concentration led to a signicant extension of the lag phase and a rather small decrease in growth rate. Devlieghere and Debevere [154] used soluble starch, which caused a pH decrease in the growth medium. Three different chitosan concentrations (0%, 0.005% and 0.01% (w/v)) and starch concentrations (0%, 1% and 30% (w/v)) were tested. Without starch, 0.005% chitosan was enough to cause a signicant retardation of the growth of C. lambica at pH 5.0 and a higher concentration of chitosan even caused inactivation of the yeast. Neither the lag phase nor the growth rate of C. lambica was inuenced by low amounts of starch (1% (w/v)). On the other hand, the activity of chitosan was strongly decreased by high amounts (30% (w/v)) of starch, leading to a signicantly shorter lag phase and a signicantly higher growth rate (Fig. 22), demonstrating the
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Fig. 28. Percentage of infected strawberries as a function of storage time at 10 C for control and 1% CS coated samples. Vertical bars indicate standard deviation [178].
negative effect of the investigated type of starch on the antimicrobial activity of chitosan. It should be mentioned that only the gelatinized starch was investigated, it is possible that native starch interacts in a different way. Zhai et al. [155] investigated the effect of radiation on the antibacterial efciency of chitosan using starch/chitosan blends irradiated at room temperature by electron beam (EB) with beam current of 1 mA and acceleration energy of 2 MeV. In a similar work Liu et al. and Zhai et al. [110,156] have found that the antibacterial activity of chitosan could be enhanced by irradiation. The starch/chitosan blend lms made by irradiation were tested and Figs. 23 and 24 demonstrate the curves of optical density (OD) versus culture time for the blend lms against E. coli. The blend lms exhibited signicant antibacterial activities after irradiation by 30 kGy compared to the pure or un-irradiated blend lms (Fig. 24). OD of the blend lms decreased with irradiation does, which indicate that the antibacterial activity of blend lms improved with increasing the dose. Fig. 24 showed that even at 5 wt.% chitosan content in the blend lms an obvious antibacterial activity could be observed. Furthermore, it was also found that the antibacterial activity of blend lms enhanced by increasing the content of chitosan in blend systems. The antimicrobial activity of chitosan edible lms incorporated with garlic oil (GO), (KS) and nisin (N) against E. coli, S. aureus, S. typhimurium,
L. monocytogenes and B. cereus (common meat product contaminants) has shown that incorporating GO into chitosan lm produced high inhibitory zones for S. aureus, L. monocytogenes and B. cereus. It also reduced the bacterial growth underneath lm of E. coli and S. typhimurium. Inhibitory zone increased by the increasing the GO concentration. L. monocytogenes was the most sensitive against GO incorporated lm followed by S. aureus and B. cereus [157]. Chitosan lm incorporated with potassium sorbate (KS) showed antimicrobial activity against S. aureus, L. monocytogenes and B. cereus. There was no effect on E. coli and S. typhimurium whether in its inhibitory zone or underneath lm. Increasing KS level higher than 100 mg/g of chitosan did not signicantly improve the antimicrobial effect. Similar to GO and KS, incorporating nisin (N) did not show inhibitory zone on E. coli and S. typhimurium. However, N-incorporated chitosan lm revealed growth inhibition underneath lm disks on these organisms. Among inhibited microorganisms, L. monocytogenes was the most sensitive and susceptible to N. The mechanical, physical and antimicrobial properties of Konjac glucomannanchitosannisin ternary blend lm were studied by Li and Xie [158] Konjac glucomannan, a hetero polysaccharide derived from the konjac tuber, consists of 1,4-linked -D-mannose and -D-glucose units in a molar ratio of 1.6:1 with a low degree of acetyl groups at the side chain C-6 position and having an average molecular weight of 0.671.9 million. However, most of the lms do not have practicable mechanical properties or antimicrobial activity. The results of mechanical and physical properties tests showed that the blend lm KC2 (mixing ratio konjac glucomannan 80/chitosan 20) had the maximum tensile strength and a higher transparency greater water solubility and a lower water vapor transmission ratio among other blend ratios. This means that incorporating the chitosan to the konjac glucomannan lm enhanced the mechanical and physical properties remarkably. The antifungal activity of coatings and lms of chitosan/PLA (poly (lactic acid)) based bio-packaging for potential food applications has been investigated by Fimbeau Sebastien et al. [159]. Three mycotoxinogen fungal strains, Fusarium proliferatum, Fusarium moniliforme and Aspergillus ochraceus were tested. Exposure to mycotoxins can produce both acute and chronic toxicities ranging from death to deleterious effects upon, for example, the central nervous, cardiovascular and pulmonary systems. Their general teratogenicity, cancerogenicity and their toxicological properties constitute a high human and animal health risk. The mycotoxins also attract attention because of the signicant economic losses associated with their impact on human health and animal productivity. PLA belongs to the family of aliphatic polyester commonly made from lactic acid, which can be produced from renewable resources such as starch via fermentation processes [160]. It is a thermoplastic, high strength, high
Fig. 29. Appearance of strawberries coated with modied chitosan-based formulation containing limonene and emulsier [179].
Fig. 30. Changes in total viable counts (TVC) of sh sample during frozen storage. Chitosan-coated sh sample (lot I), control sample (lot II) [181].
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Fig. 31. L-value of minimally processed Fuji apples during storage at 5 and 20 C ( control sample, 1% chitosan, 2% AA + 0.5% CaCl2, 2% AA + 0.5% CaCl2 + 1% chitosan). Values are means of three replicates. Vertical bars represent standard deviation [187].
modulus polymer and is considered biodegradable and compostable [161]. Moreover, it is possible to use it for food contact. Since it is relatively hydrophobic it can reduce the hydrophilic nature of chitosan-based lms and consequently improve their moisture barrier properties and decrease the water/matrix interactions. However the lms produced although had antifungal capacity they lacked homogeneity and good mechanical characteristics which made them unpractical as packing materials. The antifungal properties of lms and solutions based on chitosan with different molecular weight at different concentrations have been investigated by Ziani et al. [162]. Surfactants were added to the formulation to assess their impact on treatment efciency. The antifungal activity was conducted against three fungi, Aspergillus niger, Alternaria alternata and Rhizopus oryzae. Results indicated important and signicant differences of the antifungal activity between chitosan based solutions and chitosan based lms. Furthermore, the antifungal activity of the different treatment depended on the type of fungus treated. Thus, chitosan lm treatments were signicantly more effective on A. niger than solution treatments. On the other hand, solution treatments resulted in higher radial inhibition when applied against A. alternata or R. oryzae. The highest radial inhibition was observed against A. alternata (97%) using chitosan solution. The inuence of the other parameters (concentration, molecular weight and surfactant type) on treatment efciency was not as important and their signicance depended on treatment type and fungus nature [163]. Antimicrobial activity of edible coating solutions based on chitosan and blends of chitosantapioca starch with or without potassium sorbate (KS) addition against Lactobacillus spp. and Zygosaccharomyces bailii was studied by Vasconez et al. [1]. They found that the chitosan antibacterial action suffered the antagonist effect of the presence of KS and/or tapioca starch. Interactions between chitosanstarch and chitosanKS, might inhibit chitosan amino groups bonding to the cell
membrane, depressing its antimicrobial activity. The lms studied were not effective against Lactobacillus spp. Therefore, among the lms studied, the one formulated with chitosan and tapioca starch could have possible applications as a barrier against Z. bailii contamination in a high water product of reduced pH. Their results suggested that the chitosan antibacterial action depended on the technique of application. Chitosan was more effective in the coating solution than in the lm matrix. The antimicrobial activities of biodegradable lms of sweet potato starch containing KS or chitosan on E. coli and S. aureus have been studied by Shen et al. [52]. The sweet potato lm control did not show any inhibitory effect on E. coli or S. aureus. Films incorporated with potassium sorbate (KS) 15% or chitosan 5% were found to have an anti-E. coli effect. S. aureus could be effectively suppressed by incorporation of chitosan at 10%. While KS lowers the tensile strength and elongation at break, and raises the oxygen permeability, WVP and water solubility, chitosan has the opposite effect. Among the food-borne bacteria, E. coli and S. aureus are observed in a wide range of food products. Furthermore, they are the human pathogens that cause the most economically important food-borne diseases throughout the world [164] E. coli is the most common bacteria from human feces, and S. aureus is one of the indigenous microbiota on human skin [165]. The antibacterial activity of chitosanstarch lm using microwave treatment has been carried out using agar plate diffusion method [166]. The antibacterial activity of the lm and their same solution has been evaluated against three different test cultures viz. Gram-negative bacteria E. coli, Gram-positive bacteria S. aureus and Gram-positive bacteria Bacillus subtilis. It was found that the solution of chitosanstarch showed inhibitory effect against above said test cultures but lm proved to be negative.
Fig. 32. a-value of minimally processed Fuji apples during storage at 5 and 20 C (control sample, 1% chitosan, 2% AA + 0.5% CaCl2, 2% AA + 0.5% CaCl2 + 1% chitosan). Values are means of three replicates. Vertical bars represent standard deviation.
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Fig. 33. Mean values and standard deviations of rmness, variation with storage time at 5 C ( control sample, 1% chitosan, 2% AA + 0.5% CaCl2, 2% AA + 0.5% CaCl2 + 1 % chitosan). Values are means of three replicates [187].
Fig. 35. Effect of edible coatings on the initial respiration rate of fresh-cut apple slices stored at 5 C for 8 days ( control sample, 1% chitosan, 2% AA + 0.5% CaCl2, 2% AA + 0.5% CaCl2 + 1% chitosan). Values are means of three replicates [187].
Incorporating chitosan and lauric acid into starch based lm showed more effective antimicrobial ability against B. subtilis and E. coli [167], and the lm had synergistic antimicrobial effect when chitosan and lauric acid were combined. The starch-based lm incorporated with lauric acid and chitosan showed better exibility than when purely starch-based lm was formulated. The solution of starch and chitosan with different mixing ratios (w/w) 8:2 and 9:1 were the most effective ratio with greater inhibition on both B. subtilis and E. coli than other solution in agar plate and liquid culture test. The control (pure wheat starch) and antimicrobial (AM) lm (incorporated with chitosan and lauric acid) were produced by casting method. The antimicrobial effectiveness of control (pure wheat starch) and AM lm incorporated with chitosan and lauric acid are shown in Fig. 25A and B. A wide clear zone on solid media was observed for B. subtilis growth inhibition whereas inhibition for E. coli was not as effective as B. subtilis. From the liquid culture test, the AM lms clearly demonstrated a better inhibition against B. subtilis than E. coli. 8. Increasing the shelf life of foods Edible coatings could reduce moisture transfer, restrict oxygen uptake, lower respiration, retard ethylene production, seal in avor volatiles and carry additional functional ingredients (such as antioxidants and antimicrobial agents) that retard microbial growth and potential discoloration. Many authors have investigated chitosan coatings for their potential to enhance the quality and extend the storage life of food products [12,17,168172]. Elsabee et al. [172] used the modied polypropylene lms by chitosan and chitosan/pectin multilayer as a packaging device for storing and increasing the shelf life of tomato they fabricated bags 20 20 cm using 12 multi layers (composed of chitosan/pectin) over corona treated
Fig. 34. Weight loss from Fuji apple slices stored 8 days at 5 C and 85%RH ( control sample, 1% chitosan, 2% AA + 0.5% CaCl2, 2% AA + 0.5% CaCl2 + 1% chitosan). Values are means of three replicates [187].
polypropylene (PP) lms. A fresh tomato fruits of regular size (50 g) were collected cleaned and stored in bag (A). Another similar fruit was stored in regular PP bag (B) and a third one was kept in air (C). The three species were kept in a refrigerator at 4 C. The above experiment was done in triplicate. The samples were investigated at intervals, and after 13 days the samples were compared and Fig. 26 shows the state of the three samples. It can be seen that samples B and C deteriorated completely while the sample in the treated bag was kept almost intact with no apparent rotting infection. Application of chitosan coating to browning control and quality maintenance of fresh-cut Chinese water chestnut (CWC) was investigated by Pen and Jiang [173]. Fresh-cut CWC were treated with aqueous solution of 0.5, 1 or 2 g chitosan/100 ml, placed into trays overwrapped with plastic lms, and then stored at 4 C. The result of their work is shown in Fig. 27 surface discoloration of fresh-cut CWC appeared after 3 days of storage at 4 C and became more serious after 6 days, while the eating quality decreased markedly. Treatment with chitosan coating delayed the development of the discoloration. Furthermore, increasing the concentrations (from 0 to 2 g) of chitosan/100 ml coating enhanced the inhibition of the discoloration and resulted in better appearance maintenance. Application of chitosan coating also inhibited effectively the disease development of fresh-cut CWC. In the current study, as the use of chitosan coating in combination with low temperature storage was effective for control of overgrowth of spoilage organisms, the surface discoloration of the fresh-cut CWC appears to be major factor limiting storage life. Carrot (Daucus carota L.) is one of the most popularly consumed vegetables, but marketing is limited by its fast deterioration during storage, due to physiological changes that reduce its shelf life [174]. The product loses its rmness and develops odors characteristic of anaerobic catabolism, due to the high respiration rate and microbiological deterioration [175]. Minimally processed carrot quickly loses their bright orange color during storage, developing a whitish appearance or white blush on its surface. Durango et al. [14] developed an edible antimicrobial coating based on a starchchitosan matrix to evaluate its effect on minimally processed carrot by means of microbiological analyses. The results of this experiment showed that the use of an antimicrobial coating consisting of chitosan-added yam starch is a viable alternative in controlling the microbiota present in minimally processed carrot, since the growth of lactic acid bacteria, total coliforms, psychrotrophs, yeasts and molds and mesophilic aerobes, was substantially inhibited by the application of 1.5% chitosan coating. Based on the concept of protection barrier technology, the use of such coating may contribute to improve safety in minimally processed carrot thereby prolonging its shelf life. Coating may be applied on minimally processed fruits and vegetables, combined to other types of controls, such as quality raw material, hygienic processing conditions and storage temperatures. The combination of these treatments
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as barrier offers a greater potential for shelf-life extension of minimally processed vegetables. Mango pulp is very perishable and so has a short shelf life, which both marketers and consumers would like to be longer. Chien et al. [176] manually treated sliced mango with aqueous solutions of 0%, 0.5%, 1% or 2% chitosan; Chitosan coating retarded water loss and the drop in sensory quality, increasing the soluble solid content, the acidity and ascorbic acid content. It also inhibited the growth of microorganisms. The data reveal that applying a chitosan coating effectively prolongs the quality attributes and extends the shelf life of sliced mango fruit. Chitosan (CS1, 1% w/w solution) was used for producing chitosan lm and used for glazing skinless pink salmon lets by Sathivel et al. [171] Chitosan glazing delayed lipid oxidation in skinless pink salmon lets after eight months frozen storage. Chitosan lm was a very good barrier to oxygen, while having low WVP. Chitosan coated lets had a higher thaw yield than that of the control non-glazed. Their study demonstrated the potential of chitosan solution as an edible glazing for pink salmon llets. Casariego et al. [26] aimed to determine the effects of the concentrations of glycerol and sorbitol (as hydrophilic plasticizers), Tween 80 (as surfactant) and chitosan on the wettability of Cuban chitosan-based edible coatings in view of their application on tomato and carrot and to develop a model allowing the optimization of coating composition. Their results indicated that chitosan obtained from lobster of the Cuban coasts can be recommended as an edible coating to be applied on fruits and vegetables, possibly contributing to extend their shelf life. Strawberry (Fragaria x ananassa) is a highly perishable nonclimacteric fruit. It must be harvested at full maturity to achieve maximum quality in terms of visual appearance (freshness, color and absence of decay or physiological disorders), texture (rmness, juiciness and crispness), avor and nutritional value (vitamins, minerals, dietary ber and phytonutrients). Gray mold, caused by Botrytis cinerea Pers. Fr., is the most economically signicant postharvest pathogen of strawberry fruits. Strawberry spoilage after harvest can also occur by mechanical injury and desiccation. Low storage temperatures and modied atmospheres with elevated CO2 levels are common tools for avoiding, at least partially, mold growth and senescence, and for extending fruit shelf-life. However, prolonged exposure of berries to high CO2 concentrations can cause off-avor development [177]. Hernandez-Munoz et al. [178] studied the effect of chitosan coatings combined with calcium gluconate on strawberry (Fragaria x ananassa cv. Camarosa) quality attributes during refrigerated storage. Strawberries were treated with 1% or 1.5% chitosan acetate solution, with or without the addition of calcium gluconate. Assessment of the treatments is based on their effects on fungal decay, respiration rate, quality attributes, and the visual appearance of strawberries stored for 6 days at 10 C. Strawberries were randomly distributed into ve groups. Four groups were assigned to one of four treatments while the fth group provided the untreated control. The treatments consisted in immersing fruits for 5 min in: (a) 1% chitosan acetate; (b) 1.5% chitosan acetate; (c) 1% chitosan+0.5% calcium gluconate; and (d) 1.5% chitosan +0.75% calcium gluconate solution. Fruits were allowed to dry for 2 h at 20 C and were subsequently stored at 10 C and 705% RH. Uncoated strawberries showed signs of fungal decay after the third day of storage at 10 C (Fig. 28). After 6 days of storage, 33.5% of uncoated fruit was infected by molds while no sign of fungal decay could be detected by visual inspection of fruits coated with 1.5% chitosan or 1.5% chitosan+0.75% calcium gluconate. Of the fruit coated with 1% chitosan, 12.5% was observed to be infected on the sixth day of storage. In summary, chitosan coating was seen to delay fruit senescence and fungal decay of strawberry fruits stored at 10 C and 70 5% relative humidity. Vu et al. [179] developed edible bioactive coating based on modied chitosan for increasing the shelf life of strawberry during storage. They found that, the functionalized chitosan-based edible coating could become a promising method to carry specic antifungal agents without
detrimental effects on strawberries or other fruits. In this context, future research will focus on developing a new coating formulation which consists of modied chitosan, lipid (fatty acids, acetylated monoglycerides, etc.), plasticizers (polyols) and reinforcement agents (nanocellulose) to improve the functional properties of coatings applied on strawberries and increase the shelf life of strawberries during storage. Fig. 29 shows the appearance of strawberries coated with modied chitosan. Duan et al. [180] used acid-soluble chitosan (ACS) and water-soluble chitosan (WCS) for enhancing the shelf life and retaining the antioxidant properties of pre-washed, ready-to-eat high bush blueberry cultivars under commercial storage conditions. Their results from this study indicate the possibility of using edible coatings to develop ready-to-eat fresh blueberries with no reduction in shelf life. The key for success is using an appropriate coating material, container, and method of applying the coatings. In this study, different coatings showed various effects on the post-harvest quality of pre-washed fresh blueberries. Both acid-soluble and water-soluble chitosan coatings showed potential for reducing rate of decay of blueberry during room temperature storage. The effects of chitosan coating on quality and shelf life of silver carp during frozen storage were investigated by Fan et al. [181]. Fish samples were treated with aqueous solution of 2% chitosan, and then stored at 3 C for 30 days. Total viable counts are shown in Fig. 30. Fish samples were given a dip treatment in 2% chitosan solution (lot I) and in 1% glacial acetic acid (lot II) as a control, respectively for 120 min and then drained well. After that, they were individually packed in plastic trays and airproofed with polyvinyl dichloride (PVDC); then all the packs were kept in a refrigerator maintained at 3 C for 30 days [182,183]. Fish samples were taken randomly every 5 days for microbiological, chemical and sensory evaluation. The results of microbiological (total viable count), chemical (pH, TBA, TVB-N, and K-value), and sensory evaluation analyses indicate that chitosan coating on silver carp (Hypophthalmichthys molitrix) can lead to retention of the good quality characteristics and extension of the shelf life during frozen storage. Shelf-life extension of Ricotta cheese was studied by Di Pierro et al. [184] using chitosan/whey protein lm as active coating and stored under modied atmosphere at 4 C. The chitosan/whey protein lm had 35% and 21% lower oxygen and carbon dioxide permeability, respectively, and about three times higher WVP than lm prepared with chitosan alone, they found that edible lm reduced growth of microbial contaminants and extended the shelf-life of the product packed under modied atmosphere. The coating delayed the development of undesirable acidity, better maintained the texture and did not seem to modify sensory characteristics. It is possible that the benets derived from the biopolymers can also be realized with other dairy products. A composite coating has been developed by Maqbool et al. [185] by combining Arabic gum and chitosan to evaluate its potential to control anthracnose in banana during and after cold storage. They found that Arabic gum alone did not show any fungicidal effects while the combination of 1.0% chitosan with all tested Arabic gum concentrations had fungicidal effects. However, the potato dextrose agar (PDA) medium amended with 10% Arabic gum incorporated with 1.0% chitosan showed the most promising results among all treatments in suppressing the mycelial growth (100%) and conidial germination inhibition (92.5%). Xing et al. [186] investigated the effect of chitosan coating containing anti-browning agents and modied atmosphere packaging (MAP) on the browning and shelf life of fresh-cut lotus root stored at 4 C for 10 days. Their study has industrial impact where fresh-cut vegetables have drawn the attention of industry as a novel lightly processed product. Both edible coating and (MAP) treatment cause changes in atmosphere composition and respiration rate of lotus root slices. This combined treatment could be used to control the browning and improve the storage life of this fresh-cut vegetable. This information could be useful for the development of novel application to edible coating and (MAP) design for lightly processed lotus root.
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The effect of coatings in combination with anti-browning agents (1% chitosan; 2% ascorbic acid+0.5% CaCl2 and 2% ascorbic acid+0.5% CaCl2 +1% chitosan) on minimally processed apple slices was studied during storage by Qi et al. [187]. Their results show that chitosancoating treatments effectively retarded enzymatic browning on minimally processed apples during storage and they effectively retarded or avoided tissue softening, apple slices underwent a little loss of rmness. Chitosan-coating did not perform very well as water vapor barriers in apple slices. Figs. 31 and 32 show effects of chitosan-coating on L* value (lightness) and a* value (colorimetric) of apple pieces. In comparison with control sample, chitosan sample almost remained stable L* and a* values at 20 C for 24 h. L* values of all sample decreased rapidly after 24 h for 20 C and decreased slightly after 24 h at 5 C (Fig. 31B). But the a* values of all samples increased rapidly after 24 h at 20 C and increased slightly after 24 h at 5 C (Fig. 32B). This indicated that low temperature storage was better than high temperature storage to retard browning of apple pieces. Their results (Fig. 33) showed that 0.2% AA+ 0.5% CaCl2 + 1% chitosan treated apples had the highest rmness, since calcium chloride, a known rming agent, helped apple slices maintain rmness. Chitosan at 1% content treated apples also showed constant rmness throughout 8 days of storage due to low level of Ca2+ contained in aqueous chitosan solution. In contrast with chitosan coatings, non-coated apples showed reduced rmness. After 2 days of storage, control apples lost around 19% of their weight, while coated apples lost 15% of their weight (p> 0.05). Chitosan coatings on apple slices did not prove to work effectively as water vapor barriers during the entire storage period (Fig. 34). The physical damage or wounding caused by peeling and cutting increases respiration rate within minutes, thus the need to reduce initial respiration rate is critical in extending shelf-life of minimally processed fruits so that Qi et al. [187] studied also the respiration rate as shown in Fig. 35. The effect of chitosan edible coatings on initial respiration rate, all formulations tested reduced initial respiration rate, and 2% AA+0.5% CaCl2 +1% chitosan had a signicantly greater effect than others. Minimally processed broccoli was coated with either chitosan or carboxymethyl-cellulose (CMC) with or without a previous application of a mild heat shock of 1.5 min at 50 C. This work was made by Ansorena et al. [188]. They found that the edible coatings, chitosan and carboxymethyl-cellulose, seemed to have a benecial impact on quality retention of minimally processed broccoli by retarding their weight loss, browning and yellowing processes, reducing stem hardening, microbial growth and improving total chlorophyll and ascorbic acid retention. Moreover, both edible coatings were able to inhibit the orets opening, which is an important quality improvement for broccoli. However significant differences were observed among these coatings: chitosan was superior during storage maintaining broccoli in higher quality levels relative to CMC coating by reducing total microbial counts, hardening, O2 consumption and improving ascorbic acid retention. 9. Conclusion In view of the severe environmental pollution caused by plastic food packaging, there is a considerable interest in edible and biodegradable lms made from renewable and natural polymers. Chitosan, a natural, non-toxic, biodegradable polymer, available commercially, has been employed in a variety of applications in food industry as a new edible packaging material to control the food quality; it can form transparent lms, which may nd application in a variety of packaging needs. Blending of chitosan with other natural polymers gives lms and coatings with good properties, chitosan addition in edible lms leads to good lm forming and mechanical properties, no toxicity, biodegradability, relative more hydrophobic nature that could provide higher moisture barrier and water resistance. Many researchers studied different properties of chitosan and chitosan blends (preparation, physical, mechanical, rheological, water
vapor permeability and antimicrobial properties) their results show that chitosan and chitosan blends are extremely promising materials for bio-based active lms preparation and that chitosan based edible lms and coatings can be useful for preserving and extending the shelf life of foods. References
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Materials Science and Engineering C 33 (2013) 18191841

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Materials Science and Engineering C

Chitosan based edible lms and coatings: A review

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