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LWT - Food Science and Technology 43 (2010) 837–842

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LWT - Food Science and Technology
journal homepage: www.elsevier.com/locate/lwt

Review

Chitosan application for active bio-based films production and potential in the food industry: Review
Mohammed Aider*
´ Department of Food Engineering, Pavillon P. Comtois, Laval University, Quebec, Canada G1K 7P4

a r t i c l e i n f o
Article history: Received 12 June 2009 Received in revised form 5 October 2009 Accepted 24 January 2010 Keywords: Chitosan Bioactivity Food Preservation Antibacterial Film Package

a b s t r a c t
During the past decade, there was an increasing interest to develop and use bio-based active films which are characterized by antimicrobial and antifungal activities in order to improve food preservation and to reduce the use of chemical preservatives. Biologically active bio-molecules such as chitosan and its derivatives have a significant potential in the food industry in view of contaminations associated with food products and the increasing concerns in relation with the negative environmental impact of conventional packaging materials such as plastics. Chitosan offers real potential for applications in the food industry due to its particular physico-chemical properties, short time biodegradability, biocompatibility with human tissues, antimicrobial an antifungal activities, and non-toxicity. Thus, chitosanbased films have attracted serious attention in food preservation and packaging technology. This is mainly due to a fact that chitosan exhibits high antimicrobial activity against pathogenic and spoilage micro-organisms, including fungi, and both Gram-positive and Gram-negative bacteria. The aim of the present review was to summarize the most important information on chitosan from its bioactivity point of view and to highlight various preparative methods used for chitosan-based active bio-films and their potential for applications in the food preservation and packaging technology. Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction The modern food industry is facing challenges and requires specific approaches to surmount theme. One of these challenges is related to the packaging of food products with a short shelf life period. Although the use of conventional packaging materials such as plastics and their derivatives is effective for food preservation, they create serious environmental problems that continue to present the food industry as a source of pollution and social concerns. This problematic requires that all stakeholders in this industry and especially scientists specializing in the food engineering and packaging to seek alternatives to overcome this serious problem which is related to the packaging materials. A nonnegligible aspect which is the total cost of the final product is also related to the packaging materials because it is well known that the contribution of the packaging to the product total cost is highly significant. So, the search for more economical packaging materials is a very important subject in the food industry. Edible bio-based films have been investigated for their abilities to avoid moisture loss or water absorption by the food matrix,

* Corresponding author. Tel.: þ1 418 656 2131x4051. E-mail address: mohammed.aider@fsaa.ulaval.ca (M. Aider) 0023-6438/$ – see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.lwt.2010.01.021

oxygen penetration to the food material, aromas loss and solute transports (Dutta, Tripathi, Mehrotra, & Dutta, 2009). Until now, the edible and biodegradable bio-based films are always not meant to totally replace the conventional packaging materials (Schou et al., 2005). However, the use of active bio-based films as packaging materials is still one of the most promising ways for effective methods of maintaining food quality. One of the most perspective active bio-film is the one based on chitosan combined with different materials such as plant and animal proteins, polysaccharides and antimicrobial peptides (bacteriocin) such as nisin and divergicin which is a new class bacteriocin produced by Carnobacterium divergens (Tahiri et al., 2004; Tahiri, Desbiens, Lacroix, Kheadr, & Fliss, 2009). Chitosan; a linear polysaccharide consisting of (1,4)-linked 2amino-deoxy-b-d-glucan, is a deacetylated derivative of chitin, which is the second most abundant polysaccharide found in nature after cellulose. Chitosan has been found to be non-toxic, biodegradable, biofunctional, biocompatible and was reported by several researchers to have strong antimicrobial and antifungal activities (Darmadji & Izumimoto, 1994; Jo, Lee, Lee, & Byun, 2001). Chitosan has been compared with other biomolecule-based active films used as packaging materials and the reported results showed that chitosan has more advantages because of its antibacterial activity and bivalent minerals chelating ability (Chen, Zheng, Wang, Lee, & Park,

Chitosan films have been successfully used as a packaging material for the quality preservation of a variety of foods (Ouattara.3) at which this functional group carries 50% of its total electric charge allows the interactions with negatively charged microbial cell membranes.5) increase the antimicrobial activity of chitosan because of its higher solubility and protonation in the acidic pH interval. This effect can be considered as synergetic for the reasons of the hurdle effect of the acid stress on the bacterial cells (Rhoades & Roller. Low pH values (up to 5. 2000). it is well recognized that the surrounding matrix has the greatest influence on the antimicrobial activity of chitosan. However.838 M. As theory. ionic strength and presence of solutes susceptible to react with chitosan through electrostatic interaction and/or covalent binding which can screen or completely block the reactivity of the active amine group. However. All these experimental findings are highly dependent of several intrinsic and extrinsic factors that affect the antimicrobial and antifungal activity of chitosan. 3. Piette. 2009) and that the degree of polymerisation of at . 1964). & Roller. 1989). A study on the effect of chitosan on yeast growth was reported and authors demonstrated that baker’s yeast Saccharomyces cerevisiae showed halted fermentation activity by chitosan concentration as little as 3. Cytosporina sp.1. At the same time. 2004). Begin. the growth of which was stopped by 4 mg/L chitosan in a liquid nutrient medium (Kendra & Hadwiger. even if low molecular weight chitosan is suitable. pectins. 3.6 mg/L in a buffer system solution (Ralston. High deacetylation degree increases chitosan solubility and charge density. there is no direct evidence demonstrating this behaviour against bacteria. lower molecular weight fractions have little or no antibacterial or antifungal activity. However. inorganic polyelectrolytes such as polyphosphate. 1999). even if this is a well recognized explanation of chitosan antimicrobial effect. it has been suggested that the positive charge of the amine group (NHþ) at pH values lower than 3 the pKa (pH < 6. Because of its unique cationic character. molecular weight. it is generally recognized that yeasts and moulds are the most sensitive group to chitosan. particularly the degree of deacetylation. The mechanism of the antimicrobial activity of chitosan and its derivatives is well studied. However. Factors influencing antibacterial activity of chitosan films 3. This behaviour can be explained by a fact that low molecular weight chitosan is more soluble in aqueous media than high molecular weight chitosan and this solubility is of great importance to react with the active sites of the targeted microorganisms. A synergetic effect of chitosan positive charge and acidic media (low pH) has been also pointed out by several researchers. as a result of its greater antimicrobial activity under these conditions (Quintavalla & Vicini. when the gradient of ion concentration between the inside of the polymer matrix and the outside environment was high. Du. occasionally. the target organism and the conditions of the medium in which it is applied. 2.. It has been demonstrated that lower molecular weight chitosan with an average molecular weight less than 10 kDa have greater antimicrobial activity than native chitosan (Dutta et al. Effect of pH It has been shown that the antimicrobial activity of chitosan and chitosan-based films increases by decreasing pH.. It was shown that at 37  C the antimicrobial activity of chitosan was significantly higher than at refrigeration temperatures (Tsai & Su. even if the available literature information on chitosan antimicrobial activity vary somewhat and.Food Science and Technology 43 (2010) 837–842 2002). Highly deacetylated chitosans are more antimicrobial than those with a higher proportion of acetylated amino groups. The aim of the present review was to highlight the potential of chitosan as ingredient for active bio-based films production and to summarize the different methods used for chitosan-based films preparation and their perspectives in the modern food packaging technology. and with films containing cinnamaldeyde. Antimicrobial films have been prepared by including various organic acids and essential oils in a chitosan matrix. Aider / LWT . Strongest inhibition was observed on surfaces with lower water activity values (bologna) onto which acid release was slower. Antimicrobial activity Several studies showed that chitosan is characterized by an antimicrobial activity against a wide range of target microorganisms. This factor is a good indication that the promising results obtained in vitro with model systems in buffers or microbiological media are not necessarily applicable in real food systems which are complex matrices. 2001). Tracey. the above mentioned particularity can decrease chitosan antimicrobial effect (Kubota & Kikuchi. & Holley. & Wrench. similar antifungal activity has been reported against the mould Fusarium solani. Temperature effect on chitosan antimicrobial activity was also reported.2. isolate was completely inhibited by 75 mg/L chitosan. liquefaciens was delayed or completely inhibited after storage during 21 days at 4  C. it was shown that the antimicrobial activity of the bio-based films under study did not affect growth and activity of lactic acid bacteria. followed by Gram-positive and Gram-negative bacteria. Wang. Ahvenainen. nevertheless a degree of polymerisation of at least seven basic units (glucosamine) is required. a phenomenon which is susceptible to cause a leakage of intracellular constituents (Helander. Simard. 2009). chitosan has the potential to bind to many different food components such as alginates. proteins. and the ability of these bio-based films to inhibit the growth of indigenous (lactic acid bacteria and Enterobacteriaceae) or inoculated bacteria (Lactobacillus sakei and Serratia liquefaciens) onto the surfaces of vacuum-packed cured meat products have been investigated. Rhoades. Intrinsic factors Chitosan intrinsic factors significantly affect its antimicrobial and antifungal activity. contradictory findings have been reported. it has the particularity to bind to bacterial cell wall through electrostatic interaction and may cause damage by perturbing solute or nutrients transport to the cell (Liu. 1979). then decreased as the release of acids progressed. Also. 2002). & Ohtakara. Release of organic acids (acetic and propionic acid) was found to be initially fast. Recently. whereas the growth of Enterobacteriaceae and S. & Sun. 2000). a chitosan–starch film has been prepared using microwave treatment which may find potential application in the food packaging technology (Dutta et al. 1984). Variation in sensitivity between closely related microorganisms was illustrated in an experiment in which phytopathogenic fungi were screened for sensitivity to chitosan in liquid media. and positively charged ion species through donor/acceptor interaction. while a second isolate of the same genus was completely unaffected by chitosan concentration up to 1000 mg/L (Allan & Hadwiger. Izume. NurmiahoLassila. It has been shown that low molecular weight chitosan with an average molecular weight less than 10 kDa have greater antimicrobial activity than native chitosan of high molecular weight (Uchida. especially pH. In complex food matrices. These two factors are important for chitosan adhesion to the bacterial cell. Chitosan antimicrobial activity varies considerably with the type of chitosan. This can be explained by the temperature effect on chitosan solution viscosity which decreases as temperature increases. 1998). Chitosan is a unique cationic polysaccharide in the nature.

The obtained results showed that chitosan nanoparticles and copper-loaded nanoparticles could inhibit the growth of various bacteria tested. Chitosan-metal complex Five chitosan–zinc complexes with different zinc content were prepared (Wang. Authors stated that a decrease of water content decreased the total amount of the active sites that can participate in the sorption phenomenon. Chitosan-polysaccharides based films In the food industry. which were from 2 to 8 and 4 to 16 times higher than those of chitosan alone and zinc sulphate. The temperature of film preparation practically does not influence the sorption properties. Hu.. Authors reported that the exposure of S. and the minimum bactericidal concentration (MBC) values of nanoparticles reached 1 mg/ mL. Chitosan–tapioca starch based edible films and coatings Antimicrobial activity of edible coating solutions based on chitosan and blends of chitosan–tapioca starch with and without ´ potassium sorbate addition was studied (Vasconez et al.1. Chitosan concentration for nanoparticles preparation was 2. Their minimum inhibitory concentration (MIC) values were less than 0. The chitosan–Zn complexes showed wide spectrum of effective antimicrobial activities. Du. coli and S aureus. The antibacterial effect has been shown to increase by increasing zinc ions content in the complex. thermal stability and scanning electron microscopy of the films were analyzed. & Liu. In the study reported by Buzinova and Shipovskaya (2008) on chitosan-based films.3. 2004) and their effects have been tested against pathogenic micro-organisms. Chitosan solubility and charge density which allows the appearance of the antimicrobial effect is directly affected by the degree of deacetylation (Kubota. 2009). 2002). Tatsumoto. 3.. It was found that the chitosan–Zn complexes with different zinc content had different molecule structure. A salmon slice coating assay showed that the chitosan solution was the best coating since aerobic mesophilic and psychrophilic cell counts were reduced. & Zou. Hydroxypropyl methylcellulose edible films with chitosan Chitosan with an average molecular weight of 71. & Krochta. Chitosan films were formed by casting 2% (w/w) chitosan solution is 2% (v/v) acetic acid solution. This particularity can be used for active chitosan-based films for different foods coating. Clinical tests of four film samples have shown their high efficiency at burn treatment. The solvent was evaporated at 22 and 45  C. Authors showed that moisture content of chitosan films had significant effect on their bactericide effect which decreased by decreasing film moisture content.4. they have attracted particular attention and have been considered in the food preservation because of their ability to be used as food coating materials to extend the shelf life of different food products (Franssen. 2004). 4.14 and 3. non-polluting ´ and low cost (Vasconez. Sorption and bactericides properties of chitosan films The sorption and bactericide properties of chitosan films with various humidity and preparation temperatures were studied. Campos. & Toya.Food Science and Technology 43 (2010) 837–842 839 least seven monomeric units is required to get significant antibacterial effect. This was demonstrated by the decreased diameter of the inhibition zone. & Gerschenson. 2003). Chitosan–tapioca starch based films reduced Zygosaccharomyces bailii external spoilage in a semi-solid product but were not effective against Lactobacillus spp. pH and weight loss remained acceptable throughout the refrigerated storage period. 2008).15 mg/mL and tripolyphosphate concentration was 0. coli and S aureus and it has been shown that diameter of the inhibition zone was 5 and 3 times higher than control for E. coli. The reported results suggest that antibacterial action is dependent on the application technique due to the fact that chitosan is more available in a coating solution than in a film matrix. The agar well diffusion assay showed an antagonist effect of chitosan against Lactobacillus spp. Salmonella choleraesuis. Aider / LWT .25 mg/mL. especially cheese and meat products such as fermented sausages (Wang et al.3 and 0. it was reported that the antibacterial activity of chitosan–Zn complex was better than its antifungal activity. choleraesuis to the chitosan nanoparticles led to the disruption of cell membranes and the leakage of cytoplasm (Qi et al. Jiang. Also it was demonstrated that highly deacetylated chitosan showed more antimicrobial activity than chitosan with higher proportion of acetylated amino groups. For these reasons. when potassium sorbate and/or tapioca starch were present. Chitosan/ tripolyphosphate nanoparticles were prepared and incorporated in hydroxypropyl methylcellulose films. 3. water vapour permeability.000313% (w/v) of chitosan–Zn concentration.. Sano. 2009). Interactions between chitosan–starch and/or potassium sorbate could affect film physical properties and the antimicrobial activity of chitosan. 2009). Very low molecular weight fractions have little or no antimicrobial activity. respectively. and bactericide effect increase by increasing chitosan film humidity. barrier properties against pathogenic micro-organisms. The mechanical properties. Xu. Rumsey.6 mg/mL. aesthetic appearance. Flores. Authors showed that the addition of chitosan reduced ´ water vapour permeability and solubility of starch films (Vasconez et al. respectively.2. Alvarado. Zheng & Zhu. Antibacterial activity of the produced chitosan-based films has been evaluated against E. Antimicrobial activities of the complexes were evaluated against 11 species of bacteria and fungi in vitro. edible active bio-based films and coatings offer many advantages because or their edibility. and Staphylococcus aureus was evaluated by calculation of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) (Qi.5 times. 4. 2004). sorption rate. under the studied conditions. However. biocompatibility with human tissues. 2004). Chitosan-based film samples have been found to possess high transport properties to water and hydrochloric acid vapours and to show bactericide activity. Decrease of film moisture content from 22% (w/w) down to 12% (w/w) decreased the bactericide activity by 2. This finding can be exploited in the cheese-making industry for cheese coating with chitosan films in the maturation chambers in order to avoid mould and pathogenic bacteria growth on cheese surface (Buzinova & Shipovskaya. non-toxicity. increasing the collapse of the pores and thereby improving film tensile properties and water . The swelling degree. 2000. extending global quality up to 6 days. 4.M. The antibacterial activity of chitosan nanoparticles and copperloaded nanoparticles against E..3 kDa and a degree of desacetylation of 94% has been successfully used for edible hydroxypropyl methylcellulose films preparation. The highest antibacterial activity has been shown against Escherichia Coli and Corynebacterial at a minimal inhibitory concentration (MIC) value of 0. Salmonella typhimurium. Authors showed that chitosan nanoparticles tend to occupy the empty spaces in the pores of the matrix. It has been shown that incorporation of chitosan nanoparticles in the films significantly improved their mechanical and film barrier properties. It has been found that sorption capacity of chitosan films was significantly affected by moisture content of the films. chitosan with viscosity average molecular weight of 280 kDa and degree of deacetylation of 81% was used.

It was shown the by increasing the protein amount the elongation at break and tensile strength decreased. After 2 weeks.1. which could be leached out easily. The yellow or brown coloration has been reported to be associated with the Maillard reaction (Damodaran. Delgadillo. Chitosan/pectin laminated films with lactic acid Chitosan films might be laminated to pectin films as it was suggested by Lehr. As a consequence. the blended bio-based films. lactic acid was used to replace glycerol in the pectin film without significant change in dynamic mechanical properties. The prepared films were round scad (Decapterus maruadsi) protein-based. When attacked by natural fungi. Colour of the studied films was also evaluated and it was reported that all films became darker. chitosan molecules or between chitosan and proteins might induce the migration of glycerol to the surface. in the absence of transglutaminase when compared with those obtained with chitosan alone (Di Pierro et al. The storage modulus and loss modulus of chitosan/pectin laminated films were significantly greater than respective moduli of chitosan films alone. They also offer the potential of membrane construction through cross-linking of amino groups or insolubilization through alteration of pH (Yang & Zail. but protein solubility decreased continuously during the storage period. Angulo. 1993. 1996). Water interacts with the polymer matrix of a strongly hydrophilic polymer and the water vapour permeation of the film increases (Cervera et al. Chitosan films are compatible with animal tissue. the interaction between protein molecules. Round scad protein–chitosan based film Recently. The difference in composition and hydrophilicity between both surfaces increases with the amount of protein incorporated in the film.. This yellowness increased as the storage time was increased. 4. Authors of the study showed that during the storage period of 8 weeks under conditions of 54% relative humidity and temperature of 28–30  C.Food Science and Technology 43 (2010) 837–842 vapour permeability (Pereira de Abreu. in the reported study by Ferreira et al. Prodpran. In addition. may have useful applications in those food systems where the edible bio-based films should break up during the cooking such as pizza or mastication process. 2007). chitosan films have a built-in source of nitrogen to enhance biodegradation. At the same time. The yellowness was the most pronounced trend of the films colour. Round scad muscle proteinbased films were used to cover dried fish powder. a combination of hydrogen bonding. No significant differences in moisture content of all samples covered with different films were recorded. 1979). Aider / LWT .. The prepared films have included control films without palm oil and chitosan addition. 1994) was selected for investigation with a readily available commercial chitosan. & Cruz. Chitosan-protein based films 5. The samples covered with the film containing 25% palm oil and 40% chitosan showed lower thiobarbituric acid reactive substances values and yellowness than the other samples during the extended storage up to 21 days. 1993. It was suggested that round scad proteinbased film incorporated with palm oil and chitosan could be a promising packaging material to prevent lipid oxidation in oil enriched foods (Artharn et al. Chitosan/lactic acid films were cast upon pectin films with either glycerol or lactic acid as plasticizer to give clear laminated films with dynamic mechanical properties similar to those of pectin films alone (Hoagland & Parris. Addition of palm oil to the hydrophilic polymer improved the moisture barrier properties of film to some extent. Chitosan–whey protein films Recently. Water vapour permeation of pectin or chitosan films made with lactic acid was unchanged by lamination (Hoagland & Parris. Schacht. authors of the present work did not report any changes in water barrier properties throughout the storage time up to 4 weeks. A chitosan film laminated to a pectin film could be expected to alter water vapour permeability (WVP) and water solubility. tensile strength of the films without and with 25% palm oil or 25% palm oil in combination with 40% chitosan increased continuously. especially at amino group or hydroxyl groups (Park. Nunes. 5. & Krochta. The surface richer in protein was more hydrophobic than that richer in chitosan. and films prepared with 25% palm oil and 40% chitosan as protein substitution. 2009).840 M. Jun. pectin and lactic acid for biodegradable films processing and use in the food industry as active coating materials. but in general. For this reason. only chitosan films had mucoadhesive capability with standard pig intestinal mucosa. while elongation at break significantly decreased when the storage time reached 8 weeks. Very strong electrostatic interactions can be expected to produce a precipitate or a thin membrane. 1984). including the human eye. Paseiro Losada. 2009). Authors reported that the obtained chitosan–whey protein based bio-based films were biphasic and characterized by a compositional gradient with the downward film surface containing a lower amount of protein than the upward surface.2. This study seems to be interesting because of the potential of chitosan. 2009) and film were studied for storage stability. and Junginger (1992). Avena-Bustillos. 5. except those covered with high density polyethylene films which had the lowest moisture content. this parameter had little effect on water vapour permeability of the prepared films. Authors explained this finding as fellows: in the presence of oil. moderately unesterified pectin (65% degree of methylation) which forms good films with glycerol as plasticizer (Coffin & Fishman. & Benjakul. It was also reported that chitosan films were extremely good oxygen but poor water vapour barriers because of their hydrophilic nature. .. glycerol was most likely imbibed in the film matrix and could not be leached out easily. To prevent fungal growth. The thermal stability of the films increased with addition of nanoparticles (Habig McHugh. 2001). Glycerol could bind with chitosan. the capability to produce blend chitosan–whey protein bio-based films at acidic pH carrying a high amount of protein was demonstrated even though under the studied conditions a pure whey protein film could not be obtained (Ferreira. & Lopes-da-Silva. 2006). Bouwstra. 2009). They also showed that film solubility slightly increased. Authors stated that although some of the film functionality might be compromised due to the incompatibility between the polysaccharide (chitosan) and the protein components within the film matrix. Among all the natural polysaccharide wet films tested. and are resistant to microbiological growth (Allan & Hadwiger. 1996). 1996).3. Other previous studies have also shown a reduction of the mechanical resistance and flexibility of whey protein–chitosan films. but a subject needs further studies. films with 25% palm oil as glycerol substitution additive. (2009) it was anticipated that the blend bio-based films would also have useful antimicrobial properties due to the presence of chitosan.. de Moura et al. a more rigid structure of polymers in film matrix was formed and glycerol was most likely imbedded in the matrix tightly. 2004). highly promising study on active chitosan-based film processing has been reported (Artharn. including pectin. especially those with intermediated protein amount. and compatible water activities makes possible a stable interface between pectin and chitosan film. Therefore. electrostatic interactions between carboxylate groups of pectin and protonated amino groups of chitosan. & Marsh.

On the other hand. respectively. Each film was easily peeled from the dish by inserting a razor blade at the film-rim interface and pulling up around the edge with forceps (United States Patent 5919574). cherries. Cellulose derivatives such as hydroxyl-propyl cellulose. The same process can be used for chitosan-based active film preparation using the extrusion methodology which is widely used in the packaging film preparation industry. After that. fresh beans. w/w) cross-linked with transglutaminase (TGase) or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) was studied (Kolodziejska & Piotrowska. low density polyethylene (LDPE).. Filtrate (25–30 mL) was poured directly into a plastic Petri plate or onto a chitosan film preformed in a similar plastic Petri plate. Wibowo et al. & Moghadam. Ghomashchi.1. However. the extruded material is cooled and solidified as it is pulled through the die or water. it was shown that tensile strength of the prepared films decreased after modification of the components with TGase or EDC. (2005) have investigated cellulose acetate (CA) nano-composites. Chitosan/pectin laminated films It has been demonstrated that chitosan films may be cast upon pectin films to give clear laminated films having dynamic mechanical properties similar to those of pectin films alone (United States Patent 5919574). 6.3. Moreover. 2007). carboxyl methylcellulose and ethyl cellulose are widely reported as edible films and coatings in the scientific literature (Akbari. Han. the antimicrobials incorporated into PLA and LDPE showed retained slight antimicrobial activity. Conclusion Considering the health tendency of the modern food technology. The screw forces the resin through a die forming the resin into the desired shape. Among the natural compounds under study. it seems important to combine it with other films forming biopolymers such as plant and animal protein as well as polysaccharides. It was concluded that the properties of the gelatine-chitosan films offer real potential permitting to widen the practical applications of these films as packaging material (Kolodziejska & Piotrowska. 2007). other advantages will become apparent from the following description of the preparation procedure which can be summarized as follows: lime pectin (2–4 g) and methylated at 65% was added to rapidly stirred water (200 ml) containing either glycerol (1%) or 85% lactic acid (1%). it is possible to produce novel films comprising pectin and chitosan layers. tensile modulus by approximately 33% were observed after adding 5% (w/w) clay to the fabricated cellulose acetate plastic matrix. This is mainly due to its unique cationic character and versatile properties. as well as on the water solubility of fish gelatin–chitosan bio-based films (4:1. Incorporating a small amount of appropriate compatibilizer is expected to enhance the miscibility of CA matrix and clay nanofillers and thus further improve mechanical and thermal properties of the nano-composites. It was shown that the addition of glycerol in a concentration up to 30% (of the substrate mass) to the fish gelatin–chitosan based films modified with TGase or EDC did not change their solubility in buffers at pH 3 and 6 at 25  C or during heating at 100  C for 60 min. respectively. Chitosan (2–4 g) with 15 degree of acetylation was added to rapidly stirred water (200 mL) containing the same amount of lactic acid. thus having lost some activity due to higher processing temperature. considering the cost of chitosan preparation. This technology can be successfully exploited for active bio-based films preparation. the films were dried at room temperature in a vacuum oven for 30 min. strawberries. Research on the mechanical properties improvement.5 and 5 times lower. Thus.M. They were fabricated using extrusion followed by compression or injection moulding.Food Science and Technology 43 (2010) 837–842 841 5. Moreover. The elongations of the enzymatically modified films containing 20% of glycerol and of chemically modified films containing 15% of glycerol were. mangoes and bananas. 7. the tensile strengths of the plasticized films were 2. In accordance with the reported results. pectin-chitosan blends may also be utilized. and lysozyme were used as antibacterial agents. In particular. according to the manufacturer’s recommended procedure. Edible films or bio-based nano-composites based on cellulose have been extensively applied to delay loss of quality in fresh products such as tomatoes. the obtained clear solution was filtered through glass wool to remove undissolved bits of material. In addition. Improvements in tensile strength by approximately 38%. plasticizers and/or starch may be added to either the chitosan or pectin solutions used for films preparation. where the layers optionally comprise plasticizer and/or starch. At the same time. According to United States Patent 5919574. All these used techniques can be used or adapted for chitosan-based active films preparation. 2007). Active packaging by extrusion processing of recyclable and biodegradable polymers was reported (Del Nobile et al. water vapour transport and . & Izydorczyk. the use of bio-based active films as packaging materials is very important. After 1 h. chitosan is recognized as non-toxic and thus it can be consumed together with the preserved food. the obtained viscous solution was filtered through glass wool. Bio-based active films preparation by extrusion Extrusion is commonly used for film synthesis such as plastics and polymer based packaging materials. According to the authors. 6. After air drying for at least 72 h. PCL was processed at a lower temperature. The chitosan-lactate filtrate (30 mL) was either poured directly into a polystyrene Petri dish or onto a pectin film preformed in a similar Petri dish. lysozyme showed the higher thermal stability. Lemon extract. However. chitosan seems to be highly promising as additive for bio-based active films preparation. Water vapour permeability of the prepared films modified with EDC and TGase was not affected by glycerol at all concentrations up to 25% of the substrate mass. methylcellulose. thymol. 2007). polylactic acid (PLA) as well as polycaprolactone (PCL) were used as environmentally friendly polymeric matrices with the former being recyclable and the latter two biodegradable for active film production using an extrusion method. The authors reported that the obtained results suggest that processing temperatures play a major role in determining the antimicrobial efficiency of the investigated active films. The polymers are heated to molten state by a combination of two main parameters: heating and shear heating from the extrusion screw. The chemical and enzymatic cross-linking of the components did not increase the water barrier properties of the films. Chitosan-based films preparation 6. chitosan-based active packaging materials can be useful for preserving and extending the shelf life of foods. Several researchers recognize that antimicrobial packaging is highly promising for the future improvement of food quality and preservation during processing and storage of different food materials.2. about 8 and 13 times higher than those of unplasticized films. Aider / LWT . by about 25% and 40%. After 4 h. respectively. Fish gelatin–chitosan films The effect of glycerol on the mechanical and water barrier properties. which allowed less degradation of antimicrobial activity. Among the known biopolymers. 2009). Similar study was also reported on extrusion of pea starch containing lysozyme (Nam. Scanlon.

. Z. 43–48. E. T.. M. T. X. R. Biomacromolecules. Damiao. Journal of Food Engineering.. 499–502. A simple preparation of half N-acetylated chitosan highly soluble in water and aqueous organic solvents. Damodaran. & Izydorczyk... Misra. M. Food Research International. (2004). M. Antimicrobial food packaging in meat industry. S. Quintavalla. & Dutta. 7(3). 768–773.. 1238–1244. Yang. M. Preparation of chitosan oligomers with purified chitosanase and its application. Poster 28-5. Quality properties of pork sausage prepared with water-soluble chitosan oligomer. a natural-grade medium.. & Roller. 652–655. Prodpran. Nam. V. M. I. (2001).. 42(7). 91–93. & O’Sullivan. 285–287. Schalek.). R. physical properties and applications (pp. Journal of Agricultural and Food Chemistry.458:544. R. Purification. I. (2000). (1984). 103(2). K. C. 65(5). Rhoades... 72(9). Desbiens.. J. (2009). Y. Molecular affinity and permeability of different molecular weight chitosan membranes. 114(4). (2002). Journal of Food Science. E. M. & Zhu. Coffin. Liu.. D.. T.... J. (1992). LWT – Food Science and Technology. (2004).. S. Carbohydrate Research. S.. Part A. M. (1994). McHugh. (2004). M. Tahiri. characterization and amino acid sequencing of divergicin M35: a novel class IIa bacteriocin produced by Carnobacterium divergens M35. Polysaccharides: Structural diversity and functional versatility (pp. Tsai. X. J. Ghomashchi. Y. Characterization of the smallest chitosan oligomer that is maximally antifungal to Fusarium solani and elicits pisatin formation in Pisum sativum. & Benjakul. M... Kendra.. A. M. J.. Meat Science. A. Mehrotra. & Marsh. L... 42(7).. (2009).. N. Journal of Agricultural and Food Chemistry. Biochimica et Biophysica Acta (BBA) – General Subjects. H. mechanical properties and solubility of fish gelatin-chitosan films modified with transglutaminase or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and plasticized with glycerol. (2009).. B.. C. H. Artharn. 1192–1197. 59(4). 97(2).. T. 93(3).723. C. Tahiri. R. 42(7). Hu. A. characterization and antimicrobial activity of chitosan–Zn complex. Development of new polyolefin films with nanoclays for application in food packaging.. Lee. A. & Toya. L.. B. J. Incoronato. C. K. 44(7).. Wang. (1996). ¨ ¨ Cervera. (1999). (1979).. O. 807–813. & Hadwiger. Montesinos-Herrero. 78(1–3). Izvestya of Saratov University. P. Tatsumoto.. 66(1). Ferreira. (2008). Rantanen. 54(4). M. R. 295–300. M. Buzinova. 58(4). Z. H. Rhoades. Alvarado. 624–632.. G. Viscoelastic properties of pectin/starch blends. Aouada. L. (1996). G. Journal of Food Science. C.. K. (2004).. Meat Science. Chitosan kills bacteria through cell membrane damage. Carbohydrate Research.. H. Chico. Food Chemistry.. Skjak-Bræk (Ed. In G.. F. Z. & Zou. M. 5915–5918.. UK: Elsevier Applied Science. L. R. Izume.. Applied and Environmental Microbiology... Xu. 239–243. 268–274. International Journal of Food Microbiology. B. Heinamaki. Nunes. Avena-Bustillos. In vitro evaluation of mucoadhesive properties of chitosan and some other natural polymers. Wibowo.. et al. 1428–1433. (2004).. C. Meat Science. Sorption and sactericide properties of chitosan films. Airaksinen.. Aider / LWT . International Journal of Pharmaceutics. M. 50(21). Du. & Junginger. G.. Darmadji. 80–84. & Parris. Improvement in food packaging industry with biobased nanocomposites. (2009). S. L. M. A.. & Kikuchi. Krochta. Hoagland. 93(1). & Holley. (2005). L. DOI:547. The fungicidal effect of chitosan on fungi of varying cell wall composition. Journal of Food Science. biochemistry.. W. H. A. Avena-Bustillos. E. M. Coffin. (1989). (2002). & Fishman.. 339(16). H. C. & Byun. Sano. Wang. Allan.. Y. morphological. Qi. 1915–1919. The water vapour permeability. Massaro. (2007). et al. (2009). J. M.. P. C. Ahvenainen. Bouwstra. 123–136. D.. et al. S. Antimicrobial actions of degraded and native chitosan against spoilage organisms in laboratory media and foods. 1311–1320. S. M. 49(1). R. Jiang. Preparation. K. J. Schacht. M. & Liu.. In O. Longares.. (1984).-Y. & Fliss. Effect of chitosan in meat preservation. Jun. Carbohydrate Polymers. W. Begin. Round scad protein-based film: storage stability and its effectiveness for shelf-life extension of dried fish powder.. Pereira de Abreu. 448–453. Drzal. C. & Krochta. Kheadr. 2693–2700. S.. Lehr. gas permeation ability are also necessary. (2001). K. S. & Su. Kubota. International Journal of Food Microbiology. G. Growth of Carnobacterium divergens M35 and production of Divergicin M35 in snow crab by-product. Lee. 41(8). Del Nobile. S. Physical and mechanical properties of highly plasticized pectin/starch films. Ouattara.. 8(2). Benech.. Y. L... Journal of Food Engineering. E477–E484. California: Institute of Food Technologists Annual Meeting. 62(3). Chitosan/pectin laminated films.-F. Flores. K. A. European Polymer Journal. 605–610. C. 58(1). A. (1993). Experimental Mycology.. & Izumimoto. Lacroix. Journal of Food Protection. R. M. (1964). & Vicini..-M. S. A. C. S. I. L. Article 3. G. 71(2-3). M. D.. Tripathi. L. & Shipovskaya. 38(2). Di Pierro. Angulo. L. (2007). 1–6. LWT – Food Science and Technology. Lacroix. X. 62(3). H. Improved barrier and mechanical properties of novel hydroxypropyl methylcellulose edible films with chitosan/tripolyphosphate nanoparticles. Tracey. Dutta. & Piotrowska. (2006). Antimicrobial activity and physical properties of chitosan-tapioca starch based edible films and coatings. & Wrench. B. 43(6). Rumsey.. . H.. 42(2). 373–382).. 276–281.. 38(6). Food chemistry (pp. 369–375.. Anaheim. Kubota. Ralston. E. X. Active packaging by extrusion processing of recyclable and biodegradable polymers. Paseiro Losada. A. 595–628). D. J. 744–749. I. P. Finding of low coast technologies for chitosan-based active films preparation is a key for the success of this unique biopolymer as a real packaging material. 324(4). C... 8(3). R. L. (2002). S.. 1173–1182. Franssen. L. 243–254. Desbiens. R. B. Journal of Applied Polymer Science.. R.. H.. & Roller. E. N. Kheadr. Chitosan–whey protein edible films produced in the absence or presence of transglutaminase: analysis of their mechanical and barrier properties.. A. Helander. European Journal of Pharmaceutics and Biopharmaceutics. J. O. Chitosan membranes for reverse osmosis application. Dumitriu (Ed.. & Mattoso. J. Chen. & Sun. R. Characterization of chitosan-whey protein films at acid pH. 235–244. Biodegradable nanocomposites from cellulose acetate: mechanical. Fennema (Ed. & Cruz. M. & Gerschenson. Journal of Agricultural and Food Chemistry. M. Physical properties of PVOH/chitosanblended films cast from different solvents. P. and thermal properties. H. Chitin and chitosan: Sources. O’Riordan. J.. 899–903. & Lopes-da-Silva.. X. Physical stability and moisture sorption of aqueous chitosanamylose starch films plasticized with polyols. 15(4–6). & Krochta. & Moghadam.. Krogars. Modeling of natamycin and potassium sorbate diffusion in whey protein isolate films for application to cheddar cheese. Study on antimicrobial activity of chitosan with different molecular weights. T. 37. USA: Marcel Dekker Inc.. T. peptides and protein. L.... & Fishman. F. A. N. D. Piette. I.. & Zail. Macromolecular complexes of chitosan. chemistry. Zheng. Food Chemistry. M. J. Hydrophilic edible films: modified procedure for water vapor permeability and explanation of thickness effects. Monahan. A.. B. P. Zheng... Y. LWT – Food Science and Technology. Ohtakara. 373–380. 92(4). United States Patent 5919574.. R. 69–76. 527–530. I. (1994). (1993). R... (1998). Y. Extrusion of pea starch containing lysozyme and determination of antimicrobial activity. In S.. The inhibition of fermentation in baker’s yeast by chitosan. Karjalainen. S. Conte.. Carbohydrate Polymers. Food Research International. Park. R. Masi.. International Journal of Food Microbiology. A.. N. J. Lee..Food Science and Technology 43 (2010) 837–842 Kolodziejska. 56(1). Antibacterial activity of shrimp chitosan against Escherichia coli. M. A. K. 321–429). Chitosan disrupts the barrier properties of the outer membrane of Gram-negative bacteria. A. R. D. London.. Delgadillo. Villalonga. A. 3(3). J. (2007). Perspectives for chitosan based antimicrobial films in food applications. Jo. 147–155.-J. I.. New York. T... de Moura. J. Preparation and antibacterial activity of chitosan nanoparticles. S.. A. & Mohanty.. F. & Panza. G. Thibault.. Scanlon.. Schou. References Akbari. ´ Vasconez. F.. Diffusion of acetic and propionic acids from chitosan-based antimicrobial packaging films. E. Composites. D.. W. 21–26. (2000).. P. A. & Hadwiger. L. Du. N. (2001). K. 3(4). T. Experimental Mycology. R.. (2005). (2007). G. 2229–2243. et al. L. 95(2).). (2000). New York: Marcel Dekker. Amino acids.). 762–769. (2009).842 M. G. Buonocore. J. C. (2009). Habig McHugh. S.. Food Hydrocolloids. Nurmiaho-Lassila. P. 54(9). Uchida. Journal of Food Science. A. & Park. J.. T. International Journal of Food Engineering. Han...-H.. Simard. A. Properties of edible sodium caseinate films and their application as food wrapping.. J. A. Wang.. E.. L. Park. Mariniello. (2003). Campos.