Chitosan application for active bio-based films production and potential in the food industry: Review

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, chitosan-based 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.     

Optimization of the biocide properties of chitosan for its application in the design of active films of interest in the food area

The influence on biocide performance of some unprecedented physicochemical features of chitosan cast films such as film thickness, pH of the nutrient broth, film neutralization, film autoclave sterilization and temperature exposure were analyzed against Staphylococcus aureus and in some experiments also against Salmonella spp. The work demonstrates for the first time the influence of the release or positive migration of protonated glucosamine fractions from the biopolymer into the microbial culture as the responsible event for the antimicrobial performance of the biopolymer under the studied conditions. From the results, a reliable and reproducible method for the determination of the bactericidal activity of chitosan-based films was developed in an attempt to standardize the testing conditions for the optimum design of active antimicrobial food packaging films and coating applications.     

Chitosan-based biodegradable functional films for food packaging applications

Chitin is the structural material of crustaceans, insects, and fungi, and is the second most abundant biopolymer after cellulose on earth. Chitosan, a deacetylated derivative of chitin, can be obtained by deacetylation of chitin. It is a functionally versatile biopolymer due to the presence of amino groups responsible for the various properties of the polymer. Although it has been used for various industrial applications, the recent one is its use as a biodegradable antimicrobial food packaging material. Much research has been focused on chitosan-based flexible food packaging and edible food coatings to compete with conventional non-biodegradable plastic-based food packaging materials. Various strategies have been used to improve the properties of chitosan - using plasticizers and cross-linkers, embedding the polymer with fillers such as nanoparticles, fibers, and whiskers, and blending the polymer with natural extracts and essential oils and also with other natural and synthetic polymers. However, much research is still needed to bring this biopolymer to industrial levels for the food packaging applications.Industrial relevanceAs a major by-product of the seafood industry, a massive amount of crustacean shell waste is generated each year, which can be used to produce value-added chitin, which can be converted to chitosan using a relatively simple deacetylation process. Being extracted from a bio-waste product using many energy-efficient methods, chitosan is much cheaper as compared to other biopolymers. Nevertheless, the exceptional properties of chitosan make it a relatively stronger candidate for food packaging applications. Chitosan has already been used in various industries, such as biomedical, agriculture, water treatment, cosmetics, textile, photography, chromatography, electronics, paper industry, and food industry. This review article compiles all the essential literature up to the latest developments of chitosan as a potential food packaging material and the outcomes of its practical utilization for this purpose.     

Characterization and antimicrobial analysis of chitosan-based films

Chitosan-based films for food packaging applications were prepared by casting and dried at room temperature or heat-treated in order to study functional properties and antimicrobial activity. In all cases, films were flexible and transparent, regardless of chitosan molecular weight, glycerol content, and temperature. Regarding antimicrobial activity, chitosan film forming solutions showed antimicrobial behaviour against Escherichia coli and Lactobacillus plantarum. It was also observed that the bacteriostatic property of chitosan-based films against bacteria employed in this study was notably affected by temperature. Moreover, temperature produced significant variation in the functional properties of chitosan-based films, such as colour, wettability, resistance against UV light and mechanical properties. In good agreement with this behaviour, total soluble matter (TSM), fourier transform infrared (FTIR) spectroscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction (XRD) results suggested a change in the chemical structure of chitosan films, possibly due to Maillard reaction when heat treatment was used.     

Development and evaluation of a novel biodegradable film made from chitosan and cinnamon essential oil with low affinity toward water

Combining antimicrobial agents such as plant essential oils directly into a food packaging is a form of active packaging. In this work chitosan-based films containing cinnamon essential oil (CEO) at level of 0.4%, .0.8%, and 1.5% and 2% (v/v) were prepared to examine their antibacterial, physical and mechanical properties. Scanning electron microscopy was carried out to explain structure–property relationships. Incorporating CEO into chitosan-based films increased antimicrobial activity. CEO decreased moisture content, solubility in water, water vapour permeability and elongation at break of chitosan films. It is postulated that the unique properties of the CEO added films could suggest the cross-linking effect of CEO components within the chitosan matrix. Electron microscopy images confirmed the results obtained in this study.     

Chitosan Polymer as Bioactive Coating and Film against Aspergillus niger Contamination

ABSTRACT: The inhibitory activity of chitosan-based edible coatings and films was assessed against the Aspergillus niger food pathogen and deterioration microorganism. Spore-counting assays showed an almost total inhibition of A. niger growth when either film-forming solution or film were used at a low concentration of chitosan (0.1% w/v). Epifluorescence microscopic results showed the action of chitosan on the relative proportion of RNA compared with DNA. The water vapor permeability (WVP) of chitosan film was relatively low compared with the poor moisture barrier of some polysaccharide films. Moreover, a coating with chitosan film on an agar gel, used as a food model, induced a 30% reduction in water loss. These results showed potential applications of chitosan-based films as bioactive packaging with properties to limit the food dehydration phenomenon.     

Perspectives for chitosan based antimicrobial films in food applications

Recently, increasing attention has been paid to develop and test films with antimicrobial properties in order to improve food safety and shelf life. Active biomolecules such as chitosan and its derivatives have a significant role in food application area in view of recent outbreaks of contaminations associated with food products as well as growing concerns regarding the negative environmental impact of packaging materials currently in use. Chitosan has a great potential for a wide range of applications due to its biodegradability, biocompatibility, antimicrobial activity, non-toxicity and versatile chemical and physical properties. Thus, chitosan based films have proven to be very effective in food preservation. The presence of amino group in C2 position of chitosan provides major functionality towards biotechnological needs, particularly, in food applications. Chitosan based polymeric materials can be formed into fibers, films, gels, sponges, beads or even nanoparticles. Chitosan films have shown potential to be used as a packaging material for the quality preservation of a variety of food. Besides, chitosan has widely been used in antimicrobial films to provide edible protective coating, in dipping and spraying for the food products due to its antimicrobial properties. Chitosan has exhibited high antimicrobial activity against a wide variety of pathogenic and spoilage microorganisms, including fungi, and Gram-positive and Gram-negative bacteria. The present review aims to highlight various preparative methods and antimicrobial activity including the mechanism of the antimicrobial action of chitosan based films. The optimisation of the biocidic properties of these so called biocomposites films and role of biocatalysts in improvement of quality and shelf life of foods has been discussed.     

Effects of gelatin origin,bovine-hide and tuna-skin,on the properties of compound gelatin–chitosan films

With the purpose to improve the physico-chemical performance of plain gelatin and chitosan films, compound gelatin–chitosan films were prepared. The effect of the gelatin origin (commercial bovine-hide gelatin and laboratory-made tuna-skin gelatin) on the physico-chemical properties of films was studied. The dynamic viscoelastic properties (elastic modulus G′, viscous modulus, G″ and phase angle) of the film-forming solutions upon cooling and subsequent heating 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 fish gelatin–chitosan films were more water resistant (∼18% water solubility for tuna vs 30% for bovine) and more deformable (∼68% breaking deformation for tuna vs 11% for bovine) than the bovine gelatin–chitosan films. The breaking strength of gelatin–chitosan films, whatever the gelatin origin, was higher than that of plain gelatin films. Bovine gelatin–chitosan films showed a significant lower water vapour permeability (WVP) than the corresponding plain films, whereas tuna gelatin–chitosan ones were only significantly less permeable than plain chitosan film. Complex gelatin–chitosan films behaved at room temperature as rubbery semicrystalline materials. In spite of gelatin–chitosan interactions, all the chitosan-containing films 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 films, especially when using fish gelatin, without altering the antimicrobial properties.     

Functional Properties of Antimicrobial Lysozyme-Chitosan Composite Films

ABSTRACT: Lysozyme-chitosan composite films were developed for enhancing the antimicrobial properties of chitosan films. A 10% lysozyme solution was incorporated into 2% chitosan film-forming solution (FFS) at a ratio of 0%, 20%, 60%, and 100% (w lysozyme/w chitosan). Films were prepared by solvent evaporation. Lysozyme release from the film matrix, the antimicrobial activity of films against Escherichia coli and Streptococcus faecalis , and basic film properties were investigated. The lysozyme release proportionally increased with increasing initial concentration of lysozyme in the film matrix, and the amount of released lysozyme was in natural log relationship with time. The films with 60% lysozyme incorporation enhanced the inhibition efficacy of chitosan films against both S. faecalis and E. coli , where 3.8 log cycles reduction in S. faecalis and 2.7 log cycles reduction in E. coli were achieved. Water vapor permeability of the chitosan films was not affected by lysozyme incorporation, whereas the tensile strength and percent elongation values decreased with increased lysozyme concentration. Scanning electron microscopy images revealed that lysozyme was homogeneously distributed throughout the film matrix. This study demonstrated that enhanced antimicrobial activity of lysozyme-chitosan composite films can be achieved by incorporating lysozyme into chitosan, thus broadening their applications in ensuring food quality and safety.     

Biological activities of chitosan and chitooligosaccharides

Chitosan and its oligosaccharides, which are known to possess multiple functional properties, have attracted considerable interest due to their biological activities and potential applications in the food, pharmaceutical, agricultural and environmental industries. Many researchers have focused on chitosan as a potential source of bioactive materials in the past few decades. This review focuses on the biological activities of chitosan and chitooligosaccharides based on our and others’ latest research results, including hypocholesterolemic, antimicrobial, immunostimulating, antitumor and anticancer effects, accelerating calcium and iron absorption, anti-inflammatory, antioxidant and Angiotensin-I-converting enzyme (ACE) inhibitory activities and so on, which are all correlated with their structures and physicochemical properties. The bioactivities summarized here may provide novel insights into the functions of chitosan, its derivatives or oligosaccharides and potentially enable their use as functional-food components and additives.     

交联壳聚糖薄膜及其水凝胶骨架片的制备与控释性能探讨

针对活性物质生物利用度提高这一热点问题,本文以三聚磷酸钠为交联剂,研究了交联壳聚糖薄膜的相关结构性能,探讨了交联壳聚糖水凝胶骨架片对活性物质的控释性能。壳聚糖来源广泛、生物相容性好,FT-IR-ATR分析显示,通过交联反应壳聚糖薄膜上引入一定基团,增强了薄膜的三维网络结构,从而使其具有一定的溶胀吸水性能。同时,交联后的壳聚糖薄膜耐酸性能明显提升,通过扫描电镜观察,交联壳聚糖薄膜经模拟胃液运转后表面仍然致密,无破损,具有作为活性物质载体材料的潜质。另外,以5-ASA为模型活性物质,通过压制得到交联壳聚糖水凝胶骨架片,在模拟释放实验中,5-ASA在胃液中0.5~1 h的释放率明显降低。研究结果显示,交联改性壳聚糖在活性物质传递及药物控释等领域都具有良好的应用前景。     

Incorporation of nisin in poly (ethylene-co-vinyl acetate) films by melt processing: a study on the antimicrobial properties

Both industry and academia have shown a growing interest in materials with antimicrobial properties suitable for food packaging applications. In this study, we prepared and characterized thin films of ethylene-co-vinyl acetate (EVA) copolymer with antimicrobial properties. The films were prepared with a film blowing process by incorporating a nisin preparation as an antimicrobial agent in the melt. Two grades of EVA containing 14 and 28% (wt/wt) vinyl acetate (EVA 14 and EVA 28, respectively) and two commercial formulations of nisin with different nominal activities were used. The effect of the nisin concentration also was evaluated. The films with the highest antimicrobial activity were those formulated with nisin at the highest activity and EVA with the highest content of vinyl acetate. The use of the commercial formulation of nisin with high activity in the EVA films allowed reduction in the amount of nisin needed to provide antimicrobial properties. Consequently, the mechanical properties of these films were only slightly inferior to those of the pure polymers. In contrast, films prepared by incorporating more of the nisin with lower activity had poor mechanical properties. The effect of different processing temperatures used in the preparation of the films on the antimicrobial properties of the films also was evaluated. The materials displayed antimicrobial properties even when they were prepared at temperatures as high as 160 °C, probably because of the very short processing time (60 to 90 s) required for preparation.     

壳聚糖复合膜在果蔬保鲜中的应用

壳聚糖具有良好的生物相容性、可生物降解性、安全性、成膜性、抗菌性等,常用于果蔬保鲜。但由于机械性能和生物活性不足,为了增强其理化性能和生物活性,常添加生物聚合物、抗菌剂、抗氧化剂等功能成分以提高膜综合性能。综述了壳聚糖膜和壳聚糖/多糖、壳聚糖/蛋白质、壳聚糖/脂质、壳聚糖/抗菌剂、壳聚糖/抗氧化剂等壳聚糖基复合膜在果蔬保鲜中的应用进展,从壳聚糖的诱导活性、成膜特性和抗菌活性三个方面总结了壳聚糖膜的保鲜机理,分析了壳聚糖基复合膜目前在果蔬保鲜实际应用中存在的问题,并对未来发展方向进行了展望,以期为开发安全、高效、绿色、经济的壳聚糖基果蔬保鲜膜提供一定的理论指导。     

ORAC of chitosan and its derivatives

Chitosan and chitosan derivatives are receiving a lot of attention as materials of natural origin which possess radical scavengers, antioxidants and antimicrobial properties, especially in food applications. With the aim to apply the Oxygen-Radical Absorbance Capacity assay (ORAC), to detect the polysaccharides capacity to scavenge the peroxyl radical, four different grafted chitosan derivatives were synthesized.     

基于壳聚糖的抗氧化复合材料制备及其在食品包装中的应用

本文以壳聚糖为主体材料,在其侧链接枝天然的具有抗氧化作用的芳胺类化合物腺嘌呤来增加它的抗氧化活性,并选用具有更高长径比的纳米纤维素掺杂制备高强度的改性壳聚糖复合膜。通过红外光谱、核磁共振碳谱和元素分析对改性壳聚糖进行结构鉴定,证明了腺嘌呤的接枝成功。抗氧化实验结果表明,腺嘌呤改性后的壳聚糖膜抗氧化活性得到显著提升,DPPH自由基清除率能达到72.20%,而纳米纤维素的掺杂增加了壳聚糖膜的机械性能和尺寸稳定性,MCBC-CNF-2膜的拉伸强度能达到65.06MPa,吸水率和溶胀率分别仅为36.20%和6.06%,尽管随着纳米纤维素掺杂量的增加,改性壳聚糖膜的抗氧化活性有所降低,但MCBC-CNF-2膜的DPPH自由基清除率仍能达到54.20%。这种全生物质膜科生物降解并且成本较低,有望应用于食品包装材料。     

Effect of microencapsulation on morphology,physicochemical properties and flavour profiles of solid yoghurt-flavoured bases

Yoghurt-flavoured bases have many applications in food industry, but the poor stability in the volatile compounds limits their applications. In this study, the morphology and physicochemical properties of yoghurt-flavoured base microcapsules were evaluated with four different wall materials including chitosan, β-cyclodextrin, octenyl succinate anhydride and maltodextrin solution by spray drying. The encapsulation efficiencies of these four microcapsule formulations exceeded 93%. Microcapsules produced by chitosan possessed the best physical properties with improved encapsulation efficiency and smooth microstructure, so chitosan was selected as the encapsulating material of yoghurt-flavoured bases. Compared with those without chitosan, the encapsulated yoghurt-flavoured bases with chitosan had smaller particle size, better water solubility and moisture resistance as well as better stability. Furthermore, microencapsulation and spray drying technology can preserve many volatile compounds and the proportion of ketones, aldehydes, alcohols and other compounds increased. Hence, chitosan is a microcapsule material suitable for outputting solid yoghurt-flavoured bases.     

壳聚糖/植物精油可食性抗菌膜研究进展

壳聚糖包埋植物精油制备的可食性抗菌膜具有原料来源广泛、可食、可降解,抗菌效果强等优势,在食品保鲜领域显示了重要的应用价值。本文综述了壳聚糖和精油各自的结构、性质、壳聚糖/精油复合膜及添加了其它天然高分子如蛋白质、淀粉等的复合可食性抗菌膜的研究进展,同时指出了目前该研究领域中存在的问题,并对未来的研究方向进行了展望,为壳聚糖/植物精油复合可食性抗菌膜研究的进一步开发利用提供参考。     

Electrospraying method for fabrication of essential oil loaded-chitosan nanoparticle delivery systems characterized by molecular,thermal, morphological and antifungal properties

Fabrication of essential oil loaded-chitosan nanoparticles using electrospraying technique appears to be a novel strategy to develop thermally stable nanoparticles possessing higher encapsulation efficiency and particle stability. This study aims to fabricate chitosan nanoparticles (CNPs) loaded with Origanum vulgare essential oil (OEO, Origanum vulgare L.) at different proportions (OEO/CH proportions of 0:1, 0.0625:1, 0.125:1, 0.25:1 and 0.5:1 mL/g) using electrospraying technique. The CNPs were characterized in term of their particle size and stability (dynamic light scattering), encapsulation efficiency (spectrophotometry), and molecular (Fourier transform infrared spectroscopy), thermal (differential scanning calorimetry/thermogravimetric analysis), morphological (scanning electron microscopy) and antifungal (agar dilution method) and fungistatic activity properties. The average particle sizes of the CNPs ranged between 290 and 483 nm with a spherical morphology. Positively charged surface characteristics were observed to increase with the increment of OEO concentration in CNPs. The encapsulation efficiency values were determined in the range of 70.1 and 79.6%. The molecular and thermal analyses exposed very decent encapsulation of OEO into thermally stable chitosan nanoparticles. Morphological analysis verified the spherical shapes of these nanoparticles. Above all, the antifungal effectiveness of OEO against the Alternaria alternata AY1 could be significantly (p < 0.05) increased by its encapsulation into chitosan nanoparticles fabricated by the electrospraying technique. Consequently, it can be stated that the electrospraying technique developed is able to fabricate thermally stable nanoparticles owning higher encapsulation efficiency and particle stability. The results and findings suggest that the electrospraying technique would be a promising method to fabricate chitosan-based nanoparticles as an antimicrobial agent to control their release in a prolonged preservative effect in cosmetic, pharmaceutical and food applications for adjustable dosage forms.Industrial relevanceThe fungal agents such as Alternaria alternata cause great damages on post-harvest fresh fruits and vegetables, thus leading to a great economical lose. Therefore, a great variety of methods in struggling with disease have been previously proposed. Nowadays, the most effective leading methods to struggle against plant diseases are those applied with synthetic fungicides to minimize such lose in post-harvest fruit and vegetables. However, intensive and unconscious use of the fungicides leads the pathogens to develop resistance against these agents as well as to accumulation of chemical residues in soil, water and air and finally to formation of carcinogenic effects on human health. Nowadays, a great effort is being exerted to develop novel biodegradable and natural antimicrobial agents for struggling fungal spoilage in postharvest products. Essential oils are among the most widely used natural struggling methods. Essential oils obtained from plants have been extensively used since they are natural antimicrobial agents. However, they cannot be effectively used in spite of their extensive applications. Recently, some researches in the field of nanotechnology have demonstrated that the effectiveness of active substances could be increased by using some techniques. In this respect, we aimed at developing essential-oil-loaded-chitosan-nanoparticle delivery systems using an electrospraying deposition system to prevent fungal colonization on food and plant materials. By increasing antifungal effectiveness of essential oils by their encapsulation into nanoparticles, it will be possible to decrease the levels of regularly applied dose and reflect the obtained outcomes to the food and agriculture industry. This study is the first example of production of essential oil loaded nanoparticles using the electrospraying-hydrodynamic process and showed that encapsulation of oregano essential oil into chitosan based nanoparticles (CNPs) by using the electrospraying deposition technique considerably increased the antifungal effectiveness of the Origanum vulgare essential oil. Our results highlight the potential use of the chitosan nanoparticles (CNPs) loaded with different amounts of Origanum vulgare in food and agriculture industry as an effective fungicidal material against Alternaria alternata, suggesting that the CNPs can be promising tools to compete with synthetic fungicide counterparts and limit use of synthetic ones for struggling of food and plant pathogens. Therefore, the results of this study should be of great importance to industrial applications in terms of development of natural, but effective preservatives as alternative to synthetic ones. In this respect, the CNPs would find a great industrial application area in the food and agriculture industry which seek natural preservatives due to the recent health concerns.     

壳聚糖基复合膜的成膜机理和特性研究进展

壳聚糖通过分子内和分子间氢键连接形成具有粘性的成膜溶液,流延干燥后可形成高透明度的可食膜.又因壳聚糖膜具有一定的机械性能、阻气性和抑菌性,已广泛应用于食品贴体包装,来提高食品质量.纯壳聚糖膜的力学性能、阻水性等不能满足理想包装的高保护性、高防潮性的要求,限制了其在食品包装方面的应用.在实际生产中,壳聚糖常与其他成膜材料...     

Development of protein-based bioplastics with antimicrobial activity by thermo-mechanical processing

This study focuses on the development of new bio-active protein-based bioplastics through a thermo-mechanical processing, which involves a first compounding step followed by compression-moulding of the resulting material into the desired shape. Two types of proteins, wheat gluten and egg-white albumen, and two different bioactive agents, formic acid and oregano essential oil, were selected. The effect of biocide addition on the material rheological response, its antimicrobial activity and biocide release behaviour have been assessed. Rheological tests demonstrated that formulation and processing may exert a notable effect on the material linear viscoelasticity. Kirby–Bauer tests carried out on four selected types of microorganisms revealed that oregano essential oil into a wheat gluten-based matrix may be suitable for applications where the active agent must be progressively delivered (for up to 7 days). Moreover, this biocide can inhibit microorganisms’ growth even if the bioplastic is not in direct contact with the substrate.