Physicochemical,Microstructural, and Antibacterial Properties of β‐Chitosan and Kudzu Starch Composite Films

Abstract: This study investigated physicochemical, microstructural, and antibacterial properties of β‐chitosan–kudzu starch composite films with addition of 0%, 20%, 60%, or 100% kudzu starch (w starch/w chitosan) in 1% chitosan solution. Molecular interactions between chitosan and kudzu starch and the crystal structure of the films were also determined. Adding 60% kudzu starch reduced water vapor permeability and solubility of pure β‐chitosan film by about 15% and 20%, respectively, whereas mechanical strength and flexibility of the film were increased about 50% and 25%, respectively. Micrograph showed that β‐chitosan film was totally amorphous, and the composite films generally became rougher with more starch added. Fourier transform infrared and X‐ray diffraction spectra showed that the 2 film‐forming components were compatible with each other. Pure β‐chitosan film resulted in 9.5 and 11.5 log CFU/mL reduction in Escherichia coli and Listeria innocua based on plate count method, respectively. Addition of kudzu starch reduced the antibacterial activity of film, but still achieved 8.3 and 10.3 log CFU/mL reduction in E. coli and L. innocua, respectively when kudzu starch to chitosan weight ratio was 1:1. Reduced antibacterial activity might attribute to the interaction of amino groups in β‐chitosan with the hydroxyl groups in kudzu starch. This study demonstrated that kudzu starch effectively improved water barrier of β‐chitosan film, and the composite films retained strong antibacterial ability. Practical Application: One percent of β‐chitosan containing 60% kudzu starch (w/w chitosan) composite films possessed better mechanical and water barrier properties than pure β‐chitosan films, and showed strong antibacterial activity against both Gram‐positive and Gram‐negative bacteria. The films may be used as wraps or coatings to prolong the shelf life of different foods or other similar applications.     

Permeability and Mechanical Properties of Cellulose-Based Edible Films

Factors affecting barrier properties [oxygen permeability (OP) and water vapor permeability (WVP)] and mechanical properties [tensile strength (TS) and elongation (E)] were investigated for methyl cellulose (MC) and hydroxypropyl cellulose (HPC) films. OP, WVP and TS of MC and HPC films increased as the molecular weight (MW) of the cellulose increased. E of MC films increased as MW increased, but E of HPC films was highest for the intermediate MW of 370,000. OP, WVP and TS of MC films were not a function of thickness, but E slowly increased as film thickness increased. OP and WVP of HPC films were not relatable to film thickness, but TS and E of HPC films slowly increased as film thickness increased. TS decreased and E increased for both film types as concentration of plasticizers was increased. Plasticizers enhanced or retarded OP and WVP of cellulose-based films, depending on their concentrations.     

Physical properties of PVOH/chitosan-blended films cast from different solvents

Homopolymer films of chitosan and polyvinyl alcohol (PVOH) and blended films consisting of PVOH and chitosan were cast from different organic acid solvents: acetic acid (AA), citric acid (CA), lactic acid (LA) and malic acid (MA) and characterized for mechanical and barrier properties. Intermolecular interactions were investigated with FTIR. Cross-linking and interactions with the solvent system resulted in a wide range of properties. Also, the effect of blends and acid solvent on the mechanical properties [tensile strength (TS), % breaking elongation (%BE)] and barrier properties [water vapor permeability (WVP)] was investigated. The organic acid used as a solvent affected mechanical properties and the WVP of PVOH/chitosan films blends. TS and %BE of PVOH/chitosan films were 13.5–221.9 Mpa and 5.2–451.8%, respectively. The WVP ranged from 0.19 to 0.62 ng m/m² s Pa. The range of properties, both intermediate from the component polymers and extending beyond either individual component suggests molecular interactions and cross-linking within the blends. Elucidation of these interactions continues.     

Characteristics of Different Molecular Weight Chitosan Films Affected by the Type of Organic Solvents

ABSTRACT: Chitosan films were prepared using 3 chitosan molecular weights and 4 organic acid solvents without plasticizer. Tensile strength (TS) and elongation (E) ranged from 6.7 to 150.2 MPa, and from 4.1 to 117.8%, respectively. Water vapor permeability (WVP) and oxygen permeability (OP) ranged from 0.3 to 0.7 ng-m/m²-s-Pa and OP from 0.4 to 5.8 × 10 ⁻⁸ cc/m²-day-atm, respectively. TS increased with chitosan molecular weight. Acetic acid resulted in the toughest films followed by malic, lactic, and citric acid, respectively. Films prepared with citric acid had the highest E values. WVP was not influenced significantly by the molecular weight of chitosan. OP of films prepared with malic acid was the lowest, followed by acetic, lactic, and citric acid.     

甘油与甲基纤维素对高直链玉米淀粉- 壳聚糖复合膜性能的影响

以高直链玉米淀粉(HACS)和壳聚糖(CS)为基本材料,甘油为增塑剂,甲基纤维素(MC)为增强剂制备可食性复合膜,研究高直链玉米淀粉与壳聚糖的质量比,甘油的添加量以及甲基纤维素的添加量对复合膜物理性能的影响,包括抗拉强度(TS)、断裂伸长率(E)、水蒸气透过系数(WVP)和色度。结果表明,壳聚糖添加量的增大与甘油添加量的增加都使高直链玉米淀粉- 壳聚糖复合膜的抗拉强度降低,断裂伸长率和WVP 显著增大,膜颜色变黄;甲基纤维素的添加改善了复合膜的机械性能和WVP,随着甲基纤维素添加量的增加,复合膜的抗拉强度和断裂伸长率都随之增大,WVP 逐渐降低,且对膜的颜色没有显著影响。     

Water Vapor Permeability and Mechanical Properties of Soy Protein Isolate Edible Films Composed of Different Plasticizer Combinations

Water barrier and mechanical properties were measured for soy protein isolate (SPI) films plasticized with glycerol (GLY) and 1 of the plasticizers (propylene glycol [PG], polyethylene glycol [PEG], sorbitol [SOR], or sucrose [SUC]) at a ratio of 25:75, 50:50, 75:25, and 0:100. Plasticizer type as well as the plasticizer ratio in the GLY: plasticizer mixtures affected the film water barrier and mechanical properties. An addition of as little as 25% of a less hygroscopic plasticizer in the mixture induced significant reduction in water vapor permeability (WVP) of SPI films. However, at least 50% of the mixture needs to be GLY to show significant improvement in tensile strength (TS). From our experimental design, 50:50 GLY:SOR was the recommended combination because of its comparatively low WVP value and relatively high flexibility and strength. Incompatibility of GLY:PEG plasticizer mixture in SPI film was observed by surface migration of PEG from the film matrix.     

Mechanical Properties, Water Vapor Permeabilities and Solubilities of Highly Carboxymethylated Starch-Based Edible Films

ABSTRACT: Tensile strength (TS), elongation (E), water vapor permeabilities (WVP) and solubilities were determined for highly carboxymethylated starch (HCMS)-based edible films plasticized with sorbitol (S), xylitol (X), mannitol (M) and glycerol (G). TS and E of HCMS-based film increased as the concentration of plasticizer S, M or × increased. TS of the HCMS-based film containing combined plasticizers were higher than those of films containing single plasticizer. The WVP of HCMS-based films seemed to decreased as the concentration of M, X or G plasticizer increased. Increasing plasticizer concentrations in HCMS-based film resulted in decreasing solubility of the films.     

Preparation and properties of rice starch–chitosan blend biodegradable film

Biodegradable blend films from rice starch–chitosan were developed by casting film-solution on leveled trays. The influence of the ratio of starch and chitosan (2:1, 1.5:1, 1:1, and 0.5:1) on the mechanical properties, water barrier properties, and miscibility of biodegradable blend films was investigated. The biodegradable blend film from rice starch–chitosan showed an increase in tensile strength (TS), water vapor permeability (WVP), lighter color and yellowness and a decreasing elongation at the break (E), and film solubility (FS) after incorporation of chitosan. The introduction of chitosan increased the crystalline peak structure of starch film; however, too high chitosan concentration yielded phase separation between starch and chitosan. The amino group band of the chitosan molecule in the FTIR spectrum shifted from 1541.15 cm⁻¹ in the chitosan film to 1621.96 cm⁻¹ in the biodegradable blend films. These results pointed out that there was a molecular miscibility between these two components. The properties of rice starch–chitosan biodegradable blend film and selected biopolymer and synthetic polymer films were compared; the results demonstrated that rice starch–chitosan biodegradable blend film had mechanical properties similar to the other chitosan films. However, the water vapor permeability of rice starch–chitosan biodegradable blend film was characterized by relatively lower water vapor permeability than chitosan films but higher than polyolefin.     

Storability of Antimicrobial Chitosan-Lysozyme Composite Coating and Film-Forming Solutions

ABSTRACT:  Chitosan-lysozyme (CL) film and coating solutions were prepared aseptically by incorporating 60% lysozyme (w/w chitosan) into 3% chitosan solution. The solutions were stored at 10, 21, and 37 °C up to 6 mo for monthly evaluation of physicochemical and antimicrobial properties. Solutions were made into films at each sampling time to investigate lysozyme release, water solubility, water vapor permeability (WVP), tensile strength (TS), and elongation (EL) of the films. During the 6-mo storage, the pH and translucency of CL solutions did not change ( P > 0.05) and microorganisms were not detected with total aerobic count media. CL solutions became darker, with a more saturated yellow hue developing with increased storage time and temperature. Storage enhanced the antimicrobial activities of the solutions against E. coli and L. monocytogenes , and films made of solutions stored at 37 °C exhibited higher antimicrobial activities against these 2 pathogens than those stored at 10 and 21 °C. Increased water solubility and lysozyme release and decreased TS and EL were observed in films made from solutions stored at 37 °C. WVP was not significantly affected by storage temperature and time. These changes might be attributed to increased chitosan degradation by lysozyme hydrolysis at a higher storage temperature and longer storage time. Results indicated that with storage at 10 to 20 °C, premade CL solutions are stable and may be distributed as a commercial product for coating or film applications or both in different foods for at least 6 mo.     

Mechanical and Barrier Properties of Lactic Acid and Rennet Precipitated Casein-Based Edible Films

Tensile strength (TS), percent elongation (%E), oxygen permeability (OP), and water vapor permeability (WVP) of lactic acid and rennet precipitated casein-based edible films were studied to determine the effect of protein to plasticizer ratio (0.6:1, 1:1, 1.4:1) and plasticizer type (sorbitol, glycerol) on these properties. TS increased (p<0.05) with increase in protein to plasticizer ratio. Sorbitol plasticized films were stronger (p<0.05) than glycerol plasticized films. However, films plasticized with glycerol were more extensible (p<0.05). Film %E decreased with increase in protein/plasticizer ratio for lactic acid casein films, whereas it increased for rennet casein films. Films plasticized with sorbitol were more effective (p<0.05) moisture and oxygen barriers than glycerol plasticized films. Overall, lactic acid casein films plasticized with sorbitol had the most effective mechanical and barrier properties.     

Effect of the presence of glycerol and Tween 20 on the chemical and physical properties of films based on chitosan with different degree of deacetylation

Chitosans with two different deacetylation degree (DD) (60.9% and 96%) were used to elaborate edible films. The influence of the degree of deacetylation and the presence of glycerol and Tween 20 in the formulation on the surface tension of the film forming solutions as well as on the chemical structure, optical and mechanical properties and water vapor permeability (WVP) of the resulting films were studied.IR spectra showed no significant differences on the chemical structures of chitosan of the different films. However, X-ray diffraction analysis indicated that the use of chitosan with higher DD and the use of glycerol as additive resulted in higher crystallinity. Films made of chitosan with the lower DD (60.9%) were found to have higher tensile strength (TS) and elongation (E) in a tensile test. Degree of deacetylation did not have any effect on WVP. The presence of glycerol resulted in less resistant, more elastic and more permeable films.The presence of Tween 20 improved the wettability of film solutions and affected significatively mechanical, optical and barrier properties of the films. A positive interaction between glycerol and Tween 20 was observed for WVP.     

Emulsifier Composition of Solid Lipid Nanoparticles (SLN) Affects Mechanical and Barrier Properties of SLN‐Protein Composite Films

Protein films can be applied to improve food quality and to reduce packaging waste. To overcome their poor water barrier properties, lipids are often incorporated. The function of incorporated lipid depends on the interface between filler and matrix. This study aimed to tailor the properties of a protein–lipid film by designing the oil/water interface to see if the concept of inactive/active filler is valid. Therefore, we varied the emulsifier stabilizing solid lipid nanoparticles (SLN) to promote (via β‐lactoglobulin) or to minimize (via Tween 20) interactions between particle surface and protein. SLN were incorporated into protein films and film properties were determined. Addition of SLN led to significantly decreased water vapor permeability (WVP) of protein films. However, WVP was mainly affected by the emulsifiers and not by the lipid. Protein‐stabilized SLN (BS) replaced a lacking protein in the protein network and therefore did not influence the mechanical properties of the films at ambient temperature. BS‐composite films were temperature sensitive, as lipid and sucrose palmitate melted at temperatures above 40 °C. Tween 20‐stabilized SLN (TS) led to reduced tensile strengths, probably due to perturbative effects of TS and plasticizing effects of Tween 20. Dynamic mechanical analysis showed that TS and Tween 20 increased film mobility. Melting of lipid and emulsifiers, and temperature‐dependent behavior of Tween 20 led to a strong temperature dependence of the film stiffness. By designing the interface, particles can be used to tailor mechanical properties of protein films. Tuned edible films could be used to control mass transfers between foods.     

Properties of Laminated Films from Whey Powder and Sodium Caseinate Mixtures and Zein Layers

Corn zein-stearic acid films were laminated to whey powder (WP) and sodium caseinate (SC) mixture (WSM) films. WSM films were prepared at three mass ratios of WP and SC (50:50, 60:40, and 70:30 in w/w) by casting method. WSM films with poor mechanical and barrier properties were produced as the whey powder ratio of WSM increased from 50:50 to 70:30. Corn-zein lamination improved the mechanical and water barrier properties of WSM films by increasing tensile strength (TS) from 4.7-14.5 to 14.0-26.8 MPa and by decreasing water vapor permeabilities (WVP) from 0.432-0.490 to 0.386-0.422 ng m/m² s Pa. However, elongations of corn-zein laminated films were reduced from 64.5-128.0 to 2.6-4.5%. Mechanical and water barrier properties of corn-zein laminated WSM films were affected by the mass ratio of whey powder to sodium caseinate in WSM films. Addition of stearic acid up to 10 g/100 g of corn zein decreased TS and WVP of laminated films to approximately 12 MPa and 0.36 ng m/m² s Pa regardless of mass ratio in WSM film. However, no significant differences in TS and WVP were found with further addition of stearic acids.     

Nanocellulose Reinforced Chitosan Composite Films as Affected by Nanofiller Loading and Plasticizer Content

ABSTRACT: Chitosan is a biopolymer obtained by N-deacetylation of chitin, produced from shellfish waste, which may be employed to elaborate edible films or coatings to enhance shelf life of food products. This study was conducted to evaluate the effect of different concentrations of nanofiller (cellulose nanofibers, CNF) and plasticizer (glycerol) on tensile properties (tensile strength—TS, elongation at break—EB, and Young's modulus—YM), water vapor permeability (WVP), and glass transition temperature (T_g) of chitosan edible films, and to establish a formulation to optimize their properties. The experiment was conducted according to a central composite design, with 2 variables: CNF (0 to 20 g/100 g) and glycerol (0 to 30 g/100 g) concentrations in the film (on a dry basis), which was produced by the so-called casting technique. Most responses (except by EB) were favored by high CNF concentrations and low glycerol contents. The optimization was based on maximizing TS, YM, and T_g, and decreasing WVP, while maintaining a minimum acceptable EB of 10%. The optimum conditions were defined as: glycerol concentration, 18 g/100 g; and CNF concentration, 15 g/100 g. AFM imaging of films suggested good dispersion of the CNF and good CNF-matrix interactions, which explains the good performance of the nanocomposite films. Practical Application: Chitosan is a biodegradable polymer which may be used to elaborate edible films or coatings to enhance shelf life of foods. This study demonstrates how cellulose nanofibers (CNF) can improve the mechanical and water vapor barrier properties of chitosan films. A nanocomposite film with 15% CNF and plasticized with 18% glycerol was comparable to some synthetic polymers in terms of strength and stiffness, but with poorer elongation and water vapor barrier, indicating that they can be used for applications that do not require high flexibility and/or water vapor barrier. The more important advantage of such films when compared to synthetic polymer films is their environmentally friendly properties.     

Water Vapor Permeability and Solubility of Films from Hydrolyzed Whey Protein

ABSTRACT: The effects of whey protein hydrolysis on film water vapor permeability (WVP) and solubility at 3 plasticizer levels were studied. Little or no significant difference (p > 0.05) appeared for film WVP between unhydrolyzed whey protein isolate (WPI), 5.5% degree of hydrolysis (DH) WPI and 10% DH WPI films at comparable plasticizer contents. However, increase in glycerol (gly) content significantly increased film WVP. Thus, reduction in WPI molecular weight (MW) through hydrolysis may be a better approach to improving film flexibility than addition of plasticizer. Both 5.5% and 10% DH WPI had significantly different (p ≤ 0.05) film solubility compared to unhydrolyzed WPI. Soluble Protein (SP) and total soluble matter (TSM) of hydrolyzed WPI films were much higher than for unhydrolyzed WPI films.     

Characterization of edible film fabricated with channel catfish (Ictalurus punctatus) gelatin extract using selected pretreatment methods

ABSTRACT:  Farm-raised catfish are important to the economy of the southeastern states in the United States, and catfish processing produces about 55% of by-products for inexpensive sale. Therefore, the utilization of catfish by-products is of great interest to the catfish industry. The objectives of this research were to determine the optimum pretreatment method to extract catfish gelatin for edible film application, and to characterize physical, mechanical, and barrier properties of edible films fabricated with catfish skin gelatin. Catfish skins obtained from a local plant were treated with 6 selected pretreatment methods. The main extraction was performed with deionized water at 50 °C after pretreatment. The gelatin yield was calculated and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) was performed to characterize molecular weight (MW) profile. Color, tensile strength (TS), elongation, and water barrier property were determined to characterize the fabricated catfish gelatin films. From the results of gelatin yield, color, SDS-PAGE, as well as mechanical and barrier properties of the film, the pretreatment method with 0.25 M NaOH and 0.09 M acetic acid, followed by extraction at 50 °C for 3 h, was determined as the optimum extraction method. The catfish gelatin exhibited higher MW fractions than commercial mammalian gelatin. The catfish gelatin extracts possessed film-forming properties determined by TS, elongation, and water vapor permeability (WVP) comparable to those of commercial mammalian gelatin. The selected formula for catfish gelatin film was determined as 1% gelatin and 20% glycerol, resulting in greatest TS and lowest WVP.     

Mechanical and Barrier Properties of Egg Albumen Films

Films were cast and dried from heated, alkaline aqueous egg albumen solutions containing glycerin (GLY) at 30, 40, or 50% w/w of protein, polyethylene glycol (PEG) at 50 or 60%, or sorbitol (S) at 50 or 60% as plasticizers. PEG-plasticized (60%) films also were prepared by substituting 10, 30, 50, or 70% of albumen with yolk solids. Film tensile strength (TS), elongation at break (E), water vapor permeability (WVP), and Hunter color values were measured. At a plasticizer content of 50%, films with S had the lowest WVP while films with PEG had the greatest E. S- and PEG-plasticized films had greater TS than GLY-plasticized films. Yolk solids decreased film TS, E, and WVP while increasing film yellowness.     

Mechanical and water vapor barrier properties of extruded and heat-pressed gelatin films

Gelatin-based edible films were produced by extruding hot melt of gelatin-based resins through a die with slot orifice and followed by heat-pressed method. The resins were plasticized with glycerol, sorbitol and the mixture of glycerol and sorbitol (MGS). The effect of type of plasticizer on extruded and heat-pressed (EHP) film-forming capacity was studied, and the mechanical and water barrier properties of resulting EHP gelatin films were compared with those of gelatin films prepared by solution casting method. Stretchable films were formed when glycerol or MGS were used as plasticizer, whereas resins plasticized with sorbitol were extruded in non-stretchable sheets. Glycerol plasticized gelatin film showed the highest flexibility and transparency among the EHP films tested. Tensile strength (TS), elongation (E) and water vapor permeability (WVP) of glycerol plasticized EHP gelatin films were 17.3 MPa, 215.9% and 2.46 ng m/m² s Pa, respectively, and EHP gelatin films had higher E values, lower TS values and higher WVP values compared to the glycerol plasticized cast gelatin films.     

Composite and bi-layer films based on gelatin and chitosan

The aims of this work were: to develop composite, bi-layer and laminated biodegradable films based on gelatin and chitosan, to determine film barrier and mechanical properties and to characterize their microstructure.Gelatin and chitosan concentrations used were 7.5% and 1% (w/w), respectively. Glycerol (0.75%) was added as plasticizer.Physicochemical properties such as moisture content, transparency and color were analyzed. Composite and bi-layer systems showed a compact structure indicating a good compatibility between components.Water vapor permeability (WVP) was independent of film thickness up to 120 μm for gelatin films and 60 μm for chitosan ones. Both, bi-layer and laminated systems resulted effective alternatives to reduce WVP of composite films (at least 42.5%). Bi-layer systems showed better mechanical properties than laminated ones. The resistance at break increased from 54.3 for composite to 77.2 MPa for bi-layer films, whereas elongation at break values of both composite and bi-layer films were similar (2.2–5.7%).     

Mechanical and barrier properties of biodegradable soy protein isolate-based films coated with polylactic acid

Polylactic acid (PLA)-coated soy protein isolate (SPI) films were prepared by dipping SPI film into PLA solution. The effects of coating on improvements in mechanical and water barrier properties of the film were tested by measuring selected film properties such as tensile strength (TS), elongation at break (E), water vapor permeability (WVP), and water solubility (WS). TS of SPI films increased from 2.8±0.3 up to 17.4±2.1 MPa, depending on the PLA concentration of the coating solution, without sacrificing the film's extensibility. In contrast, the extensibility of SPI film coated with solution containing more than 2 g PLA/100 ml solvent, increased. WVP of PLA-coated SPI films decreased from 20 to 60 fold, depending on the concentration of PLA coating solution. Water resistance of SPI films was greatly improved as demonstrated by the dramatic decrease in WS for PLA-coated films. The improvement in water barrier properties was mainly attributed to the hydrophobicity of PLA.