Wettability, surface microstructure and mechanical properties of films based on phosphorus oxychloride-treated zein

BACKGROUND: Zein, the predominant protein in corn, has been extensively studied as an alternative packaging material in edible and biodegradable films. However, films made from 100% zein are brittle under normal conditions. The aim of this investigation was to improve the film‐forming properties of zein by chemical phosphorylation. The surface hydrophobicity, surface microstructure and mechanical properties of films based on untreated and phosphorus oxychloride (POCl₃)‐treated zein were evaluated and compared. The effect of POCl₃ treatment on the rheological properties of zein solutions was also studied. RESULTS: POCl₃ treatment, especially at pH 7 and 9, led to an increase in the apparent viscosity of zein solutions. Atomic force microscopy (AFM) analysis showed that the film based on POCl₃‐treated zein at pH 7 had a stone‐like surface microstructure with a higher roughness (R_q) than the untreated zein film. The AFM data may partially account for the phenomenon that this film exhibited high surface hydrophobicity (H₀). POCl₃ treatment diminished the tensile strength (TS) of zein films from 4.83–6.67 to 1.3–2.29 MPa. However, the elongation at break (EAB) of the films at pH 7 and 9 increased from 3.0–4.5% (control film) to 150.1–122.7% (POCl₃‐treated film), indicating the potential application of zein films in wrapping foods or in non‐food industries such as sugar, fruit or troche that need good extension packing materials. CONCLUSION: The data presented suggest that the properties of zein films could be modulated by chemical phosphorylation treatment with POCl₃ at an appropriate pH value. Copyright © 2011 Society of Chemical Industry     

Effects of glycerol,sorbitol, xylitol and fructose plasticisers on mechanical and moisture barrier properties of pullulan–alginate–carboxymethylcellulose blend films

The effects of glycerol, sorbitol, xylitol and fructose plasticisers on water sorption, mechanical properties, water vapour permeability (WVP) and microstructure of pullulan–alginate–carboxymethycellulose (PAC) blend films were investigated. At low plasticiser concentrations (below 7% w/w dry basis), antiplasticisation effect was observed, causing an increase in tensile strength (TS) but a decrease in the equilibrium moisture content. As glycerol concentration increased from 0% to 7%, TS increased from 68.1 to 69.6 MPa, whereas equilibrium moisture contents at 0.84 a_w decreased from 0.37 to 0.3 g H₂O g^?1 dry basis. At higher plasticiser concentrations (14–25% w/w), an opposite trend was observed on the PAC films, resulting in the reduction of TS and elevation of moisture content. Among the four plasticisers tested, the fructose‐plasticised films were the most brittle, showing the highest TS, but had the lowest elongation at break (EAB), WVP and equilibrium moisture content values than films plasticised with other polyols. On the other hand, glycerol resulted in the most flexible film structure, exhibiting opposite materials' properties as compared with the fructose‐plasticised films. For instance, at 25% (w/w) plasticiser concentration, EAB and WVP values of fructose‐plasticised films were 33.5% and 3.48 × 10^?6 g m Pa^?1 h^?1 m^?2, which were significantly lower than that of glycerol‐plasticised films (58.6% and 4.86 × 10^?6 g m Pa^?1 h^?1 m^?2, respectively). Scanning electron microscopy showed that the plasticised PCA films were less homogeneous and more porous than the unplasticised counterparts, indicating that plasticisers had an effect on the microstructural morphology of the film matrix.     

Liquid and vapour water transfer through whey protein/lipid emulsion films

BACKGROUND: Edible films and coatings based on protein/lipid combinations are among the new products being developed in order to reduce the use of plastic packaging polymers for food applications. This study was conducted to determine the effect of rapeseed oil on selected physicochemical properties of cast whey protein films. RESULTS: Films were cast from heated (80 °C for 30 min) aqueous solutions of whey protein isolate (WPI, 100 g kg^?1 of water) containing glycerol (50 g kg^?1 of WPI) as a plasticiser and different levels of added rapeseed oil (0, 1, 2, 3 and 4% w/w of WPI). Measurements of film microstructure, laser light‐scattering granulometry, differential scanning calorimetry, wetting properties and water vapour permeability (WVP) were made. The emulsion structure in the film suspension changed significantly during drying, with oil creaming and coalescence occurring. Increasing oil concentration led to a 2.5‐fold increase in surface hydrophobicity and decreases in WVP and denaturation temperature (T_max). CONCLUSION: Film structure and surface properties explain the moisture absorption and film swelling as a function of moisture level and time and consequently the WVP behaviour. Small amounts of rapeseed oil favourably affect the WVP of WPI films, particularly at higher humidities. Copyright © 2010 Society of Chemical Industry     

Development and characterization of an edible chitosan–whey protein nano composite film for chestnut (Castanea mollissima Bl.) preservation

Chitosan (CHI) and whey protein are usually used to prepare edible films for food preservation. However, the composite film composed of the two components does not yield satisfactory properties for chestnut preservation. In this study, nano-cellulose and cinnamaldehyde (CMA) were added to CHI and whey protein, creating a new composite film with strong water retention, bacteriostatic, and mechanical properties. The water vapor permeability (WVP) of the film decreased by 21.61% with the addition of 0.5% (w/v) nano-cellulose, and 23.02% with the addition of 0.3% (w/v) CMA. Furthermore, water solubility (WS) decreased 22.05%, and the density of the film was significantly improved with the addition of 0.3% (w/v) CMA. The optimized formula of the film was CHI 2.5% (w/v), whey protein 3.0% (w/v), nano-cellulose 0.5% (w/v), CMA 0.3% (w/v), and pH 3.8, as determined by orthogonal testing L9(3⁴), with fuzzy comprehensive assessment, of WVP, WS, tensile strength, and elongation at break. The film clearly inhibited the growth of E. coli, S. aureus, and Chinese chestnut fungus, destroying the mycelial structure of the fungus. In addition, coating effectively reduced the weight loss, mildew rate, and calcification index during 16 days of storage of chestnuts at 25 °C.     

Fatty Acid Distribution and Its Effect on Oxygen Permeability in Laminated Edible Films

Lipid contents, distributed fatty acid concentrations and oxygen permeability of laminated methylcellulose/corn zein-fatty acid films and methylcellulose films separated from the laminate were investigated. Total lipid contents ranged from 0.056 to 0.157 g/cm³ for the laminated edible film structure, and distributed fatty acid contents ranged from 0.062 to 0.220 g/cm³ in the methylcellulose layer. Fatty acid distribution increased with chain length and fatty acid concentration. Oxygen permeabilities of both laminated methylcellulose/corn zein-fatty acid films and methylcellulose films separated from the laminate increased as chain length of fatty acid decreased and concentration of fatty acid increased. Scanning electron microscopy and Soxhlet extraction appeared to show distribution of fatty acids from the corn zein layer into and through the methylcellulose layer.     

Antimicrobial Effects of Lactoferrin, Lysozyme, and the Lactoperoxidase System and Edible Whey Protein Films Incorporating the Lactoperoxidase System Against Salmonella enterica and Escherichia coli O157:H7

Lactoferrin (LF), lysozyme (LZ), the lactoperoxidase system (LPOS), and edible whey protein isolate (WPI) films incorporating LPOS were studied for inhibition of Salmonella enterica and Escherichia coli O157:H7. Antimicrobial effects of LF (5 to 40 mg/mL), LZ (1 to 20 mg/mL), and LPOS (0.5% to 5.0% [w/v] [0.03–.25 g/g, dry basis]) were examined by measuring turbidity of antimicrobial‐containing media after inoculation and by examining cell inhibition by WPI films incorporating LPOS (LPOS‐WPI films) on an agar recovery medium. Elastic modulus (EM), tensile strength (TS), percent elongation (%E), oxygen permeability (OP), and Hunter L, a and b of WPI films incorporating 0.03 to 0.25 g/g of LPOS were compared with those of plain WPI films without LPOS. The growth of S. enterica and E. coli O157:H7 (4 log colony‐forming units [CFU]/mL) in tryptic soy broth (TSB) was not prevented by LF at ≥20 and ≥40 mg/mL, respectively. S. enterica and E. coli O157:H7 in TSB were not inhibited by LZ at ≥ 6 and ≥ 20 mg/mL, respectively. LPOS at concentrations of 2.75% (w/v) and 1.0% (w/v) reduced S. enterica and E. coli O157:H7 to below the limit of detection (1 CFU/mL) in TSB, respectively. LPOS‐WPI films (0.15 g/g) completely inhibited S. enterica and E. coli O157:H7 (4 log CFU/cm²), inoculated either onto agar before placing the film disc or onto top of the film disc. Incorporation of 0.25 g/g of LPOS decreased EM, TS, and %E. The oxygen barrier property of WPI films was improved with the incorporation of LPOS at 0.15 to 0.25 g/g.     

Nanofibre-based bilayer biopolymer films: enhancement of antioxidant activity and potential for food packaging application

This study aimed to enhance the antioxidant property of biopolymer film without the incorporation of external agents. The active bilayer film with improved antioxidant activity has been developed by electrospinning zein, a prolamine of corn as nanofibre (average diameter of 286 nm) on solvent cast chitosan film. Zein nanofibres exhibited a slight increase in antioxidant activity as compared to solvent cast zein film. But, zein nanofibre coating on chitosan films significantly improved its antioxidant activity from 12.41% to 44.17%. The developed bilayer films were evaluated for its ability to prevent browning in minimally processed apple slices and compared with those of chitosan and zein films plasticised with polyethylene glycol. Higher surface to volume ratio and better affinity of zein nanofibres in the bilayer film helped enhance its anti-browning ability. Thus, zein nanofibre-coated chitosan bilayer films can be used as an effective anti-browning packaging material for the packing of minimally processed fruits.     

QUALITY PRESERVATION OF COMMERCIAL FISH BALLS WITH ANTIMICROBIAL ZEIN COATINGS

ABSTRACT

To enhance the practical application of active edible coatings in the food industry, edible zein coatings incorporated with nisin (54.4 AU/cm²) or nisin/ethylenediaminetetraacetic acid (EDTA; 568 µg/cm²) were used to preserve the quality of commercially manufactured fish balls. The microbial load, total basic volatile nitrogen (TVB‐N) content and weight loss were served as quality indicators. The increase of microbial load of fish balls coated with antimicrobial zein during a 15‐day refrigeration storage period was less than 1 log cfu/g, while the microbial load increased about 3 log cfu/g for the control group without the coating treatment. The formation of TVB‐N was significantly (P < 0.05) reduced when fish balls were coated with antimicrobial zein. With or without antimicrobial agent, coated fish balls exerted significantly (P < 0.05) less weight loss than uncoated fish balls.

PRACTICAL APPLICATIONS

Although edible coatings or films containing bioactive substance have been intensively studied over the last few decades, most of these, still, have not had widespread commercial applications because the majority of studies were conducted with food‐simulated systems or food samples produced in laboratory. The fish balls commercially manufactured in a fishery product factory was used to demonstrate the efficacy of antimicrobial edible coating will enhance the confidence of food manufactures to apply the technology in their products.     

Physicochemical, nutritional, and antimicrobial properties of wine grape (cv. Merlot) pomace extract-based films

Abstract: Wine grape pomace (WGP) (cv. Merlot) extract‐based films were studied in terms of their physicochemical, mechanical, water barrier, nutritional, and antibacterial properties. Pomace extract (PE) was obtained by hot water extraction and had a total soluble solid of 3.6% and pH 3.65. Plant‐based polysaccharides, low methoxyl pectin (LMP, 0.75% w/w), sodium alginate (SA, 0.3% w/w), or Ticafilm^® (TF, 2% w/w), was added into PE for film formation, respectively. Elongation at break and tensile strength were 23% and 4.04 MPa for TF‐PE film, 25% and 1.12 MPa for SA‐PE film, and 9.89% and 1.56 MPa for LMP‐PE film. Water vapor permeability of LMP‐PE and SA‐PE films was 63 and 60 g mm m^?2 d^?1 kPa, respectively, lower than that of TF‐PE film (70 g mm m^?2 d^?1 kPa) (P < 0.05). LMP‐PE film had higher water solubility, indicated by the haze percentage of water after 24 h of film immersion (52.8%) than that of TF‐PE (25.7%) and SA‐PE (15.9%) films, and also had higher amount of released phenolics (96.6%) than that of TF‐PE (93.8%) and SA‐PE (80.5%) films. PE films showed antibacterial activity against both Escherichia coli and Listeria innocua, in which approximate 5‐log reductions in E. coli and 1.7‐ to 3.0‐log reductions in L. innocua were observed at the end of 24 h incubation test compared with control. This study demonstrated the possibility of utilizing WGP extracts as natural, antimicrobial, and antioxidant promoting film‐forming material for various food applications. Practical Application: WGP extract‐based edible films with the addition of a small amount of commercial polysaccharides showed attractive color and comparable mechanical and water barrier properties to other edible films. The films also demonstrated their potential antioxidant and antimicrobial functions. Hence, they may be used as colorful wraps or coatings for food, pharmaceutical, or other similar applications.     

Mechanical properties and water vapour permeability of hydrolysed collagen–cocoa butter edible films plasticised with sucrose

The aim of this study was to develop and characterise edible films produced from hydrolysed collagen and cocoa butter and plasticised with sucrose. The mechanical properties, water vapour permeability, opacity and morphology of the films were characterised. The film composition that yielded the best results was used to produce a coating for application in chocolate panned products. A water-based coating with desirable barrier properties that could replace shellac is important for the environment as well as health, and also because chocolate products have great appeal among children. The films obtained were easily manageable and flexible. Sucrose reduced tensile strength (TS), while hydrolysed collagen at concentrations above 15% increased it. Cocoa butter resulted in less-resistant films. The elongation at break values (EAB%) were higher for films containing higher sucrose concentrations. The water vapour permeability (WVP) ranged from 0.32 to 0.63 g mm m⁻² h⁻¹ kPa⁻¹. For the same concentration of cocoa butter, the WVP was directly affected by the thickness of the film, i.e., the greater the thickness, the higher the WVP. Cocoa butter increased film opacity, while sucrose decreased it, particularly at concentrations above 17.5%. High concentrations of hydrolysed collagen produced films with more homogeneous surfaces. The brightness of the product with the coating developed in this study was attractive; however the brightness of the product with shellac was considered more intense. The properties of these films indicate that they are promising systems for coating chocolate panned products.     

Development and characterization of a novel biodegradable edible film obtained from psyllium seed (Plantago ovata Forsk)

In this study, the physical, thermal and mechanical properties of a novel edible film based on psyllium hydrocolloid (PH) were investigated. PH films were prepared by incorporation of three levels of glycerol (15%, 25%, and 35% w/w). As glycerol concentration increased, water vapor permeability (WVP), percent of elongation (E%) and water solubility of PH films increased whilst, tensile strength (TS), surface hydrophobicity and glass transition point (T_g) decreased significantly. At the level of 15% (W/W) of glycerol, PH films showed the lowest WVP values (1.16 × 10⁻¹⁰ g H₂O m⁻² s⁻¹ MPa⁻¹), E% (24.57%) and water solubility (47.69%) and the highest values for TS (14.31 MPa), water contact angle (84.47°) and T_g (175.2 °C). By increasing glycerol concentration, PH films became slightly greenish and yellowish in color but still transparent in appearance. This study revealed that the psyllium hydrocolloid had a good potential to be used in producing edible films with interesting specifications.     

制备条件对玉米醇溶蛋白膜机械性能的影响

以玉米醇溶蛋白为原料制备蛋白膜时,研究了乙醇浓度、蛋白质浓度等制备条件对蛋白膜机械性能的影响。在单因素实验基础上,以蛋白质浓度、甘油添加量、聚乙二醇400添加量、半胱氨酸添加量4个因素为变量进行响应面优化,结果表明:当乙醇体积分数为75%、水浴成膜温度70℃、蛋白质浓度0.103 4g/ml、甘油质量分数30%、聚乙二醇400质量分数24%、半胱氨酸质量分数0.80%时,蛋白膜的拉伸强度为7.5MPa,断裂延伸率为202.7%。     

Incorporating phenolic compounds opens a new perspective to use zein films as flexible bioactive packaging materials

To eliminate their classical brittleness and flexibility problems zein films were plasticized by incorporation of different phenolic acids (gallic acid (GA), p-hydroxy benzoic acid (HBA) or ferulic acids (FA)) or flavonoids (catechin (CAT), flavone (FLA) or quercetin (QU)). The use of GA, CAT, FA and HBA at 3 mg/cm² eliminated the brittleness of films and gave highly flexible films showing elongations between 135% and 189%, while FLA and QU caused no considerable effect on film elongation. The films containing FA and HBA showed extreme swelling and lost their structural integrity when hydrated in distilled water. In contrast, CAT and GA containing films maintained their integrity following hydration. Most of the GA (up to 93%) and a considerable portion of CAT (up to 60%) in the films existed in soluble form. Therefore, the films showed antioxidant and/or antimicrobial activity. The TEACs of soluble phenolic compounds in 3 mg/cm² CAT and GA containing films were 21.0 and 86.2 ??mol trolox/cm², respectively. The GA containing films showed antimicrobial activity on Listeria monocytogenes and Campylobacter jejuni, while CAT showed no antimicrobial activity on these bacteria at the studied concentration. This work opens a new perspective for using zein in flexible bioactive packaging.     

Listeria monocytogenes Inhibition by Whey Protein Films and Coatings Incorporating the Lactoperoxidase System

Antimicrobial effects of whey protein isolate (WPI) films and coatings incorporating the lactoperoxidase system (LPOS) against Listeria monocytogenes were studied by turbidity, plate counting, disc‐covering, and disc‐surface‐spreading tests using various growth media. Survival of L. monocytogenes applied to smoked salmon before or after the coating was monitored immediately after application and during storage at 4 °C and 10 °C for up to 35 d. Tensile properties (elastic modulus [EM], tensile strength [TS], elongation [E]), oxygen permeability (OP), and color (Hunter L, a, b) of WPI films, with and without LPOS, were also compared. LPOS inhibited L. monocytogenes in broth and on agar media. WPI films incorporating 29 mg of LPOS per gram of film (dry basis) inhibited 4.2 log colony‐forming units (CFU)/cm² of L. monocytogenes inoculated on agar media. WPI coatings prepared with LPOS at 0.7% (w/w) in a coating solution (40 mg LPOS/g coating [dry basis]) initially reduced >3 and 1 log CFU/g of L. monocytogenes and total aerobic microorganisms in smoked salmon, respectively. The WPI coatings incorporating LPOS prevented the growth of L. monocytogenes in smoked salmon at 4 °C and 10 °C for 35 d and 14 d, respectively. The tensile properties, oxygen permeability, and color of WPI films were not significantly changed by incorporation of LPOS (P >0.05).     

Development of a defatted mustard meal-based composite film and its application to smoked salmon to retard lipid oxidation

An antioxidant composite film was developed from defatted mustard meal (DMM) without incorporating external antioxidants and its applicability as a coating to smoked salmon has been investigated. Film-forming variables included the concentration of xanthan, heat treatment, and high pressure homogenisation. Tensile strength, elongation, water vapour permeability, and water solubility of composite films of DMM and xanthan were 5.1–8.8 MPa, 2.9–5.0%, 1.5–2.4 g mm/kPa/h/m², and 1.1–1.6%, respectively. The composite film with xanthan at 5% (w/w) demonstrated antioxidant properties and the coating with the solution forming the composite film (5% xanthan) retarded lipid oxidation and significantly reduced volatile changes in smoked salmon during storage at 4, 10, and 20 °C for 21 days. Coated salmon was preferred to uncoated salmon in glossiness and fish smell. The composite coating improved the stability of smoked salmon against lipid oxidation without imparting a negative sensory quality to the salmon.     

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.     

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.     

Effects of the free and pre‐encapsulated calcium ions on the physical properties of whey protein edible film

Effects of the free and the pre‐encapsulated calcium ions on the physical properties of the whey protein isolate film were studied for improving calcium content in the edible films. At pH 8, the film‐forming process was hindered by serious protein aggregation and gelation caused by 0.5% (w/w) free calcium ions added in an 8% whey protein isolate solution. If the calcium ions were pre‐encapsulated in the protein microparticles (contained 17% Ca²⁺) using spray drying method, and then added in the film‐forming solution prepared using the same protein, the calcium content could be doubled (1%, w/w) without significant effects on the physical properties of the film. The calcium release ability (55% at pH 1.2, 32% at pH 7.4 and more than 75% with the enzymes) of the film was also investigated.     

Utilization of Zein Coating and Sorbic Acid to Reduce Listeria monocytogenes Growth on Cooked Sweet Corn

Several proteins, lipids and waxes were tested as edible coatings on sweet corn. Only zein, a natural constituent of corn, gave a continuous adhesive and stable coating with satisfactory sensory properties. After 8 days at 10 °C, the population of L. monocytogenes was 10‐fold lower on coated sweet corn than on non‐coated sweet corn indicating a barrier effect of zein coating. Sorbic acid was incorporated in the coating at a concentration required to inhibit L. monocytogenes growth (approximately 1 mg sorbic acid/g of sweet corn). The inhibitory concentration was the same for both coated and non‐coated sweet corn. Zein coating therefore did not improve the preservative effect of sorbic acid.     

Edible oxygen barrier bilayer film pouches from corn zein and soy protein isolate for olive oil packaging

An edible oxygen barrier film pouch was fabricated from a heat sealable corn zein (CZ) layer laminated on soy protein isolate (SPI) film and used to package olive oil condiments for use with instant noodles. The mechanical, barrier, and physical properties of the CZ/SPI bilayer films were then investigated and the oxidative stability of olive oil in the pouches was measured during storage under dry and intermediate relative humidity conditions. When compared to the SPI film, lamination with an additional layer of CZ film led to increased tensile strength and water barrier properties, while it had a lower elongation at break and decreased oxygen barrier properties. Nevertheless, the oxygen permeability of the CZ/SPI film (0.81 × 10⁻¹⁸ m³ m/m² s Pa) was lower than that of nylon-metalocene catalyzed linear low-density polyethylene (NY/mLLDPE) film (3.51 × 10⁻¹⁸ m³ m/m² s Pa) which is the material usually used for such condiments. The CZ/SPI bilayer films generated here were heat sealable at 120-130 °C and produced a seal strength greater than 300 N/m. The higher oxygen barrier property of the CZ/SPI bilayer films resulted in reduced oxidative rancidity of olive oil packaged in the CZ/SPI film when compared to olive oil packaged in NY/mLLDPE films.