硬脂酸-胱氨酸-大豆分离蛋白复合膜的机械特性和吸湿性研究

以硬脂酸作为增塑剂，胱氨酸作为交联剂制备具有一定力学性能和良好抗湿性能的大豆分离蛋白复合膜。将膜放在25℃，相对湿度为50%的干燥器中平衡两天，用质构仪测定膜的抗拉强度(TS),延伸率(E(%))。在水分活度a_w为0.10～0.90的范围内研究了复合膜在25℃的吸湿特性。吸湿速率和吸湿等温线数据分别拟合到Peleg's 方程和GAB(Guggenheim-Anderson-de Boer)模型。结果表明：大豆蛋白复合膜的TS、延伸率E(%)以及吸湿速率随着硬脂酸和胱氨酸的添加比率显著地变化。硬脂酸和胱氨酸的最佳添加比率为40∶60(w/w)(每升蛋白质溶液中加入10 g混合添加剂)，此时，大豆蛋白膜的强度比原来提高2倍，并且有最佳的吸湿速率。吸湿数据和GAB 模型有很高的拟合度，拟合系数最高达0.99。     

Plasticizers for Zein: Their Effect on Tensile Properties and Water Absorption of Zein Films

Cast zein films are brittle at room conditions, so plasticizers are added to make them more flexible. The tensile properties of these films are known to be affected by the relative humidity (RH) of the ambient air. However, little is known about how the plasticizers are affected by RH. Cast zein films were plasticized with either glycerol (GLY), triethylene glycol (TEG), dibutyl tartrate (DBT), levulinic acid (LA), polyethylene glycol 300 (PEG), or oleic acid (OA). Mechanical properties and moisture content (MC) of the films were measured after one week of storage at 3, 20, 50, 70, 81, and 93% RH. The relative humidity of the films' storage had a great effect on the films' tensile properties. All the films' tensile strength and Young's modulus values decreased as RH increased. Films containing DBT, TEG, LA, or PEG showed an increase in the percent elongation with increasing RH. Films containing GLY, OA, or no plasticizer did not show any increase in percent elongation as RH increased. The changes seen in tensile properties with increasing RH are because of zein's hygroscopic nature. The absorbed water will further plasticize the zein. The type of plasticizer used determined the extent of the changes seen in the tensile properties of films stored at different RH values. Depending on the plasticizers used in the film, there were large differences in the amount of water absorbed. Films increasingly absorbed water depending on the plasticizer they contained in the order GLY > TEG > LA > PEG > NONE > DBT > OA. Films containing hygroscopic plasticizers like TEG absorbed too much water at high RH and became weak, but they absorbed enough water at lower RH values to not be brittle. While films containing the more hydrophobic plasticizer DBT were brittle at intermediate RH values, they had good mechanical properties at high RH values.     

Water sorption properties of extruded zein films

Water interactions in extruded zein films were investigated through moisture sorption isotherms. Sorption isotherms of zein products were affected by composition and structure morphology. Zein powder showed moisture sorption hysteresis, which was not observed in extruded samples. Extruded samples held less moisture than zein powder, while films containing oleic acid showed further reduction in moisture uptake. Brunauer, Emmett, and Teller (BET) and Guggenheim, Anderson, and De Boer (GAB) models fitted well the moisture sorption isotherms of zein products. Monolayer values estimated by BET and GAB models were consistent with predictions based on zein structural models. Water vapor permeability (WVP) of zein films was affected by the relative humidity of testing environment. Higher relative humidity resulted in higher WVP.     

Water Vapor Barrier Properties of Zein Films Plasticized with Oleic Acid

Water sorption, water vapor permeability, and tensile properties were evaluated for zein films plasticized with oleic acid. The effect of relative humidity on water vapor permeability and tensile properties of films was investigated. Samples were produced by two different methods: casting from a zein solution and stretching from a zein-fatty acid resin. Films were also coated with linseed oil. Results indicated that preparation method affected water sorption and permeability of zein films. Resin films showed lower water sorption than cast films, especially at high A_w values. Water vapor permeability was also lower for resin films. Coating with linseed oil further improved water vapor barrier ability of resin films. Permeability was affected by environmental relative humidity; higher relative humidity resulted in increased permeability. Environmental relative humidity also affected tensile properties of resin films. Toughness and elongation were improved when relative humidity increased from 50 to 85% rh. Tensile strength showed a maximum at 75% rh. Coating improved elongation and toughness of films. Maximum elongation and toughness were observed for coated samples at 85% rh. Zein resin films showed good tensile and water barrier properties that were maintained through environmental humidity levels from 50 to 98% rh.     

Development and characterization of biodegradable films made from wheat gluten protein fractions

Gliadins and glutenins were extracted from commercial wheat gluten on the basis of their extractability in ethanol and used to produce film-forming solutions. Films cast using these gliadin- and glutenin-rich solutions were characterized. Glycerol was used as a plasticizer, and its effect on the films was also studied. Films obtained from the glutenin fraction presented higher tensile strength values and lower elongation at break and water vapor permeability values than gliadin films. Gliadin films disintegrated when immersed in water. The GAB isotherm model was used to describe the equilibrium moisture sorption of the films. The glycerol concentration largely modified mechanical and water vapor barrier properties of both film types.     

Effects of lamination and coating with drying oils on tensile and barrier properties of zein films.

Zein films plasticized with oleic acid have been considered potentially useful for biodegradable packaging applications. However, moisture was found to affect their tensile and gas barrier properties. We investigated the effects of two converting processes, fusion lamination and coating with drying oils, on tensile properties and gas permeability of zein films. Zein films were laminated to 4-ply sheets in a Carver press and coated with tung oil, linseed oil, or a mixture of tung and soybean oils. Tensile properties and permeability to water vapor, oxygen, and carbon dioxide were measured according to ASTM methods. Laminated films were clearer, tougher, and more flexible, and had a smoother finish than nontreated sheets. Lamination decreased O(2) and CO(2) permeability by filling in voids and pinholes in the film structure. Coating increased tensile strength and elongation and decreased water vapor permeability. Coatings acted as a composite layer preventing crack propagation and increasing film strength. They also formed a highly hydrophobic surface that prevented film wetting.     

Extrusion and Characterization of Starch Films

Starch plasticized with water, glycerol, and stearic acid was extruded and sheeted into films 0.4–0.6 mm thick. The ingredients were extruded in a conical twin‐screw extruder at a temperature profile of 50–120–120–120°C and a screw speed of 45 rpm. The effects of glycerol, water, and stearic acid on selected physical and functional properties of the films were studied. The tensile strength, tensile strain at break, and Young's modulus were 0.23–2.91 MPa, 45.79–90.83%, and 2.89–37.94 MPa, respectively. Differential scanning calorimetry thermograms exhibited two glass transitions and multiple melting endotherms, including that of amylose‐lipid complexes formed during extrusion. The enthalpy of gelatinization of starch in the extruded films was 0.7–4.1 J/g and was dependent largely on the plasticizer content. Fourier‐transform infrared spectra revealed significant interactions between the starch and plasticizer but the peaks shifted to higher wave numbers with increasing glycerol content. During extrusion in the presence of glycerol, the A‐type crystalline structure of starch was transformed to B‐type. It also was observed that the V_h crystallinity increased with increase in glycerol content due to tight packing of starch chains. The water vapor permeabilities of the starch films were 12.3–19.9 g·mm/hr·m²·kPa.     

Properties and Microstructure of Zein Sheets Plasticized with Palmitic and Stearic Acids

Interest in biodegradable materials for packaging and agricultural uses has grown in recent years. Plant proteins have been proposed as inexpensive, renewable, and abundant feedstock. Corn zein was investigated based on value-added considerations and on the unique thermoplastic and hydrophobic properties of zein. Films prepared from zein are known to be tough and resistant, but also hard and brittle, thus requiring the addition of plasticizers to improve flexibility. The objectives of this research were to study the tensile properties, water absorption, and microstructure of zein sheets plasticized with palmitic and stearic acids. Both palmitic and stearic acids showed similar effects as plasticizers of zein. Tensile strength of zein sheets increased with the addition of low levels of plasticizers. However, beyond a critical point, tensile strength decreased with further addition of fatty acids. Water absorption decreased continuously with increasing fatty acid content. Kinetic parameters indicated fatty acids decreased water absorption by decreasing the saturation level of zein sheets. Coating zein with flax oil decreased the rate of water absorption by sealing off surface pores. Scanning electron micrographs of zein sheets showed the development of layered structures as fatty acid content increased. Zein-fatty acid layers were believed to be responsible for the increased tensile strength of plasticized zein sheets and to have contributed to increased resistance to water absorption.     

Antimicrobial and physicochemical properties of chitosan-HPMC-based films

To prepare composite films from biopolymers with anti-listerial activity and moisture barrier properties, the antimicrobial efficiency of chitosan-hydroxy propyl methyl cellulose (HPMC) films, chitosan-HPMC films associated with lipid, and chitosan-HPMC films chemically modified by cross-linking were evaluated. In addition, the physicochemical properties of composite films were evaluated to determine their potential for food applications. The incorporation of stearic acid into the composite chitosan-HPMC film formulation decreased water sensitivity such as initial solubility in water and water drop angle. Thus, cross-linking of composite chitosan-HPMC, using citric acid as the cross-linking agent, led to a 40% reduction in solubility in water. The water vapor transfer rate of HPMC film, approximately 270 g x m(-2) x day(-1) x atm(-1), was improved by incorporating chitosan and was further reduced 40% by the addition of stearic acid and/or cross-linking. Anti-listerial activity of films was determined on solid medium by a numeration technique. Chitosan-HPMC-based films, with and without stearic acid, inhibited the growth of Listeria monocytogenes completely. On the other hand, a loss of antimicrobial activity after chemical cross-linking modification was observed. FTIR and 13C NMR analyses were then conducted in order to study a potential chemical modification of biopolymers such as a chemical reaction with the amino group of chitosan. To complete the study, the mechanical properties of composite films were determined from tensile strength assays.     

Effect of endogenous triacylglycerol hydrolysates on the mechanical properties of Zein films from ground corn

Dry-milled yellow corn and freshly ground food and nonfood grade yellow and white hybrid corn kernels were pretreated in a solution of lactic acid and sodium metabisulfite followed by extraction with 70% ethanol. Zein was precipitated from the extract by reducing the ethanol content of the extract to 40%. Lipid associated with the zein isolates was between 15 and 20% and contained mostly endogenous free fatty acids. The effect of the endogenous free fatty acids on zein isolate films, with and without free fatty acids, was determined by measuring various film properties. Stress-strain measurements indicated 40-200% greater elongation for zein films containing endogenous free fatty acids. Films prepared from zein isolated from preground corn stored for approximately 4 months (27 degrees C, 17% relative humidity) had approximately 3 times greater elongation values than zein films prepared from freshly ground corn.     

Properties and Microstructure of Plasticized Zein Films

A new method for preparation of zein films involving plasticization of zein with oleic acid to form an intermediate moldable resin was presented. The resin was stretched over rigid frames to form thin membranes that were set in flexible films. The objective of the study was to investigate the effect of film preparation method on film properties. Tensile properties, microstructure, and thermal behavior of zein films plasticized with oleic acid were investigated for films prepared by conventional casting from ethanol solutions and by stretching of plasticized resins. Cast films were stiff and brittle, whereas resin films showed more flexibility and toughness. Differential scanning calorimetry thermograms of cast films indicated phase separations were generated when heated that were not observed for resin films. Microstructure images showed a higher degree of structure development and orientation in resin than in cast films. Glass-transition temperatures of resin films were measured at -94 and 104.4° C, indicating the film remained flexible through a wide temperature range. Resin film flexibility and toughness were attributed to effective plasticization that led to fiber formation and orientation.     

Water Barrier Properties of Zein‐Oleic Acid Films

Free‐standing films were prepared from zein formulations containing 30, 40, 50, 60, 70, and 80% oleic acid (OA). Zein/OA formulations were also used as coating films for rodent diet bars. Water vapor permeability (WVP) of films and moisture loss rate (MLR) of coated rodent diet bars were measured at 4 and 25°C. Temperature affected the water barrier properties of films and coatings. At 4°C, WVP of films decreased with OA concentration while it increased at 25°C. WVP behavior was attributed to oleic acid phase changes due to temperature. At 4°C, OA is a crystalline solid that limits water diffusion through the films. At 25°C, liquid OA increased the system free volume and allowed for water diffusion. The effect was more pronounced the higher the OA concentration in films. Differential scanning calorimetry (DSC) of zein/OA films showed endothermic peaks at 12–18°C, confirming the melting of OA in that temperature range. MLR of coated rodent diet bars was also affected by temperature and OA concentration in coating formulations. In this case, formulations containing 40, 50, and 60% OA were better moisture barriers than coatings with higher OA content at both 4 and 25°C. Moisture losses were reduced at 4°C due to OA solidification.     

Solubility and moisture sorption isotherms of whey-protein-based edible films as influenced by lipid and plasticizer incorporation

Plasticized whey-protein and whey-protein emulsion films were produced using sorbitol and glycerol as plasticizers and butterfat and candelilla wax as lipids. Protein, plasticizer, and lipid ratios were optimized to obtain acceptable free-standing flexible films. Water solubility (20 degrees C, 24 h) and moisture sorption isotherms (0.18-0.90 a(w), 25 degrees C) of the films were determined. The experimental moisture sorption isotherm values were fitted using the Guggenheim-Anderson-DeBoer (GAB) model. Solubility and equilibrium moisture contents (EMC) of the films were influenced by plasticizer and lipid incorporation. EMCs of all films increased rapidly at a(w) > or = 0.65. Incorporation of lipids reduced solubilities and EMCs of sorbitol- and glycerol-plasticized films. The effects of plasticizer and lipid type on GAB constants were also determined.     

电场处理改善玉米醇溶蛋白膜理化性质

传统浇铸法制备的玉米醇溶蛋白薄膜表面粗糙,机械性质及耐水性较差。为了改善玉米醇溶蛋白理化性质,在传统浇铸法膜制备过程中引入平行匀强电场(1~5 A/m2)处理蛋白成膜液。经过电场处理后,玉米醇溶蛋白表面光滑、形状完整。试验结果表明:电场处理可改善薄膜力学性质、表面疏水性、水蒸气透过率等性质;随着电流密度的增大,薄膜拉伸强度、断裂伸长率、水蒸气透过率、吸水率以及表面接触角呈现规律性增加或者减小;电场处理下薄膜热特性改变,与未处理组相比变性温度略有提高,最大增幅为19.5℃。当电流密度为4 A/m2时,薄膜理化性质较佳:拉伸强度、断裂伸长率分别为73.09 MPa和9.68%,吸水率降低至14.87%,水蒸气透过率为2.55×10-8 g·m/(m2·h·Pa),静态接触角为62.18°,变性温度提高到118.39℃,热稳定性提高,薄膜表面光滑。电场可诱导成膜液中分子有序性排列,提高薄膜均一性;通过调节电流密度可得到具有一定力学强度和亲/疏水性的薄膜。试验结果为制备具有特定功能性的纯玉米醇溶蛋白薄膜材料提供了理论依据。     

Development of flexible antimicrobial packaging materials against Campylobacter jejuni by incorporation of gallic acid into zein-based films

In this study, antimicrobial films were developed against Campylobacter jejuni by incorporation of gallic acid (GA) into zein-based films. The zein and zein-wax composite films containing GA between 2.5 and 10 mg/cm(2) were effective on different C. jejuni strains in a concentration-dependent manner. Zein and zein-wax composite films showed different release profiles in distilled water but quite similar release profiles at solid agar medium. Depending on incorporated GA concentration, 60-80% of GA released from the films, while the remaining GA was bound or trapped by film matrix. The GA at 2.5 and 5 mg/cm(2) caused a considerable increase in elongation (57-280%) of all zein films and eliminated their classical flexibility problems. The zein-wax composite films were less flexible than zein films, but the films showed similar tensile strengths and Young's modulus. Scanning electron microscopy indicated different morphologies of zein and zein-wax composite films. This study clearly showed the good potential of zein and GA to develop flexible antimicrobial films against C. jejuni.     

Properties of cast films from hemp (Cannabis sativa L.) and soy protein isolates. A comparative study

The properties of cast films from hemp protein isolate (HPI) including moisture content (MC) and total soluble mass (TSM), tensile strength (TS) and elongation at the break (EAB), and surface hydrophobicity were investigated and compared to those from soy protein isolate (SPI). The plasticizer (glycerol) level effect on these properties and the interactive force pattern for the film network formation were also evaluated. At some specific glycerol levels, HPI films had similar MC, much less TSM and EAB, and higher TS and surface hydrophobicity (support matrix side), as compared to SPI films. The TS of HPI and SPI films as a function of plasticizer level (in the range of 0.3-0.6 g/g of protein) were well fitted with the exponential equation with coefficient factors of 0.991 and 0.969, respectively. Unexpectedly, the surface hydrophobicity of HPI films (including air and support matrix sides) increased with increasing the glycerol level (from 0.3 to 0.6 g/g of protein). The analyses of protein solubility of film in various solvents and free sulfydryl group content showed that the disulfide bonds are the prominent interactive force in the HPI film network formation, while in the SPI case, besides the disulfide bonds, hydrogen bonds and hydrophobic interactions are also to a similar extent involved. The results suggest that hemp protein isolates have good potential to be applied to prepare protein film with some superior characteristics, e.g., low solubility and high surface hydrophobicity.     

Structural investigation of edible zein films/coatings and directly determining their thickness by FT-Raman spectroscopy

Near-infrared Fourier transform Raman (FT-Raman) spectroscopy was employed to study the molecular structure of edible zein films/coatings, which were fabricated directly from zein protein. The secondary structure of zein protein was mainly in alpha-helix and remained unaltered during film formation as evidenced by the vibrational modes of amide I at 1656 cm(-1) and amide III at 1274 cm(-1). Raman results indicated that hydrophobic interaction played an important role in the formation of zein film and disulfide bonding might be responsible for the structural stability of zein protein during film formation. To enhance its antimicrobial property, an antimicrobial zein film was manufactured by incorporating zein protein with benzoic acid whose structure was then characterized by FT-Raman. It showed that physical entrapment or hydrophobic interaction was crucial to the incorporation of benzoic acid with zein protein, and the secondary structure of the antimicrobial film was still maintained in alpha-helical form. In addition, FT-Raman exhibits its preference in directly determining the thickness of zein films/coatings. By correlating the Raman intensity ratio of nu(1003) to nu(84) (I(1003/84)) versus the thickness of zein film, a linear relationship with high coefficient (R(2) = 0.9927) was obtained, which was then used pragmatically to determine the thickness of zein coatings on apple. It showed that the FT-Raman result (thickness = 0.27 +/- 0.01 mm) was consistent with that of classical micrometric measurement (thickness = 0.28 +/- 0.02 mm). Consequently, FT-Raman provides a direct, simple, and reagent-free method to characterize the structure and the thickness of zein films/coatings.     

Effect of Temperature on Moisture Barrier Efficiency of Monoglyceride Edible Films in Cereal‐Based Composite Foods

The effects of temperature on moisture transfer within a composite food consisting of a sponge cake (SC) separated from a high moisture content agar gel (AG) by an acetylated monoglyceride (AMG1 and AMG2) film were investigated through moisture content profile experiments. A diffusion model was successfully used to predict moisture transfer within various composite foods (AG/SC, AG/AMG1/SC, and AG/AMG2/SC). The barrier efficiencies of the two hydrophobic films studied were reduced by temperature increase due to activation of diffusivity and equilibrium water sorption. Despite the low melting point of highly acetylated monoglyceride films, their barrier efficiency appeared to be less sensitive to temperature than monoglyceride films with a lower degree of acetylation. Consequently, in poor storage temperature conditions, these latter monoglyceride films seemed to be more effective in enhancing the shelf‐life of the composite food studied here.     

Effect of molecular weight and concentration of polyethylene glycol on physicochemical properties and stability of shellac film

The effects of molecular weight and concentration of plasticizer on physicochemical properties and stability of shellac films were investigated. Type of plasticizer was previously reported to have some effects on the stability of shellac films, and polyethylene glycol (PEG) was the plasticizer of choice for plasticizing shellac films. In this study, different molecular weights of PEG (200, 400 and 4000) were chosen at a concentration of 10% w/w of shellac films. Shellac in alcohol was prepared in a free film. The stability of shellac film was then performed at 75% RH, 40 °C for 3 months. The comparison was made between the film with and without plasticizer. Shellac films were then determined for acid value, insoluble solid, mechanical properties and water vapor permeability coefficient. It was reported that different molecular weights of PEG had some influence on physicochemical properties of the shellac films. Among different molecular weights of PEG, PEG 400 showed a suitable molecular weight that could protect the shellac chain at the carboxylic and hydroxyl groups. Therefore, the molecular weight of plasticizer played a crucial role for the protective ability at active sites. Further study was performed to investigate the effect of concentrations of PEG 400 on the stability. The results demonstrated that PEG 400 at a concentration of 10% (w/w) could prevent the polymerization process for only 4 months and a significant change of all parameters was then reported. However, a higher concentration, 20% (w/w) of PEG 400, could prolong the stability of shellac for 6 months of study. Therefore, the drawback of shellac as a natural polymer in pharmaceutical and food industries could be tackled by the appropriate size and concentration of plasticizer.     

Effects of hydrophilic plasticizers on mechanical, thermal, and surface properties of chitosan films

Chitosan films were plasticized with four hydrophilic compounds, namely, glycerol (GLY), ethylene glycol (EG), poly(ethylene glycol) (PEG), and propylene glycol (PG). Our objective was to investigate the effect of plasticizers on mechanical and surface properties of chitosan films. The stability of plasticized films was observed by storage for 3 and 20 weeks in an environmental chamber at 50 +/- 5% RH and 23 +/- 2 degrees C. Plasticization improves the chitosan ductility, and typical stress-strain curves of plasticized films have the features of ductile materials, except the film made with 5% PG that exhibits as a brittle polymer and shows an antiplasticization effect. In most cases, the elongation of plasticized films decreases with the storage time, which might be due to the recrystallization of chitosan and the loss of moisture and plasticizer from the film matrix. Although at the beginning the mechanical properties of films made with PG, at high plasticizer concentration, are comparable to those of films made with EG, GLY, and PEG, their stability is poor and they tend to become brittle materials. The surface properties, analyzed by contact angle measurement, reveal that plasticization increases film hydrophilicity. It is found that GLY and PEG are more suitable as chitosan plasticizers than EG and PG by taking into account their plasticization efficiency and storage stability. Furthermore, a plasticizer concentration of 20% (w/w) with GLY or PEG seemingly is sufficient to obtain flexible chitosan film with a good stability for 5 months of storage.