Physical Properties of Whey Protein–Hydroxypropylmethylcellulose Blend Edible Films

ABSTRACT: The formations of glycerol (Gly)‐plasticized whey protein isolate (WPI)–hydroxypropylmethylcellulose (HPMC) films, blended using different combinations and at different conditions, were investigated. The resulting WPI: Gly‐HPMC films were analyzed for mechanical properties, oxygen permeability (OP), and water solubility. Differences due to HPMC quantity and blend method were determined via SAS software. While WPI: Gly and HPMC films were transparent, blend films were translucent, indicating some degree of immiscibility and/or WPI–HPMC aggregated domains in the blend films. WPI: Gly‐HPMC films were stronger than WPI: Gly films and more flexible and stretchable than HPMC films, with films becoming stiffer, stronger, and less stretchable as the concentration of HPMC increased. However, WPI: Gly‐HPMC blended films maintained the same low OP of WPI: Gly films, significantly lower than the OP of HPMC films. Comparison of mechanical properties and OP of films made by heat‐denaturing WPI before and after blending with HPMC did not indicate any difference in degree of cross‐linking between the methods, while solubility data indicated otherwise. Overall, while adding HPMC to WPI: Gly films had a large effect on the flexibility, strength, stretchability, and water solubility of the film polymeric network, results indicated that HPMC had no effect on OP through the polymer network. WPI–HPMC blend films had a desirable combination of mechanical and oxygen barrier properties, reflecting the combination of hydrogen‐bonding, hydrophobic interactions, and disulfide bond cross‐linking in the blended polymer network.     

Whey protein isolate-based edible films as affected by protein concentration,glycerol ratio and pullulan addition in film formation

Edible films were prepared from whey protein isolate (WPI), and characterized in order to select a best combination of protein concentration and glycerol (Gly) ratio. 5%, 7% and 9% (w/v) WPI were used at three WPI:Gly ratios (3.6:1; 3:1; and 2:1). 5% WPI with a 3.6:1 WPI:Gly ratio showed the best combination with factors considered being thickness and water vapor permeability (WVP), while the 9% WPI with 3.6:1 WPI:Gly showed the best result as seen from the oxygen permeability (OP). Further studies were conducted by adding pullulan (PUL) at different WPI:PUL ratios (1:0; 1:1; 2:1; 3:1; 4:1; 5:1; 6:1; 8:1; 10:1) to a selected film in order to investigate the effect of pullulan on thickness, OP, WVP, moisture content (MC), film solubility (FS) and morphology using scanning electron microscopy (SEM). WPI–PUL film had a good appearance and 1:1 WPI:PUL resulted in films with greatest values of OP, WVP, MC, FS, and transmittance. The SEM micrographs showed many pinholes and a favorable structure for the low barrier ability. However, addition of PUL at low concentration was good enough to significantly modify these properties, hence improving the potential characteristics of WPI-based films for food applications.     

Whey protein-polysaccharide blended edible film formation and barrier, tensile, thermal and transparency properties

BACKGROUND: Films made from different protein (P) or polysaccharide (PS) materials have widely different properties. The objective of this study was to determine whether whey protein isolate (WPI)‐PS blended films possess a combination of properties intermediate and possibly superior to WPI or PS film alone. RESULTS: Oxygen permeability (OP) and tensile strength (TS) for PS‐WPI blended films were intermediate between the OP and TS properties of pure methycellulose (MC), hydroxypropylmethylcellulose (HPMC) or sodium alginate (SA) film and pure WPI film. Starch‐WPI blends gave the weakest films. Water vapor permeability values for all pure and blended films were similar. Blended films made of MC, HPMC or SA with WPI had lower transparency than pure MC, HPMC, SA or WPI films. Differential scanning calorimetry thermograms obtained from the blended films exhibited a single glass transition temperature (T_g) at an intermediate value between the T_g values of the pure films. CONCLUSIONS: Whether properties of PS‐WPI blended films are intermediate to properties of the pure PS and WPI film depends on the particular PS and specific property. In the case of MC or HPMC with WPI, the blended films reflect the higher TS of the PS and lower OP of the WPI. Copyright © 2011 Society of Chemical Industry     

Whey protein-okra polysaccharide fraction blend edible films: tensile properties, water vapor permeability and oxygen permeability

BACKGROUND: A hot‐buffer‐soluble‐solid fraction (HBSS) and an alkaline‐soluble‐solid fraction (ASS) of okra polysaccharides (OKP) were obtained using sequential extraction. These fractions were combined with whey protein isolate (WPI) and glycerol (Gly) plasticizer to form blend edible films. Effects of OKP fraction and content on tensile properties, water vapor permeability (WVP) and oxygen permeability (OP) were determined. RESULTS: HBSS film had significantly higher percent elongation (%E) and lower elastic modulus (EM), WVP and OP than ASS film. Increasing HBSS or ASS content in blend films with WPI significantly reduced film tensile strength and EM and increased film %E and WVP. OP values for WPI–HBSS blend films were significantly lower than OP for WPI or HBSS film. WPI–HBSS and WPI–ASS blend films had lower WVP and OP than WPI films with equivalent tensile properties. CONCLUSIONS: WPI–HBSS blend films have higher WVP and lower OP than WPI film or HBSS film, indicating unique interactions between WPI and HBSS. Compared to WPI film, WPI–HBSS blend films have improved flexibility, stretchability and oxygen barrier. Different HBSS and ASS compositions and structures are responsible for property differences between HBSS and ASS films and between WPI–HBSS and WPI–ASS blend films. Copyright © 2010 Society of Chemical Industry     

Physical assessment of composite biodegradable films manufactured using whey protein isolate,gelatin and sodium alginate

Composite films were manufactured using whey protein isolate (WPI), gelatin (G) and sodium alginate (SA) using a simplex centroid design. Tensile strength (TS), puncture strength (PT), percentage elongation at break point (E), tear strength (TT), water vapour permeability (WVP) and oxygen permeability (OP) of films were evaluated. The interactions between biopolymers showed quadratic effects (P < 0.01) on TS, E, PT, TT and WVP values. Scanning electron microscopy (SEM) was performed to investigate the microstructures of composite films. The proportion of ingredients required to produce the optimum composite films was determined to be: WPI (g):G (g):SA (g) = 8.0:12.0:5.0. Overall, films (WPIGSA-9) produced using the combination of WPI (g):G (g):SA (g) = 10.0:16.0:14.0 demonstrated the best barrier to oxygen (8.00 cm³ μm/m² d kPa); while films (WPIGSA-1) showed the best barrier to water vapour (48.04 g mm/kPa d m²); films (WPIGSA-6) using the combination of WPI (g):G (g):SA (g) = 10.0:17.5:22.5 had the best mechanical properties of all of the experimental composite films tested.     

Tensile and moisture barrier properties of whey protein–beeswax layered composite films

BACKGROUND: There is a lack of research on producing layered protein–lipid composite films with improved tensile and barrier properties compared to films from individual components. Several film‐forming parameters were hypothesized to influence the extent to which lipids were either dispersed within or layered upon whey protein films. Film‐forming parameters investigated were ratio of whey protein isolate (WPI) to beeswax (BW), homogenization method, sodium chloride (NaCl) concentration, and BW particle size. RESULTS: Film percent elongation (E) increased, while tensile strength (TS) and elastic modulus (EM) decreased when BW was incorporated into WPI films, demonstrating a lubricant effect of the BW. Mean water vapor permeability values for WPI film decreased by 57% when the film composition was modified by the addition of 40% BW. BW phase separation was observed in all of the tested films. Particle size of BW in the film‐forming emulsions was larger in the presence of NaCl (100 mmol L^?1), indicating a neutralization of particle charge. However, the addition of NaCl did not improve the moisture barrier of WPI‐BW film over the range of film‐forming conditions used in the study. CONCLUSION: The results from this study are useful in determining formulations and conditions for the production of composite films from WPI and BW with improved tensile and moisture barrier properties. Copyright © 2008 Society of Chemical Industry     

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.     

Effect of pH and addition of corn oil on the properties of whey protein isolate-based films using response surface methodology

Response surface methodology (RSM) was used to investigate pH and corn oil (CO) effects on the properties of films formed from whey protein isolate (WPI). Test films were evaluated for tensile strength (TS), puncture strength (PT), percentage elongation at break point (E), water vapour permeability (WVP) and oxygen permeability (OP). TS of WPI films increased with increasing pH, while addition of CO produced no trend. However, when WPI solution pH increased >10.0, film TS generally decreased with CO addition (>11%). E values increased dramatically with increasing levels of CO when pH for WPI solutions were >8.5. However, pH had no effect on E values. WPI solutions possessing high pH values (maximum pH value of 10.62) produced WPI films with the highest PT values. WVP had a quadratic relationship with pH and CO addition. OP had an inversely linear relationship with increasing pH (6.5–10.5) and a quadratic relationship with CO addition. Optimal pH (9.88) and CO level (2.93%), determined from physical test film data, were predicted by RSM.     

Physical properties of edible films made from mixtures of sodium caseinate and WPI

The physical properties of thin films (25–30 μm) made from mixtures of sodium caseinate (NaCas) and whey protein isolate (WPI) were investigated. Films were formed by mixing solutions of NaCas (2.5% w/w protein), plasticised with glycerol (NaCas–gly) at a glycerol:protein ratio of 0.32, with WPI solutions (2.3% w/w protein), plasticised (WPI-gly) at a glycerol:protein ratio 0.37. Tensile and water barrier properties of films formed from mixtures of NaCas–gly and WPI-gly were similar to films containing NaCas–gly only. Films containing only WPI-gly had higher maximum load and elastic modulus values than the mixed films. Increasing the NaCas–gly content of the films from 25 to 100% greatly increased solubility. This increased film solubility may increase the number of food applications for protein-based films.     

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.     

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.     

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.     

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).     

Mechanical and Barrier Properties of Edible Chitosan Films as affected by Composition and Storage

Oxygen permeability coefficients (OP), water vapor permeability coefficients (WVP), ethylene permeability coefficients (EP), tensile strength (TS) and percent elongation (%E) at break values were determined for chitosan films plasticized with glycerin at two concentrations (0.25 and 0.50 mL/g chitosan). Film samples were tested after 0, 2, 4, 8 and 12 wk of storage. After an initial drop in permeability during the first 2 wk of storage, mean OP (4.6 × 10^?5 cc/m-day-atm) and mean EP (2.3 × 10^?4 cc./m.day.atm) remained constant while mean WVP (2.2 × 10^?1 g/m-day-atm) decreased with respect to storage time. TS values (15–30 MPa) decreased and %E values (25%–45%) increased with respect to storage time. The stability of OP and EP values with storage was not expected, while the change in mechanical properties was as expected.     

The interaction of milk sphingomyelin and proteins on stability and microstructure of dairy emulsions

The interaction between dairy proteins [micellar casein (MC) vs. whey protein isolate (WPI)] and phospholipids [PL; soy phosphatidylcholine (PC) vs. milk sphingomyelin (SM)] in an oil-in-water emulsion system was investigated. Sole PC–stabilized emulsion (1%, wt/vol) showed a significantly larger mean particle diameter (6.5 μm) than SM-stabilized emulsions (3.8 μm). The mean particle diameters of emulsions prepared by the combination of protein (1%, wt/vol) and PL (1%, wt/vol) did not significantly differ from the emulsions prepared with a single emulsifier (MC, WPI, and SM). Emulsion instability differed significantly among samples by a centrifugation-mediated accelerated stability test. Emulsion instability increased in the order of MC+SM < MC+PC, WPI+SM < WPI+PC < MC < SM < WPI < PC. Protein surface load determined by aqueous phase depletion was significantly decreased only in WPI+PC emulsion, whereas no significant difference was found between the MC+SM and WPI+SM emulsions. Topographic and phase images of emulsion surface by atomic force microscopy showed surface layers prepared by protein+PL combinations were composites with different mechanical properties, and PL formed a more compact domain than proteins. A smoother phase image was observed in MC+PL combinations than in WPI+PL counterparts. Based on the microstructure analysis using confocal laser scanning microscopy, combination and MC+SM formed a uniform and thick surface coating of fat droplets. More PC aggregates were observed in the emulsions containing PC (sole PC, MC+PC, and WPI+PC) compared with their SM counterparts. Based on these results, the appropriate selection of the PL matrix is important to modulate the emulsion stability of dairy emulsion products.     

Diffusion of thiocyanate and hypothiocyanite in whey protein films incorporating the lactoperoxidase system

The diffusion of the thiocyanate (SCN⁻) and hypothiocyanite (OSCN⁻) components of a lactoperoxidase system (LPOS) in whey protein isolate (WPI) films was investigated. Diffusion coefficients for these molecules were measured for the LPOS-incorporated WPI films prepared with different WPI:glycerol ratios (1:1, 3:1, and 5:1). WPI film disks were coated on the surfaces of smoked salmon samples, and the samples were stored at 4, 10 and 22 °C. The diffusion coefficients were determined by fitting a mathematical model to the amounts of SCN⁻ and OSCN⁻ released from the disks during a period of time. The diffusion coefficients for SCN⁻ (D₁) and OSCN⁻ (D₂) in the films were 0.19–5.2 × 10⁻¹² m² s⁻¹ and 0.13–6.5 × 10⁻¹³ m² s⁻¹, respectively. The D₁ and D₂ decreased as the WPI:glycerol ratio increased and the storage temperature decreased. The E_a values for diffusion in 1:1, 3:1, and 5:1 WPI:glycerol films were 13.3, 29.5, and 35.6 kJmol⁻¹, respectively, for SCN⁻ and 15.8, 30.1, and 39.9 kJmol⁻¹, respectively, for OSCN⁻.     

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。     

Solubility and mechanical properties of heat-cured whey protein-based edible films compared with that of collagen and natural casings

Water solubility, tensile strength (TS), wet strength (WS) and elongation at break (%E) of whey protein isolate (WPI) films were compared to that of collagen films and natural casings. Increase in heat-curing temperature and time caused decreased ( P <  0.001) water solubility and increased TS and WS of the films. Heat-cured WPI films with similar properties (solubility, TS, WS and %E) to collagen films were obtained by optimizing heat-curing conditions. Overall, natural casings had lower solubility, TS and %E but higher WS than collagen and heat-cured WPI films. Heat-cured WPI films have the potential as an alternative to collagen films and casings.     

高直链玉米淀粉复合膜的应用特性及其对荷兰豆的保鲜研究

以高直链玉米淀粉(HACS)、壳聚糖(CS)和甲基纤维素(MC)为原料制备可食性复合膜,研究了HACS/CS质量配比分别为1∶0、2∶1、1∶1、1∶2及0∶1,MC添加量(占干基淀粉)分别为0%、2%、4%、6%及8%时的成膜性能,并从中选取HACS/CS质量比为2∶1、1∶2、1∶1添加8%MC的3种膜进行荷兰豆保鲜实验。结果表明:3种膜均能有效降低荷兰豆的失重率和霉变率,减缓叶绿素和Vc的损失。其中,质量比HACS/CS为2∶1的膜,综合保鲜效果最好。     

Assessment of film-forming potential and properties of protein and polysaccharide-based biopolymer films

This study assessed the film‐forming abilities of six types of proteins, as well as six types of polysaccharides at various concentrations (proteins: 0–16%; polysaccharides: 0–4%) and heating temperatures (60–80 °C). Biopolymer films evaluated included: sodium caseinate (SC), whey protein isolate (WPI), gelatine (G); caboxymethyl cellulose (CMC), sodium alginate (SA) and potato starch (PS). Screening trials showed that optimal film‐forming conditions were achieved using SC and G (4% and 8%), WPI (8% and 12%), PS, CMC (2% and 3%) or SA (1% and 1.5%) solutions heated to 80 °C in combination with 50% (w/w) glycerol. Films manufactured from 1.5% SA, 8% G and 3% CMC had the highest tensile strength (24.88 MPa); flexibility (89.69%)/tear strength (0.30 N) and puncture resistance (22.66 N), respectively. SC, WPI and G‐based films were more resistant to solvent than SA, CMC and PS. Film permeability to water vapour and oxygen decreased in the order: 12% WPI to 1% SA and 12% WPI to 1% SA. All films tested were impermeable to oil.