Cross-linked soy protein as material for biodegradable films: Synthesis, characterization and biodegradation

The modification of soy protein isolate (SPI) with different amounts of a naturally occurring cross-linking agent (genipin, Gen) and glycerol used as plasticizer was carried out in this work. The films yielded were cast from heated and alkaline aqueous solution of SPI, glycerol and Gen and then dried in an oven. Total soluble matter, water vapor permeability and mechanical properties were improved by adding small amounts of Gen. These properties were not significantly affected (P ? 0.05) by additions exceeding 2.5% (w/w of SPI). The opacity and cross-linking degree were linearly increased with the addition of Gen, whereas the swelling ratios in water were decreased. All the films were submitted to degradation under indoor soil burial conditions and the weight loss of the films was measured at different times. This study revealed that the film biodegradation time can be controlled or modified from at least 14 to 33 days. The tests performed showed the potential of Gen to improve the SPI film properties, in which the possibility of employing such new films as biodegradable food packaging was raised.     

几种多糖和交联剂对可食性大豆分离蛋白膜性能的影响

为了提高可食性大豆分离蛋白膜的性能,研究了多糖和交联剂对可食性膜性能的影响。结果表明,在大豆分离蛋白成膜液中添加0.5%(W/V)的果胶能有效增加膜的机械强度,添加0.1%(W/V)的葡萄糖能有效降低膜对水蒸气、氧气的透性。因此,果胶和葡萄糖对其性能的改善效果较佳,果胶和葡萄糖能改善大豆分离蛋白成膜特性的可能机理是因为它们增加了蛋白分子之间的交联。     

Mechanical properties and water vapor permeability of edible films made from fractionated soy proteins with ultrafiltration

Soy protein isolates (SPI) were fractionated by ultrafiltration unit equipped with 100 and 300 kDa cutoff size membranes. Glycerol-plasticized fractionated soy protein films were developed by casting methods. Mechanical, moisture barrier and physical properties of films, as affected by molecular weight of soy protein fraction, were investigated. Tensile strength and percent elongation at break of films increased with molecular weight of soy proteins. However, molecular weight variation did not influence the water vapor barrier properties of films. Protein solubilities of fractionated films were in the range of 3.5-4.6 g/100 g of dry film, whereas 11.9 g of proteins were solubilized from 100 g of dry SPI film. Hunter b value of fractionated protein films decreased with molecular weight of soy protein.     

Water resistance and mechanical properties of biopolymer (alginate and soy protein) coated paperboards

The effect of biopolymer coating on the water barrier and mechanical properties of paperboards used as corrugated fiberboard box liners was studied under several conditions. Paperboards were coated with selected biopolymers, such as alginate and soy protein isolate (SPI) and studied with or without further treatment, such as cross-linking through CaCl₂ or formaldehyde treatment and compositing with organically modified montmorillonite (OMMT). Biopolymer coating increased the thickness of paperboards from 9% to 16%, depending on the coating materials and treatment methods, and resulted in a smoother and more homogeneous surface. Though the tensile strength (TS) of the coated paperboards decreased from 12.5% to 37.5% of the uncoated paperboards by coating, ring crush strength was not decreased. Wetting properties, such as contact angle of water drop, dynamic change in contact angle, water vapor permeability (WVP), and water absorptivity were also affected by biopolymer coating, but the degree of change was dependent on the coating materials as well as treatment methods. For example, the rate of change in contact angle of water on paperboards decreased dramatically from 1.4 to 3.8 times depending on the coating materials as well as treatment methods. Generally, SPI-coated paperboards were more water-resistant than alginate coated ones. However, water resistance of the alginate-coated paperboards post-treated with the CaCl₂ solution was comparable to the SPI coated ones.     

Mechanical and thermal properties of soy protein films processed by casting and compression

Soy protein isolate (SPI) based films are environmentally friendly because they are biodegradable and come from renewable sources but they are brittle. Different ratios of plasticizer were incorporated into SPI-based films to improve mechanical properties. Glycerol has a plasticizing effect on the films in the range of 30–40%. Apart from the plasticizer, the processing method employed to prepare films also influenced on the mechanical properties. Films processed by compression showed much better mechanical properties, higher tensile strength and elongation at break, than the ones processed by casting. Analysis of the thermal properties revealed that denaturation temperatures of the two main globulin fractions present in SPI were influenced by the moisture content of the sample but not by the processing method employed.     

Functional properties of films based on soy protein isolate and gelatin processed by compression molding

Soy protein isolate (SPI) based films, blended with gelatin and plasticized with glycerol at pH 10, were prepared by compression molding with the aim to obtain environmentally friendly materials for packaging applications. Different contents and types of gelatin were incorporated into SPI-based mixtures to improve mechanical properties. All films obtained were flexible and transparent. Films with 15% of bovine gelatin showed higher tensile strength and similar elongation at break compared with the ones without gelatin. Moreover, contact angle measurements showed that the addition of gelatin decreased the hidrophilicity of the films, while UV barrier properties were maintained. The effect of gelatin addition has been explained using Fourier transform infrared (FTIR) and the changes observed in the intensity of the bands corresponding to the amide group showed that gelatin interacts with SPI, which was confirmed by the decrease of total soluble matter.     

Thermal behavior of emulsions manufactured with soy protein ingredients

The conformation, denaturation and aggregation behavior of proteins are important factors which dictate their ingredient functions and applications in formulated food products. The effect of variation in pre-treatment temperature (70–90 °C × 30 s), pH (6.4–7.5) and calcium supplementation (450 and 850 mg/L) on heat coagulation time (HCT at 140 °C) of model emulsions (3.6% (w/v) protein) stabilized with soy protein isolate (SPI) and soy protein hydrolysate (SPH) ingredients was determined. Generally, HCT of emulsions was not significantly affected by alteration of constituent pre-heating temperatures. Model emulsions displayed higher HCTs with increasing pH and lower levels of intrinsic ash content. At both supplementation levels, calcium addition led to decreased HCTs. Supplementation with chloride salts caused a greater decrease in HCT compared to supplementation with citrate salts. Furthermore, soy protein hydrolysis was associated with lower emulsion thermal stability. Results demonstrate that modification of ingredient and manufacturing parameters may be a useful approach for enhancing thermal stability properties of soy protein stabilized emulsions.     

大豆分离蛋白与谷朊粉可食性复合膜研究

该文报道影响大豆分离蛋白与谷朊粉复合膜成膜因素,分析各种因素对复合膜性能影响,并对正交试验结果采用极差分析和综合评分法进行评定,得到制备综合性能良好的可食性膜最佳条件为:谷朊粉与大豆分离蛋白比例为1∶5,甘油量为20%,pH为11,预热处理温度和时间分别为80℃和40min;此时,膜的透光率、拉伸强度、撕裂强度、水分含量和水蒸汽透过率依次为60.5%、38.38MPa、198.02N/mm、13.87%和0.507g·mm/kPa·h·m2。     

Edible films made from membrane processed soy protein concentrates

Edible films were prepared from membrane processed soy protein concentrate (MSC) at various film forming solution pHs, and their mechanical, barrier, and physical properties were compared with soy protein isolate (SPI) films. As the film solution pH increased from 7 to 10, the resulted MSC films were more transparent, yellowish, and had lower oxygen permeabilities. However, tensile strength (TS), modulus of elasticity (ME) and water vapor permeabilities of MSC films were not affected by film solution pHs. The values of MSC films prepared at pH 7 were not significantly (P>0.05) different from those of SPI films prepared at alkaline solutions (pH 8-10). The uniform TS and ME values of MSC film over the wide film solution pH ranges were attributed to the higher solubility of MSC at pH 7. For the films formed at neutral film solutions (pH 7.0), MSC films showed significantly (P<0.05) higher elongation value, film solubility, and transparency compared to SPI films.     

Thermal stability of soy protein isolate and hydrolysate ingredients

The objective of this study was to characterize the effects of pH, protein concentration and calcium supplementation on thermal stability, at 140 °C, of soy protein isolate (SPI) and soy protein hydrolysate (SPH) ingredients. Increasing pH between 6.4 and 7.5 led to significantly (p < 0.05) higher mean heat coagulation times (HCTs) at 140 °C, for all soy protein ingredients at 1.8, and 3.6% (w/v) protein. Increasing protein concentration from 1.8 to 7.2% (w/v) led to shorter HCTs for protein dispersions. Calcium supplementation up to 850 mg/L, except in the case of supplementation of SPI 1 with calcium citrate (CaCit), decreased HCT for soy protein ingredient dispersions, at pH 6.4 – 7.5. No significant differences (p < 0.05) were found in mean HCT for dispersions supplemented with calcium chloride (CaCl₂) and those supplemented with CaCit at 450, 650 and 850 mg/L Ca²⁺, in the pH range 6.4–7.5.     

Evaluation of microbial transglutaminase and ribose cross-linked soy protein isolate-based microcapsules containing fish oil

Soy protein isolate (SPI)-based microcapsules containing fish oil were prepared using a modified coacervation method followed by cross-linking treatments. The procedure yielded 95–98% microcapsules containing 0.5–0.6 g fish oil/g capsule with a volume mean diameter ranged from ~ 260 to ~ 280 μm. Four types of microcapsules produced were SPI with sucrose (MC-C/S), SPI with ribose (MC-C/R), SPI with sucrose and microbial transglutaminase (MC-MTG/S) and SPI with ribose and MTGase (MC-MTG/R). Protein cross-linking due to ε-(γ-glutamyl)lysine bonds and “Maillard cross-linking” were evidenced in the SDS-PAGE profiles of MC-C/R, MC-MTG/S and MC-MTG/R. Even though the microcapsules prepared with cross-linking treatments had significantly (P < 0.05) lower protein solubility as compared to that of the control, the results of fish oil release in pepsin solution at 37 °C indicated that the core release of all microcapsules prepared with ribose (MC-C/R and MC-MTG/R) was significantly (P < 0.05) lower than other microcapsules. During storage, microcapsules prepared with ribose had longer shelf life as compared to other microcapsules. This may be due to the release of antioxidative Maillard reaction products during heating and storage and a slower rate of gas permeability through the capsules.

Industrial relevance

The use of protein-based wall materials in the food industry for sensitive ingredients is limited because proteins are generally unstable with heating and damaged by organic solvents and the cross-linking agent is usually harmful. Therefore a novel method of combining two familiar cross-linking agents such as the microbial transglutaminase and ribose can convert SPI microcapsules into a stable form. The application of SPI in industry would be increased.     

十二烷基磺酸钠(SDS)在大豆分离蛋白基可食性膜中应用

该文报道研究十二烷基磺酸钠应用于以甘油作为增塑剂的大豆蛋白基可食性膜后对其物理性质影响。研究结果表明:当SDS添加量为40%(十二烷基磺酸钠质量/大豆分离蛋白质量)时,薄膜抗拉强度(TS)值显著(p<0.05)减少43%,最大断裂伸长率(E)值显著(p<0.05)增加至少5%,水分含量(MC)值显著减少(p<0.05),总可溶性物质含量(TSM)值显著增加(p<0.05);当SDS添加量>10%时,WVP值下降50%;SDS添加量为20%、30%、40%时,膜颜色值为显著+b (p<0.05),即黄色值增加。     

Development of biodegradable hot-melt adhesive based on poly-ε-caprolactone and soy protein isolate for food packaging system

A biodegradable hot-melt adhesive was developed from poly-ε-caprolactone (PCL) and soy protein isolate (SPI). PCL and SPI were mixed at varying ratios with plasticizers (coconut oil and PEG400). Thermal properties of PCL:SPI hot-melt adhesive were characterized with a differential scanning calorimeter (DSC) and softening point measurement. The surface morphology of PCL:SPI blend was examined by scanning electron microscopy (SEM). Tensile strength and elongation of PCL:SPI hot-melt adhesive films were measured using Instron testing machine. Lap shear strength of PCL:SPI hot-melt adhesives on medium density fiberboard was determined according to TAPPI UM633 method. The melting point and crystallinity of PCL in the blends decreased as the SPI content increased. The softening points of PCL:SPI hot-melt adhesive were about 59-75 °C. As the SPI concentration was increased, the tensile strength of its films decreased. The elongation of the PCL:SPI hot-melt adhesives varied with the type of plasticizer. Lap shear strength of PCL:SPI hot-melt adhesive was about 1.9 MPa.     

超声辐射对大豆分离蛋白膜性能的影响

研究了超声辐射在频率为20kHz,功率为800W条件下,不同处理时间对大豆分离蛋白膜性能的影响。结果表明,超声辐射对膜性能有明显的改善作用。经超声辐射处理2min可以显著提高膜的抗拉强度,相对于对照样提高了64.08%(P≤0.05);同时也明显降低了膜的水蒸汽透过系数,相对于对照样降低了25.70%(P≤0.05)。经超声处理后的膜机械强度和阻湿性能均得到了提高,同时具有均匀透明的外观。     

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.     

大豆分离蛋白、无机物复合膜研究

考察了通过添加碳酸钙、氧化钙、石英矿粉、磷酸氢钙到大豆分离蛋白复合膜中,通过环氧基交联剂作用后,考察几种无机物的蛋白复合膜性能的变化,对比发现:膜机械强度变化为磷酸氢钙>石英矿粉>碳酸钙>氧化钙,对比空白样品,性能有一定提高。通过溶胀系数考察了其交联程度,试验提供了复合膜的交联依据。通过3种溶剂实验发现:石英矿粉大豆复合膜交联程度较理想。     

大豆降胆固醇活性肽的初步分离纯化

研究了大豆降胆固醇活性肽的初步分离纯化,用Alcalase碱性蛋白酶水解大豆分离蛋白得到的酶水解物经过大孔吸附树脂脱盐,并用不同浓度的乙醇以疏水性大小洗脱,得出浓度为75%的乙醇洗脱物具有最高的降胆固醇活性,将此洗脱物再经过SephadexG15凝胶过滤色谱进行分子量分级,得到了部分纯化的大豆降胆固醇肽,其最高降胆固醇活性肽是分子量大多在1000以下的小肽,抑制率为81.26%。     

Microencapsulation properties of protein isolates from three selected Phaseolus legumes in comparison with soy protein isolate

The spray-drying microencapsulation properties of protein isolates from three selected Phaseolus legumes (kidney, red and mung beans; KPI, RPI and MPI), at a specific concentration (6 g/100 mL) and oil/protein ratio (1:1, w/w) were compared with soy protein isolate (SPI). The oil retention efficiency (RE), redispersion and dissolution behavior, as well as microstructure of the spray-dried powders were characterized. The influence of storage at 75% relative humidity for 7 days on these characteristics was also evaluated. The results indicated that the microencapsulation properties (except RE in the KPI case) of the three protein isolates were considerably poorer than SPI, though their emulsifying ability was even superior. The microencapsulating properties of these protein isolates were largely associated with their interfacial properties, especially the interfacial protein concentration. Among the three protein isolates, the spray-dried powders with KPI exhibited highest RE but least redispersion and/or dissolution behavior. The storage resulted in a severe loss of RE and ability to be redispersed and/or dissoluted, with much higher extent observed for the KPI powder. These results suggest that appropriate modifications, especially in interfacial properties, should be conducted on these proteins to warrant their application as wall materials in spray-drying microencapsulation.     

大豆蛋白薄膜制备及性能的研究

以大豆分离蛋白为主要原料,在一定条件下与增塑剂、还原剂等发生共价交联反应,通过单因素实验和正交实验对成膜配方、成膜条件的研究及微观结构分析,制备出可以降解,并具有一定机械强度的复合蛋白薄膜,可部分替代塑料用于食品包装领域,减少环境污染。研究结果表明,采用亚克力材质板槽制膜,60℃干燥时间2h;成膜配方是大豆分离蛋白浓度4.0%,增塑剂2.0%,还原剂0.1%;抗拉强度可达61.892N,透H2O性16.204mg/(cm2.d),透O2性0.313mg/(cm2.d),透CO2性2.899mg/(cm2.d)。     

Characterization of antimicrobial polylactic acid based films

Olive leaf extract (OLE) (Olea europaea L.), which has antimicrobial effect on many food pathogens, was incorporated as antimicrobial agent into polylactic acid (PLA) films. Antimicrobial activities of films were tested against Staphylococcus aureus. Increasing amount of the OLE in the film discs from 0.9 mg to 5.4 mg caused a significant increase in inhibitory zones from 9.10 mm to 16.20 mm, respectively. Moreover, incorporation of OLE and/or increasing the amount in the film formulation significantly enhanced the water vapor permeability (WVP). The water solubility and the degradation rates of films increased up to 19.3% and 22.4%, respectively. Thus, OLE incorporated PLA films have a prospectively potential in antimicrobial food packaging to reduce post-process growth of S. aureus with improved properties.