Partially carboxymethylated feather keratins. 1. Properties in aqueous systems

Feather keratins were extracted from chicken feathers with an aqueous solution of urea and 2-mercaptoethanol. The keratin solution obtained was dialyzed to remove the reagents. Upon dialysis, extensive protein aggregation occurred. To obtain stable solutions or dispersions in water, cysteine residues were modified prior to dialysis with iodoacetamide, iodoacetic acid, or bromosuccinic acid, thereby blocking free thiol groups and introducing hydrophilic groups. For the development of biodegradable materials with good mechanical properties from these biopolymers, disulfide bonds between the keratin molecules are needed. Therefore, cysteine residues were only partially modified by using different reagent/cysteine molar ratios. The reaction rate constants of iodoacetate with glutathione and 2-mercaptoethanol were successfully used to predict the degree of modification of keratin cysteine. It was shown that, for carboxymethylated keratin, fewer aggregates were formed for higher degrees of cysteine modification, while more protein was present as oligomers. Aggregates and oligomers were stabilized through intermolecular disulfide bonds.     

Oxygen permeability and mechanical properties of films from hydrolyzed whey protein

The effects of whey protein hydrolysis on film oxygen permeability (OP) and mechanical properties at several glycerol-plasticizer levels were studied. Both 5.5% and 10% degree of hydrolysis (DH) whey protein isolate (WPI) had significant effect (p 0.05) occurred for film OP between unhydrolyzed WPI, 5.5% DH WPI, and 10% DH WPI films at the same glycerol content. Hydrolyzed WPI films of mechanical properties similar to those of WPI films had better oxygen barrier. Therefore, use of hydrolyzed WPI allowed achievement of desired film flexibility with less glycerol and with smaller increase in OP.     

Barrier and mechanical properties of milk protein-based edible films containing nutraceuticals

Calcium caseinate (CC) and whey protein isolate (WPI) films were prepared to contain 5 or 10% Gluconal Cal (GC), a mixture of calcium lactate and gluconate, or 0.1 or 0.2% alpha-tocopheryl acetate (VE), respectively. The pH and viscosity of film-forming solutions and the water vapor permeability and tensile property of the films were determined using standard procedures. CC and WPI films have the capabilities to carry high concentration of GC or VE, but some of the film functionality might be compromised. Adding VE to CC and WPI films increased film elongation at break, whereas incorporating 0.2% VE decreased WVP of CC films and tensile strength of both CC and WPI films. Incorporation of GC reduced the tensile strength of CC films (P < 0.05), with 10% GC decreasing both elongation at break and WVP (P < 0.05). These types of films may be used for wrapping or coating to enhance the nutritional value of foods. The concentration of GC and VE added to the films must be carefully selected to meet required water barrier and mechanical properties of the films depending on their specific applications.     

Aging of whey protein films and the effect on mechanical and barrier properties

This work focuses on the aging of whey protein isolate (WPI) films plasticized with glycerol (G) and sorbitol (S). The films were cast from heated aqueous solutions at pH 7 and dried at 23 degrees C and 50% relative humidity (RH) for 16 h. They were stored in a climate room (23 degrees C, 50% RH) for 120 days, and the film properties were measured at regular intervals. The moisture content (MC) of the WPI/G films decreased from 22% (2 days) to 15% (45 days) and was thereafter constant at 15% (up to 120 days). This affected the mechanical properties and caused an increased stress at break (from 2.7 to 8.3 MPa), a decreased strain at break (from 33 to 4%), and an increased glass transition temperature (T(g)) (from -56 to -45 degrees C). The barrier properties were, however, unaffected, with constant water vapor permeability and a uniform film thickness. The MC of the WPI/S films was constant at approximately 9%, which gave no change in film properties.     

Relationship between the microstructure and the mechanical and barrier properties of whey protein films

This work was focused on the relationship between the microstructure and the mechanical and barrier properties of whey protein isolate (WPI) films. Sorbitol (S) and glycerol (G) were used as plasticizers and the pH was varied between 7 and 9. The films were cast from heated aqueous solutions and dried in a climate room at 23 degrees C and 50% relative humidity for 16 h. The microstructure of the films was found to be dependent on the concentration, the plasticizers, and the pH. When the concentration increased, a more aggregated structure was formed, with a denser protein network and larger pores. This resulted in increased water vapor permeability (WVP) and decreased oxygen permeability (OP). When G was used as a plasticizer instead of S, the microstructure was different, and the moisture content and WVP approximately doubled. When the pH increased from 7 to 9, a denser protein structure was formed, the strain at break increased, and the OP decreased.     

Analysis of genotypic and environmental effects on rice starch. 2. Thermal and retrogradation properties

Eight rice varieties with wide diversity in apparent amylose content (AC) were selected and planted in the early (HZE) and late season (HZL) in Hangzhou and in the winter season in Hainan (HN) for two consecutive years to study the genotypic and environmental effects on starch thermal and retrogradation properties of grain. Genotypic variation (all at P < 0.01) accounted for >56% of the total variation for onset (T(o)), peak (T(p)), and completion (T(c)) temperature, width at half-peak height (DeltaT(1/2)) of gelatinization, enthalpy (DeltaH(r)) of retrograded starch, percentage of retrogradation (R%), and 45.8% for enthalpy (DeltaH(g)) of gelatinization. Seasonal variation accounted for about one-fifth for T(o), T(p), and T(c) and one-third for DeltaH(g), but less for T(1/)(2), DeltaH(r), and R% of the total variation, indicating that T(o), T(p), T(c), and DeltaH(g) were highly affected by seasonal environment in addition to the genotypic variation. The T(o), T(p), T(c), and DeltaH(g) in HZL were much smaller than those in HZE and HN. Correlation analysis for the eight genotypes showed that AC was significantly correlated with DeltaH(g) (r = -0.83, P < 0.01) and R% (r = 0.734, P < 0.05). DeltaH(g) was also positively correlated with T(c) (r = 0.878, P < 0.05), but it did not have any correlation with DeltaH(r), whereas the latter was positively correlated with R% (r = 0.994, P < 0.001). The intercorrelation of T(o), T(p), T(c), and DeltaT(1/)(2) themselves was significant at P < 0.001. The correlation analysis results suggest that there are different molecular mechanisms to regulate thermal properties (T(o), T(p), T(c), and DeltaH(g)) and retrogradation properties (DeltaH(r) and R%) as affected by environmental conditions. The implications of the results for rice breeders and starch-based food processors are discussed.     

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.     

Drying temperature effect on water vapor permeability and mechanical properties of whey protein-lipid emulsion films

The water vapor permeability (WVP) and mechanical properties of whey protein isolate (WPI) and WPI-lipid emulsion films dried at different conditions were investigated. As drying temperature increased, WVPs decreased significantly. Significantly lower WVP was observed for emulsion films compared to WPI films. WPI-Beeswax (BW) and WPI-anhydrous milkfat fraction emulsion films dried at 80 degrees C and 40% RH gave the lowest WVP compared to 25 degrees C, 40% RH and 40 degrees C, 40% RH. A large drop in WVP of WPI-BW emulsion films was observed at 20% BW content. The decrease in WVP for emulsion films as drying temperature increased could be due to change in the lipid crystalline morphology and/or lipid distribution within the matrix. Mechanical properties of WPI and WPI-lipid emulsion films, on the other hand, were not modified by drying conditions.     

Influence of gallic acid and tannic acid on the mechanical and barrier properties of wheat gluten films

Vital wheat gluten, a byproduct of wheat starch production, is a highly functional ingredient having a unique viscoelasticity that makes it ideal for the production of edible biodegradable films. However, its functional properties must be modified to ensure sufficient strength and elasticity, in addition to water vapor barrier properties. In this study, vital gluten was modified using tannic and gallic acid. It was found that the addition of tannic acid resulted in stiffer, more resistant, and less resilient and flexible films, having as well decreased water vapor permeability. Tannic acid containing films became reddish brown, whereas gallic acid addition did not have an influence on the film appearance. Films containing gallic acid became more elastic. Gallic acid was found to potentially act like a plasticizer. Scanning electron microscopy was used to investigate the ultrastructure of the produced films.     

Arabinoxylan-lipids-based edible films and coatings. 2. Influence of sucroester nature on the emulsion structure and film properties.

This work is a contribution to better knowledge of the influence of the structure of films on their functional properties obtained from emulsions based on arabinoxylans, hydrogenated palm kernel oil (HPKO), and emulsifiers. The sucroesters (emulsifiers) have a great effect on the stabilization of the emulsified film structure containing arabinoxylans and hydrogenated palm kernel oil. They improve the moisture barrier properties. Several sucroesters having different esterification degrees were tested. Both lipophilic (90% of di and tri-ester) and hydrophilic (70% of mono-ester) sucrose esters can ensure the stability of the emulsion used to form the film, especially during preparation and drying. These emulsifiers confer good moisture barrier properties to emulsified films.     

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.     

Physicochemical and mechanical properties of experimental coextruded food-packaging films containing a buried layer of recycled low-density polyethylene

Migrational, permeation, and tensile properties of experimental five- and eight-layer coextruded and laminated films containing a middle buried layer of recycled low-density polyethylene (LDPE) comprising 40-50% bw of the multilayer structure were determined. Respective films containing 100% virgin LDPE as the buried layer were taken as controls. Results showed that the percentage of recycled LDPE in the multilayer structure did not affect overall migration values to distilled water, 3% acetic acid, and iso-octane. In all cases, overall migration values were lower than the upper acceptable limit (10 mg/dm(2)) set by the European Union. Transmission rate values to O(2), CO(2), and water vapor were also not affected by the percentage of recycled LDPE in the multilayer structure. On the basis of O(2) transmission rates, low-barrier, barrier, and high-barrier multilayer structures were produced. Likewise, tensile properties (tensile strength, percent elongation at break, and Young's modulus) were not affected by the percentage of recycled material in the multilayer structure. Finally, all experimental films produced no adverse effects in taste or odor of the food-contacting phase tested. The above findings are discussed in relation to the high quality of the primary LDPE scrap used throughout this work in combination with the functional barrier hypothesis. On the basis of the present results it is proposed that primary LDPE scrap may be used as a middle layer comprising 40-50% bw of multilayer food-packaging films without any compromise in migrational, barrier, mechanical, and organoleptic properties.     

Gamma-irradiation influence on the structure and properties of calcium caseinate-whey protein isolate based films. Part 2. Influence of polysaccharide addition and radiation treatment on the structure and functional properties of the films

The influence of gamma-irradiation (32 kGy) followed by the addition of polysaccharides (potato starch, soluble potato starch, and sodium alginate) and heating on the properties of the films based on calcium caseinate (CC)-whey proteins isolate (WPI) and the gels formed with CaCl(2) was evaluated. Radiation induced an improvement of the mechanical and barrier properties of all films. The polysaccharides' effect on the irradiated and non-irradiated CC-WPI gels could be predicted as the sum of their separate effects on CC and on WPI, apart from the alginate interaction with the irradiated CC-WPI. The better properties of the films achieved after admixing polysaccharides to the formerly irradiated protein solution correspond to the smaller strength of gels. Properties of the films and gels prepared using the irradiated proteins and alginate differed depending on whether alginate was admixed before or after irradiation. Results were related to the protein structure, interaction with polysaccharides, and the film's microstructure.     

Effects of pH and the gel state on the mechanical properties, moisture contents, and glass transition temperatures of whey protein films.

The mechanical properties, moisture contents (MC), and glass transition temperature (T(g)) of whey protein isolate (WPI) films were studied at various pH values using sorbitol (S) as a plasticizer. The films were cast from heated aqueous solutions and dried in a climate chamber at 23 degrees C and 50% relative humidity (RH) for 16 h. The critical gel concentrations (c(g)) for the cooled aqueous solutions were found to be 11.7, 12.1, and 11.3% (w/w) WPI for pH 7, 8, and 9, respectively. The cooling rate influenced the c(g), in that a lower amount of WPI was needed for gelation when a slower cooling rate was applied. Both cooling rates used in this study showed a maximum in the c(g) at pH 8. The influence of the polymer network on the film properties was elucidated by varying the concentration of WPI over and under the c(g). Strain at break (epsilon(b)) showed a maximum at the c(g) for all pH values, thus implying that the most favorable structure regarding the ability of the films to stretch is formed at this concentration. Young's modulus (E) and stress at break (sigma(b)) showed a maximum at c(g) for pH 7 and 8. The MC and epsilon(b) increased when pH increased from 7 to 9, whereas T(g) decreased. Hence, T(g) values were -17, -18, and -21 degrees C for pH 7, 8, and 9, respectively. E and sigma(b) decreased and epsilon(b) and thickness increased when the surrounding RH increased. The thickness of the WPI films also increased with the concentration of WPI.     

Lipid particle size effect on water vapor permeability and mechanical properties of whey protein/beeswax emulsion films

Lipid particle size effects on water vapor permeability (WVP) and mechanical properties of whey protein isolate (WPI)/beeswax (BW) emulsion films were investigated. Emulsion films containing 20 and 60% BW (dry basis) and mean lipid particle sizes ranging from 0.5 to 2.0 microm were prepared. BW particle size effects on WVP and mechanical properties were observed only in films containing 60% BW. WVP of these films decreased as lipid particle size decreased. As drying temperature increased, film WVPs decreased significantly. Meanwhile, tensile strength and elongation increased as BW particle size decreased. However, for 20% BW emulsion films, properties were not affected by lipid particle size. Results suggest that increased protein-lipid interactions at the BW particle interfaces, as particle size decreased and resulting interfacial area increased, result in stronger films with lower WVPs. Observing this effect depends on a large lipid content within the protein matrix. At low lipid content, the effect of interactions at the protein-lipid interfaces is not observed, due to the presence of large protein-matrix regions of the film without lipid, which are not influenced by protein-lipid interactions.     

Molecular determinants of the influence of hydrophilic plasticizers on the mechanical properties of cast wheat gluten films

The influence of a set of hydrophilic plasticizers varying in their chain length (ethyleneglycol and longer molecules) on the tensile strength and elongation at break of cast gluten films was studied. When considered on a molar basis (moles of plasticizer per mole of amino acid), the effect of the different plasticizers depended on their respective molecular weights for plasticizer/amino acid ratios in the range from 0.10 to 0.40. However, above a ratio of 0.40-0.50 mol/mol of amino acid, these differences were abolished and both stress and strain reached a plateau value, with all plasticizers studied. In fact, when a homologous series of molecules was considered, the ability for plasticizer to decrease stress and increase strain was closely related to the number of hydrogen bonds the molecule was able to share with the protein network. Ethyleneglycol's efficiency was, however, lower than expected from its hydrogen-bonding potential; a comparison with other diols demonstrated that this was due to the small size of this molecule. The particular effect of glycerol concentration on the films' mechanical properties suggested that other molecular features of the plasticizer, such as the number and position of hydroxide groups in the molecule, were involved in the plasticization mechanism.     

糙米机械破碎力学特性试验与分析

为了研究糙米机械破碎力学特性及其与籽粒结构特性的关系。采用物性测试仪对糙米的锥刺、三点弯曲、剪切、挤压4种机械破碎力学特性进行测试与分析,并对糙米和精米的破碎力学特性(三点弯曲)进行了比较。结果表明:糙米的断裂是由于内部胚乳组织不均匀,在外力作用下首先形成内部裂纹,裂纹尖端处的应力集中又进一步促进裂纹扩展,最终导致籽粒断裂;厚度为(1.0±0.5)mm的不同样品锥刺破碎力在10N左右,各样品籽粒内部的结合力相差较小,籽粒的断裂主要与厚度及胚乳特性有关,其中三点弯曲力更能反映籽粒的破碎特性,糙米的糠层对籽粒有一定的保护作用,糙米力学特性比精米好。该文为糙米储藏加工技术参数的确定提供依据。     

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.     

Structural and biological study of carboxymethylated Phellinus linteus polysaccharides

Polysaccharides isolated from Phellinus linteus were chemically modified by carboxymethylation, and the structural and physiological properties of the derivative were investigated. 13C NMR spectroscopy showed that the polysaccharides extracted from P. linteus contained (1-3)-beta-glucans with a (1-6)-linkage. The carboxymetehylation of the P. linteus polysaccharides was confirmed by Fourier transform infrared spectroscopy, and the degree of substitution was obtained by the potentiometric titration, which was calculated to be 0.63. The bronchoalveolar lavage experiments showed that the carboxymethylated derivative raised the nitric oxide production. In addition, the carboxymethylation stimulated in vitro cytotoxic activity against the HT1080 cell line. Thus, the derivative exhibited the enhanced activity of immune systems, which would be explained by the improved water solubility and structural changes by carboxymethylation. However, a slight decrease in the 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity of the derivative was observed.     

角蛋白材料结构与力学特性研究进展

天然生物材料精巧的结构和独特的功能为许多工程技术问题的解决提供了仿生学基础。人们在不断地寻求仿效对象，以期基于生物系统发展工程技术系统。角蛋白材料作为一类具有从纳米到厘米尺度上分级结构的天然生物复合材料有着与其它天然生物材料不尽相同的结构和功能，对其结构乃至超结构进行研究，探索其力学行为的微观机理，对于包括农业工程在内的众多工程领域中仿生材料和仿生系统设计具有重要意义。该文对蹄壁角蛋白、羽毛角蛋白、毛发角蛋白及爪子角蛋白材料的结构及力学性能和角蛋白材料的分析方法进行了综合评述。