Water transmission barrier properties of biodegradable films based on cellulosic whiskers and xylan

The reinforcement of natural biopolymers with cellulosic whiskers has been shown to be beneficial for physical strength properties including xylan films. This study examines the water transmission properties of xylan films reinforced with cellulosic whiskers prepared from kraft pulp hydrolyzed with sulfuric acid. Measurements of water transmission rate (WVTR) were accomplished by a modification of wet cup method described by ASTM E 96-95. The results showed that films prepared by xylan reinforced by 10% sulfonated whiskers exhibited a 74% reduction in specific water transmission properties with respect to xylan film and a 362% improvement with respect to xylan films reinforced with 10% softwood kraft fibers.     

Formaldehyde cross-linking of gliadin films: effects on mechanical and water barrier properties

In this study, pioneering results on specific chemical modifications of wheat gluten gliadins and the corresponding impact on mechanical and water barrier properties of derived films are presented. Films were prepared from gliadins chemically treated with formaldehyde and subsequently mixed with different concentrations of glycerol as a plasticizing agent. Water vapor barrier and mechanical properties of the films were evaluated as a function of relative humidity and glycerol concentration. Formaldehyde treatment led to enhanced mechanical properties and, to a lesser extent, improved water barrier of the films, effects which point to the formation of new intermolecular bonds between monomeric gliadins. The occurrence of cross-linking was supported by SDS-PAGE analysis. Cross-linked films maintained their integrity after immersion in water and had similar optical properties to control films. The effect of glycerol and humidity on water vapor permeability and the mechanical properties of films was less acute when proteins were treated with formaldehyde. Thus, chemical treatment of proteins is shown to be a very effective route for optimizing the use of these films in packaging applications.     

Tuning the mechanical and physicochemical properties of cross-linked protein films

Films derived from natural sources such as proteins provide an advantage over synthetic films due to their noncytotoxicity, biodegradability, and vast functionality. A new protein source gained from the cataractous eye protein isolate (CEPI) obtained after surgery has been investigated for this purpose. Glycerol has been employed as the plasticizer and glutaraldehyde (GD) as a cross-linker. Fourier transform infrared spectroscopy was employed to characterize the films. Nanoindentation and thermogravimetric analyses reveal improved mechanical and thermal properties of the cross-linked films. The films with 20% (w/w) GD exhibited properties such as the highest modulus and low water solubility. It is possible to tune the properties based on the extent of cross-linking. All the films were completely degraded by the enzyme trypsin. The similarity of these films was checked by using the prepared films as a delivery vehicle for a model compound, ampicillin sodium. The encapsulation efficiency was found to be 74%, and in vitro release studies showed significant amounts of drug release at physiological pH. This study will help us understand how the properties of protein films can be tuned to obtain the desired physicochemical properties. These biodegradable protein films could find use in pharmaceutical industries as delivery carriers.     

Physical, mechanical, and antibacterial properties of chitosan/PEO blend films

Films formed by blending of two polymers usually have modified physical and mechanical properties compared to films made of the individual components. Our preliminary studies indicated that incorporation of chitosan in polyethylene oxide (PEO) films may provide additional functionality to the PEO films and may decrease their tendency to spherulitic crystallization. The objective of this study was to determine the correlation between chitosan/PEO weight ratio and the physical, mechanical, and antibacterial properties of corresponding films. Films with chitosan/PEO weight ratios from 100/0 to 50/50 in 10% increments were characterized by measuring thickness, puncture strength (PS), tensile strength (TS), elongation at break (%E), water vapor permeability (WVP), and water solubility (WS). Additionally, the films were examined by polarized microscopy, wide-angle X-ray diffraction (WAXD), and Fourier transform infrared (FTIR) spectroscopy, and their antibacterial properties were tested against Escherichia coli. The chitosan fraction contributes to antimicrobial effect of the films, decreases tendency to spherulitic crystallization of PEO, and enhances puncture and tensile strength of the films, while addition of the PEO results in thinner films with lower water vapor permeability. Films with 90/10 blend ratio of chitosan/PEO showed the most satisfactory PS, TS, %E, and antibacterial properties of all tested ratios.     

Structure–properties relationship in cross-linked high amylose starch cast films

Cross-linked high amylose starch cast films were prepared to study the effect of cross-linking degree on various properties in normal environmental conditions. Mechanical tensile properties (Young's modulus, elongation at break, tensile strength), water vapour transmission rate (WVTR) and oxygen permeability coefficients of cast films were determined as a function of cross-linking degree and percentage of free humidity. Cross-linking degree and degree of crystallinity are closely related and seem to have non-negligible opposite effect on the properties of interest. By using increased amounts of cross-linking agents, the effect of cross-linking degree tends to reduce the degree of crystallinity modulating thus mechanical properties, water vapour permeability and oxygen permeability coefficients. Yield strength, tensile strength at break, WVTR versus cross-linking degree showed a non-monotonous behaviour. Maximal values for these properties were reached for moderate cross-linking degree. Optimal crystalline/amorphous ratio in the films may induce interactions and balanced effects, which would be responsible for the non-linear behaviour of some of the investigated properties. By cross-linking with epichlorohydrin in the range 1–10 g crosslinker/100 g polymer, the mechanical properties of films are still related to water content and water vapour permeability remains high compared to some synthetic polymeric materials.     

Characterization of edible emulsified films with low affinity to water based on kefiran and oleic acid

New edible composite films based on kefiran and oleic acid (OA) at the ratio of 15, 25, and 35% (w/w) were prepared using emulsification with the aim of improving their water vapour barrier and mechanical properties. Film-forming solutions were characterized in terms of rheological properties and particle-size distribution. The impact of the incorporation of OA into the film matrix was studied by investigating the physical, mechanical, and thermal properties of the films. The water vapour permeability (WVP) of the emulsified films was reduced by approximately 33% by adding OA. The mechanical properties of kefiran films were also affected by adding OA: tensile strength was diminished, and elongation increased considerably. Differential scanning calorimetry showed that the glass transition temperature (T_g) of the kefiran film was −16 °C and was not considerably affected by adding OA. Therefore, OA could be incorporated into these films for some food-technology applications that need a low affinity toward water.     

Effect of polysaccharide structure on mechanical and thermal properties of galactomannan-based films

Films were prepared from guar gum and locust bean gum galactomannans. In addition, enzymatic modification was applied to guar gum to obtain structurally different galactomannans. Cohesive and flexible films were formed from galactomannans plasticized with 20-60% (w/w of polymer) glycerol or sorbitol. Galactomannans with lower galactose content (locust bean gum, modified guar gum) produced films with higher elongation at break and tensile strength. The mechanical properties of films were improved statistically significantly by decreasing the degree of polymerization of guar gum with mannanase treatments (4 h) of 2 and 10 nkat/g, whereas 50 nkat/g produced films with low elongation at break and tensile strength. Galactomannans with approximately 6 galactose units per 10 mannose backbone units resulted in films with 2 peaks in loss modulus spectra, whereas films from galactomannans with approximately 2 galactose groups per 10 mannose units behaved as a single phase in dynamic mechanical analysis.     

Mechanical,barrier and morphological properties of pea starch and peanut protein isolate blend films

Mechanical, barrier and morphological properties of edible films based on blends of Pea starch (PS) and Peanut protein isolate (PPI) plasticized with glycerol (30%, w/w) were investigated. As PPI ratio in PS/PPI blends increased, the thickness of films decreased, the opacity slightly elevated and color intensified. The addition of PPI to the PS film significantly reduced tensile strength from 5.44 MPa to 3.06 MPa, but increased elongation from 28.56% to 98.12% with the incorporation of PPI into PS at 50% level. Film solubility value fell from 22.31% to 9.78% upon the incorporation of PPI ranged from 0 to 50% level. When PPI was added into PS film at 40% level, the WVP and WVTR of the films markedly dropped from 11.18% to 4.19% and 6.16 to 1.95%, respectively. Scanning electron microscopy (SEM) of the surface of films showed that many swollen starch granules were presented in the 100% PS film, while 100% PPI film was observed to have rougher surfaces with presence of pores or cavities. The PS/PPI blend films upon the incorporation of PPI at 20% and 50% level were not homogeneous. However, the smoother film surface was observed in PS/PPI blend films with the addition of PPI at 40% level. SEM image of the cross-sections of the films revealed that the 100% PS film showed a uniform and compact matrix without disruption, and pore formation and 100% PPI film displayed a smooth structure. Rougher and flexible network was shown in blend film with the addition of PPI reaching 40% level.     

Mechanical and Barrier Properties of Films from Millet Protein Pennisetin

Plastics are one of the most commonly used materials today in an immense range of applications. Since plastics originate from petroleum, which is not a renewable resource, we need to find alternatives to achieve environmentally sustainable goals. One of our most abundant renewable resources is cereals; wheat gluten is recognized as a replacement for synthetic plastics. Another cereal protein is pennisetin from pearl millet, which can grow in more arid areas and is therefore an important crop in times of climate change. In contrast to gluten, the material properties of pennisetin have as yet been relatively unexplored. This work evaluated the mechanical and barrier properties of pennisetin films, including three different plasticizers (glycerol only, glycerol/citric acid mixture, and glycerol/lactic acid/polyethylene glycol mixture). The films were cast from ethanol solutions. It was found that all of the three plasticizers resulted in approximately equal thermomechanical properties in the pennisetin films. However, the glycerol/citric acid mixture seemed to give more beneficial tensile and barrier properties. The advantage of this plasticizer mixture was believed to be due to the altered microstructure of the films. The material properties of pennisetin were found to be fully comparable to those of other cereal protein materials.     

Structure and mechanical properties of hydroxypropylated starch films

Films of acid-hydrolyzed hydroxypropylated pea starch with average molecular weight M w ranging from 3.3 x 10 (4) g/mol to 1.6 x 10 (6) g/mol were prepared from 25% (w/w) solution by casting. The structure of the films was investigated by means X-ray diffraction and calorimetry, evidencing a B-type crystalline structure. In similar drying conditions, 25 degrees C and 40% of relative humidity, the crystallinity varied from 24% for the low molecular weight (A5) to almost none for the highest molecular weight (A160). The influence of the drying temperature was also investigated. A reduction of the crystallinity from 16% to almost none was found when increasing temperature from 25 to 65 degrees C. The glass transition temperature ( T g) at different water contents was determined. The difference of T g between the first and the second scan was interpreted by changes in the water distribution between phases into the B-type crystalline structure. Mechanical properties of the films determined by tensile tests and by DMTA in the glassy state showed no effect of the average molecular weight or of crystallinity. In contrast, thermomechanical experiments by DMTA showed that the average molecular weight of the sample influenced the mechanical relaxation and the moduli in the rubbery state.     

Preparation and characterization of polyaniline/chitosan blend film

Films consisting of a blend of a chitosan hydrogel and a conductive polymer, polyaniline (PANI), were prepared and characterized for their electrical and mechanical properties. Polyaniline in emeraldine base (EB) form was dispersed in chitosan solution and blend films were obtained by solution casting. The PANI particles in the blend films were then doped with HCl where we observed reductions in the film tensile strength and Young's modulus by about 30%, but the films electrical conductivity increased by 6 orders of magnitude. The highest electrical conductivity of the blend films was of the order 10⁻⁴ S/cm. The electrical and mechanical properties of the films varied with polyaniline content, acid dopant type, acid dopant concentration, and doping time.     

Novel protein fibers from wheat gluten

Protein fibers with mechanical properties similar to those of wool and better than those of soyprotein and zein fibers have been produced from 100% wheat gluten. Wheat gluten is a low cost, abundantly available, and renewable resource suitable for fiber production. A simple production method has been developed to obtain high-quality wheat gluten fibers, and the structure and properties of the fibers have been studied. Wheat gluten fibers have breaking tenacity of about 115 MPa, breaking elongation of 23%, and a Young's modulus of 5 GPa, similar to those of wool. Wheat gluten fibers have better tensile properties than soyprotein- and casein-based biomaterials. In addition, the wheat gluten fibers have resistance similar to that of PLA fibers to water in weak alkaline and slightly lower resistance in weak acidic conditions at high temperatures.     

The construction and characterization of two xylan-degrading chimeric enzymes

Degradation of xylan requires several enzymes. Two chimeric enzymes, xyln-ara and xyln-xylo, were constructed by linking the catalytic portion of a xylanase (xyln) to either an arabinofuranosidase (ara) or a xylosidase (xylo) with a flexible peptide linker. The recombinant parental enzymes and chimeras were produced in E. coli at high levels and purified for characterization of their enzymatic and kinetic properties as well as activities on natural substrates. The chimeras closely resemble the parental enzymes or their mixtures with regard to protein properties. They share similar temperature profiles and have similar catalytic efficiencies as the parental enzymes when assayed using substrates 4-nitrophenyl-alpha-L-arabinofuranoside or 2-nitrophenyl- beta-D-xylopyranoside. The chimeras also show unique enzymatic characteristics. In xylanase activity assays using Remazol Brilliant Blue-xylan, while the parental xylanase has a pH optimum of pH 8, the chimeras showed shifted pH optima as a consequence of significantly increased activity at pH 6 (the optimal pH for ara and xylo). Both chimeras exhibited additive effects of the parental enzymes when assayed at wide ranges of pH and temperatures. The xyln-xylo chimera had the same activities as the xyln/xylo mixture in hydrolyzing the natural substrates oat spelt xylan and wheat arabinoxylan. Compared to the xyln/ara mixture, the xyln-ara chimera released the same amounts of xylose from oat spelt xylan and approximately 30% more from wheat arabinoxylan at pH 6. Our results demonstrate the feasibility and advantages of generating bifunctional enzymes for the improvement of xylan bioconversion.     

Construction of viscoelastic biocompatible films via the layer-by-layer assembly of hyaluronan and phosphorylcholine-modified chitosan

Films of hyaluronan (HA) and a phosphorylcholine-modified chitosan (PC-CH) were constructed by the polyelectrolyte multilayer (PEM) deposition technique and their buildup in 0.15 M NaCl was followed by atomic force microscopy, surface plasmon resonance spectroscopy (SPR), and dissipative quartz crystal microbalance (QCM). The HA/PC-CH films were stable over a wide pH range (3.0-12.0), exhibiting a stronger resistance against alkaline conditions as compared to HA/CH films. The loss and storage moduli, G' and G", of the films throughout the growth of eight bilayer assemblies were derived from an impedance analysis of the QCM data recorded in situ. Both G' and G" values were one order of magnitude lower than the moduli of HA/CH films. The fluid gel-like characteristics of HA/PC-CH multilayers were attributed to their high water content (50 wt %), which was estimated by comparing the surface coverage values derived from SPR and QCM measurements. Given the versatility of the PEM methodology, HA/PC-CH films are attractive tools for developing biocompatible surface coatings of controlled mechanical properties.     

Aging properties of films of plasticized vital wheat gluten cast from acidic and basic solutions

In order to understand the mechanisms behind the undesired aging of films based on vital wheat gluten plasticized with glycerol, films cast from water/ethanol solutions were investigated. The effect of pH was studied by casting from solutions at pH 4 and pH 11. The films were aged for 120 days at 50% relative humidity and 23 degrees C, and the tensile properties and oxygen and water vapor permeabilities were measured as a function of aging time. The changes in the protein structure were determined by infrared spectroscopy and size-exclusion and reverse-phase high-performance liquid chromatography, and the film structure was revealed by optical and scanning electron microscopy. The pH 11 film was mechanically more stable with time than the pH 4 film, the latter being initially very ductile but turning brittle toward the end of the aging period. The protein solubility and infrared spectroscopy measurements indicated that the protein structure of the pH 4 film was initially significantly less polymerized/aggregated than that of the pH 11 film. The polymerization of the pH 4 film increased during storage but it did not reach the degree of aggregation of the pH 11 film. Reverse-phase chromatography indicated that the pH 11 films were to some extent deamidated and that this increased with aging. At the same time a large fraction of the aged pH 11 film was unaffected by reducing agents, suggesting that a time-induced isopeptide cross-linking had occurred. This isopeptide formation did not, however, change the overall degree of aggregation and consequently the mechanical properties of the film. During aging, the pH 4 films lost more mass than the pH 11 films mainly due to migration of glycerol but also due to some loss of volatile mass. Scanning electron and optical microscopy showed that the pH 11 film was more uniform in thickness and that the film structure was more homogeneous than that of the pH 4 film. The oxygen permeability was also lower for the pH 11 film. The fact that the pH 4 film experienced a larger and more rapid change in its mechanical properties with time than the pH 11 film, as a consequence of a greater loss of plasticizer, was presumably due to its initial lower degree of protein aggregation/polymerization. Consequently, the cross-link density achieved at pH 4 was too low to effectively retain volatiles and glycerol within the matrix.     

Formulation,Characterisation and Stabilisation of Buccal Films for Paediatric Drug Delivery of Omeprazole

This study aimed to develop films for potential delivery of omeprazole (OME) via the buccal mucosa of paediatric patients. Films were prepared using hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), sodium alginate (SA), carrageenan (CA) and metolose (MET) with polyethylene glycol (PEG 400) as plasticiser, OME (model drug) and L-arg (stabiliser). Gels (1% w/w) were prepared at 40°C using water and ethanol with PEG 400 (0–1% w/w) and dried in an oven (40°C). Optimised formulations containing OME and L-arg (1:1, 1:2 and 1:3) were prepared to investigate the stabilisation of the drug. Tensile properties (Texture analysis, TA), physical form (differential scanning calorimetry, DSC; X-ray diffraction, XRD; thermogravimetric analysis, TGA) and surface topography (scanning electron microscopy, SEM) were investigated. Based on the TA results, SA and MET films were chosen for OME loading and stabilisation studies as they showed a good balance between flexibility and toughness. Plasticised MET films were uniform and smooth whilst unplasticised films demonstrated rough lumpy surfaces. SA films prepared from aqueous gels showed some lumps on the surface, whereas SA films prepared from ethanolic gels were smooth and uniform. Drug-loaded gels showed that OME was unstable and therefore required addition of L-arg. The DSC and XRD suggested molecular dispersion of drug within the polymeric matrix. Plasticised (0.5% w/w PEG 400) MET films prepared from ethanolic (20% v/v) gels and containing OME: L-arg 1:2 showed the most ideal characteristics (transparency, ease of peeling and flexibility) and was selected for further investigation.KEY WORDS: buccal drug delivery, omeprazole, oral films, paediatric, plasticiser     

Wheat gluten-thiolated poly(vinyl alcohol) blends with improved mechanical properties

A multifunctional macromolecular thiol (TPVA) obtained by esterification of poly(vinyl alcohol) (PVA) with 3-mercaptopropionic acid was characterized by a combination of NMR, IR, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC), and was used as a wheat gluten (WG) reactive modifier. The effect of TPVA molecular weight (M(w) = 2000, 9500, 50 000, and 205 000) and blend composition (5, 20, and 40% w/w TPVA/WG) on the mechanical properties of compression-molded bars indicates that TPVA/WG blends increase the fracture strength by up to 76%, the elongation by 80%, and the modulus by 25% above WG. In contrast, typical WG additives such as glycerol and sorbitol improve flexibility but decrease modulus and strength. Preliminary investigations of suspension rheology, water uptake, molecular weight distribution and electron microscopy of TPVA/WG and PVA/WG blends illustrate the different protein interactions with PVA and TPVA. Further work is underway to determine whether TPVA and WG form protein conjugates or microphase-separated morphologies.     

Improved xylanase production from a haloalkalophilic Staphylococcus sp. SG-13 using inexpensive agricultural residues

The production of an alkali-stable xylanase, with dual pH optima, from haloalkalophilic Staphylococcus sp. SG-13 has been enhanced using agro-residues in submerged fermentation and a biphasic growth system. The agro-residues such as wheat bran, sugarcane bagasse, corncobs and poplar wood when used as sole carbon source, improved the xylanase yield by five-fold as compared to xylose and xylan. Staphylococcus sp. SG-13 also produced equally good amounts of xylanase when grown simply in deionized water (pH 8.0) supplemented with agro-residues as sole carbon source. In the biphasic growth system (lower layer containing agricultural residue set in agar medium with liquid medium above it), the prime substrate, wheat bran (1% w/v), resulted in maximum xylanase production of 4525 U l^–1 (pH 7.5) and 4540 U l^–1 (pH 9.2) at an agar: broth ratio of 4.0 after 48 h of incubation at 37 °C under static conditions. In general, the cost-effective agro-residues were found to be more suitable inducers for xylanase production over expensive substrates like xylan.     

北京市某社区女性居民膳食模式与常见慢性病的关系

目的：了解北京市某社区女性居民的主要膳食模式及与常见慢性病的关系。方法：于2018年5月--2019年2月,采用多阶段整群随机抽样的方式对辖区内460名18~70岁女性居民进行问卷调查。收集基本资料、饮食行为习惯、家族病史、慢病史、治疗史等情况,分析饮食行为对常见慢性病的影响。结果：北京市白纸坊社区女性居民共有4种主要膳食模式,分别为：“传统膳食模式”（占43.1%）、“以肉类为主膳食模式”（占27.9%）、“水果蛋奶膳食模式”（占16.4%）和“主食、酒类和饮料膳食模式”（占12.6%）。Logistic 回归分析提示：在控制混杂因素后,“以肉类为主膳食模式”和“主食、酒类和饮料膳食模式”与社区女性居民高血压呈正相关性（OR=1.314和1.995,P<0.05）。“传统膳食模式”和“主食、酒类和饮料膳食模式”与社区女性居民糖尿病呈正相关性（OR=1.239和1.332,P<0.05）。“以肉类为主膳食模式”和“主食、酒类和饮料膳食模式”与社区女性居民血脂异常呈正相关性（OR=1.902和1.557,P<0.05）。“以肉类为主膳食模式”与社区女性居民冠心病呈正相关性（OR=1.338,P<0.05）。结论：社区女性居民膳食模式构成存在一定的不合理,且与主要慢性病的发生相关,应控制相关影响因素,促进健康、合理的膳食模式,降低慢性病的发生。     

Fermentation, purification, formulation, and pharmacological evaluation of a prolyl endopeptidase from Myxococcus xanthus: implications for Celiac Sprue therapy

Celiac Sprue is a multi-factorial disease characterized by an inflammatory response to ingested wheat gluten and similar proteins in rye and barley. Proline-rich gluten peptides from wheat, rye, and barley are relatively resistant to gastrointestinal digestion, and therefore persist in the intestinal lumen to elicit immunopathology in genetically susceptible individuals. In this study, we characterize the in vitro gluten detoxifying properties of a therapeutically promising prolyl endopeptidase from Myxococcus xanthus (MX PEP), and describe the development of a prototypical enteric-coated capsule containing a pharmacologically useful dose of this enzyme. A high-cell density fed-batch fermentation process was developed for overproduction of recombinant MX PEP in E. coli, yielding 0.25-0.4 g/L purified protein. A simple, scalable purification and lyophilization procedure was established that yields >95% pure, highly active and stable enzyme as a dry powder. The dry powder was blended with excipients and encapsulated in a hard gelatin capsule. The resulting capsule was enteric coated using Eudragit L30-D55 polymer coat, which provided sufficient resistance to gastric conditions (> 1 h in 0.01 M HCl, pH 2 with pepsin) and rapid release under duodenal conditions (15-30 min release in pH 6.0 in the presence of trypsin and chymotrypsin). In conjunction with pancreatic enzymes, MX PEP breaks down whole gluten into a product mixture that is virtually indistinguishable from that generated by the Flavobacterium meningosepticum (FM) PEP as judged by chromatographic assays. Competitive studies involving selected immunogenic peptides mixed with whole gluten reveal that both PEPs have a wide range of substrate specificity. Our results support further in vitro and in vivo evaluation of the MX PEP capsule as an oral therapeutic agent for Celiac Sprue patients.