Modelling of pyrolysis and combustion of gluten-glycerol-based bioplastics

Non-isothermal thermogravimetric analysis, under nitrogen and air atmospheres, has been applied to study the thermal degradation of wheat gluten and gluten-glycerol-based bioplastics. In order to explain experimental data, thermal degradation has been simulated using the so-called pseudo-components, which are related to protein fraction (mainly gliadin and glutenin), residual starch and plasticiser. Thus, the proposed models have been used to shed some light on the thermal decomposition of these materials, which have been found affected by their compositions and microstructures. Modelling confirms the experimental bioplastic and gluten isolate compositions, e.g. bioplastic moisture content, starch concentration and the expected gliadin/glutenin ratio. According to the simulation, the glycerol volatilisation is affected by bioplastic moisture content and hindered by the protein matrix. A fact pointing out that glycerol/water blend plays relevant plasticizing roles in the protein matrix through diverse physicochemical interactions.     

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.     

Synthesis and characterization of starch based bioplatics using varying plant-based ingredients,plasticizers and natural fillers

With the ever-increasing demand of plastics in the world and their consequent disastrous effects on environment, a suitable environmental-friendly substitute like bioplastics/biodegradable plastics is the need time. This study centers on green-production of a variety of bioplastic samples from (1) banana peel starch (BPP) and (2) a composite of banana peel starch, cornstarch and rice starch (COM) with varying amounts of potato peel powder and wood dust powder as fillers, respectively. Two different plasticizers – Glycerol and Sorbitol – have been utilized separately and in a 1:1 combination. A total of 12 samples of each of two types of bioplastics were made using multiple amounts and combinations of the fillers and plasticizers, to test the differences in the physical and chemical characteristics (moisture content, absorption of water, solubility in water, solubility in alcohol, biodegradation in soil, tensile strength, Young’s modulus and FT-IR) of the produced samples due to their different compositions. The differences in the properties of the bioplastic samples produced make them suitable for usage in many different applications. All 24 of the samples produced were synthesized using natural and environmentally safe raw material and showed biodegradation, thus proving to be a good alternative to the conventional plastics.     

Potential of plant proteins for medical applications

Various natural and synthetic polymers are being explored to develop biomaterials for tissue engineering and drug delivery. Although proteins are preferable over carbohydrates and synthetic polymers, biomaterials developed from proteins lack the mechanical properties and/or biocompatibilities required for medical applications. Plant proteins are widely available, have low potential to be immunogenic and can be made into fibers, films, hydrogels and micro- and nano-particles for medical applications. Studies, mostly with zein, have demonstrated the potential of using plant proteins for tissue engineering and drug delivery. Although other plant proteins such as wheat gluten and soyproteins have also shown biocompatibility using in vitro studies, fabricating biomaterials such as nano-fibers and nano-particles from soy and wheat proteins offers considerable challenges.     

Characterization of lignocellulosic curaua fibres

Curaua fibres have specific mechanical properties similar to inorganic fibres and are an important renewable raw material. Milled curaua fibres, submitted to different treatments, were characterized by mechanical and thermal properties, moisture content, water absorption, surface morphology, FTIR spectroscopy, density and X-ray diffraction. Except for moisture content and mechanical properties, no other significant changes were observed after the treatments. The treated fibres also show an increase of surface roughness.     

Reactivity of wheat gluten protein during mechanical mixing: radical and nucleophilic reactions for the addition of molecules on sulfur

Mechanical properties of gluten-based biomaterials, such as break stress, were known to be influenced by temperature and shear stresses applied during processing. It is well documented in literature that these processing parameters promoted wheat gluten protein aggregation. Exchange between disulfide bonds and thiol groups oxidation are the postulated mechanisms that lead to gluten protein solubility loss in sodium dodecyl sulfate buffers. Both nucleophilic and radical reactions were postulated to act during gluten aggregation. To graft molecules on gluten, a study was carried out to explore the reactivity of its thiol and disulfide groups during thermomechanical mixing. A range of reactants able to react via radical or nucleophilic pathways with thiol groups were synthesized. Reactivity between gluten and functions was quantified by gluten solubility measurements. This investigation and literature observations allowed proposal of a general gluten aggregation mechanism during mixing.     

Comparative analysis of the chemical treatments used in keratin extraction from red sheep’s hair and the cell viability evaluations of this keratin for tissue engineering applications

Hair waste is one of the solid substances rejected by the leather industry. This waste finds its way into the surroundings causing serious environmental pollution. This hair waste may be utilized for effective extraction of keratin, thereby generating value-added products with numerous applications. Thus we focusing on utilizing red sheep’s hair waste for extracting keratin by the application of different chemical treatments such as sodium hydroxide, sodium sulfide, mercaptoethanol, cysteine, sodium metabisulfite with urea (SMB), and SMB with SDS (SMBS). CD spectrum and FTIR results of the keratin samples indicated a predominance of the helical conformation along with β sheets. SDS-PAGE confirmed the molecular weight of the keratin samples to be in the range of 40–60 kDa. DSC and TGA analysis exhibited the extracted keratin to have a higher denaturation temperature (>200 °C) and thermal stability. The keratin samples obtained using varied chemical treatments were compared in terms of yield, protein content, and cost-effectiveness, and the sample obtained using SMBS was preferred for in vitro studies. It is indicated that keratin extracted using SMBS effectively involved for fibroblast cell growth. Thus, we suggest that these keratin could produce biomaterials that can serve as a valuable material for biomedical applications.     

From the salt marsh to the ID-card: Bacteriorhodopsin as a functional material in nanobiotechnology

Bacteriorhodopsin (BR) is an evolutionary highly optimized photochromic retinal protein, which is found in extremely halophilic bacteria, e.g., in salt marshes. We demonstrated that starting from the wildtype as a blueprint by means of gene technology and biotechnology a versatile material for optical information recording can be developed. BR is structurally related to the visual pigment rhodopsin. It is the key molecule in the halobacterial photosynthetic system — an alternative to the chlorophyll-dependent photosynthesis. Its biological function ist that of a light-driven proton pump. In the halobacterial cell — which are found e.g. in salt marshes — it converts light energy into chemical energy, i.e. a proton gradient over the cell membrane, which finally supplies ATP to the cell. The photochromic properties of BR are very attractive compared to those of known organic photochromic compounds, in particular as far as longevity under exposure to oxygen and light is concerned. This is one of the reasons why we try to utilized this evolutionary optimized biomaterial for technical applications in particular in optical data storage and processing. As the biological function of BR is optimized for energy conversion, the physical properties of BR need to be tuned to turn this molecule into a material which matches the requirements of optical applications in data storage and processing. Gene technology is a powerful tool for the controlled modification of physical properties of a biomolecule like BR. In technical applications water needs to be omitted. However, the function of biomaterials strictly depends on the presence of water. Membrane proteins are much less dependent on the presence of water which makes them good candidates for technical applications. We showed that BR can be processed into dry polymeric films where its function is preserved. In a field test where ID-cards comprising BR-based inks as security elements it has been demonstrated that biomaterials may be integrated in active form as functional components into conventional technical applications. Conventional nanomaterials supply properties to a product, biomaterials supply functions.     

Designing new materials from wheat protein

We recently discovered that wheat gluten could be formed into a tough, plasticlike substance when thiol-terminated, star-branched molecules are incorporated directly into the protein structure. This discovery offers the exciting possibility of developing biodegradable high-performance engineering plastics and composites from renewable resources that are competitive with their synthetic counterparts. Wheat gluten powder is available at a cost of less than dollars 0.5/lb, so if processing costs can be controlled, an inexpensive alternative to synthetic polymers may be possible. In the present work, we demonstrate the ability to toughen an otherwise brittle protein-based material by increasing the yield stress and strain-to-failure, without compromising stiffness. Water absorption results suggest that the cross-link density of the polymer is increased by the presence of the thiol-terminated, star-branched additive in the protein. Size-exclusion high performance liquid chromatography data of molded tri-thiol-modified gluten are consistent with that of a polymer that has been further cross-linked when compared directly with unmodified gluten, handled under identical conditions. Remarkably, the mechanical properties of our gluten formulations stored in ambient conditions were found to improve with time.     

Fennel waste-based films suitable for protecting cultivations

Biodegradable, flexible, and moisture-resistant films were obtained by recycling fennel waste and adding to fennel homogenates the bean protein phaseolin that was modified or not modified by the enzyme transglutaminase. All films were analyzed for their morphology, mechanical properties, water vapor permeability, and susceptibility to biodegradation under soil-like conditions. Our experiments showed that transglutaminase treatment of the phaseolin-containing fennel waste homogenates allowed us to obtain films comparable in their mechanical properties and water vapor permeability to the commercial films Ecoflex and Mater-Bi. Furthermore, biodegradability tests demonstrated that the presence of the enzyme in the film-casting sample significantly influences the integrity of such a product that lasts longer than films obtained either with fennel waste alone or with a mixture of fennel waste and phaseolin. These findings indicate the fennel-phaseolin film prepared in the presence of transglutaminase to be a promising candidate for a new environmentally friendly mulching bioplastic.     

Regulation of silk material structure by temperature-controlled water vapor annealing

We present a simple and effective method to obtain refined control of the molecular structure of silk biomaterials through physical temperature-controlled water vapor annealing (TCWVA). The silk materials can be prepared with control of crystallinity, from a low content using conditions at 4 °C (α helix dominated silk I structure), to highest content of ～60% crystallinity at 100 °C (β-sheet dominated silk II structure). This new physical approach covers the range of structures previously reported to govern crystallization during the fabrication of silk materials, yet offers a simpler, green chemistry, approach with tight control of reproducibility. The transition kinetics, thermal, mechanical, and biodegradation properties of the silk films prepared at different temperatures were investigated and compared by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), uniaxial tensile studies, and enzymatic degradation studies. The results revealed that this new physical processing method accurately controls structure, in turn providing control of mechanical properties, thermal stability, enzyme degradation rate, and human mesenchymal stem cell interactions. The mechanistic basis for the control is through the temperature-controlled regulation of water vapor to control crystallization. Control of silk structure via TCWVA represents a significant improvement in the fabrication of silk-based biomaterials, where control of structure-property relationships is key to regulating material properties. This new approach to control crystallization also provides an entirely new green approach, avoiding common methods that use organic solvents (methanol, ethanol) or organic acids. The method described here for silk proteins would also be universal for many other structural proteins (and likely other biopolymers), where water controls chain interactions related to material properties.     

Study of novel rosin-based biomaterials for pharmaceutical coating

The film forming and coating properties of Glycerol ester of maleic rosin (GMR) and Pentaerythritol ester of maleic rosin (PMR) were investigated. The 2 rosin-based biomaterials were initially characterized in terms of their physicochemical properties, molecular weight (Mw), and glass transition temperature (Tg). Films were produced by solvent evaporation technique on a mercury substrate. Dibutyl sebacate plasticized and nonplasticized films were characterized by mechanical (tensile zzzz strength, percentage elongation, and Young's modulus), water vapor transmission (WVT), and moisture absorption parameters. Plasticization was found to increase film elongation and decrease the Young's modulus, making the films more flexible and thereby reducing the brittleness. Poor rates of WVT and percentage moisture absorption were demonstrated by various film formulations. Diclofenac sodium-layered pellets coated with GMR and PMR film formulations showed sustained drug release for up to 10 hours. The release rate was influenced by the extent of plasticization and coating level. The results obtained in the study demonstrate the utility of novel rosin-based biomaterials for pharmaceutical coating and sustained-release drug delivery systems.     

Mechanical Properties of Thermo-moulded Biofilms in Relation to Proteins/Starch Interactions

The effects of hydrophilic and hydrophobic characteristics of proteins on the interactions with corn starch were investigated in this study. The model system included corn starch and proteins, i.e. zein, gliadin, gluten, soy protein and rapeseed protein. The blend films were prepared by thermo-moulding in gentle conditions at 70 °C in order to avoid starch gelatinization, with respect to water content, and avoid protein denaturation. The effects of different kinds of proteins on structure and mechanical behaviour of blend biomaterials were characterised by scanning electron microscopy (SEM) and tensile test, respectively. The effects of different kinds of proteins on intermolecular interactions between proteins and starch were investigated by dynamical mechanical thermal analysis. Based on the solubility measurement results, almost all protein films showed the similar solubility to the natural protein powders, resulting from the weak influence of mild thermo-moulding treatment on protein inner structure. Different morphologies were observed for different proteins and corresponding blends, which are relatively loose protein architecture that appeared for hydrophobic protein and blend films, and uniform and densely packed architecture for hydrophilic ones. Moreover, different mechanical behaviours were obtained for different proteins and corresponding blends. No significantly increased strength for hydrophilic protein blends with starch added can be explained that there is weak intermolecular interaction between both components based on SEM observation. However, the addition of corn starch granules in hydrophobic protein networks was assumed that starch destroyed or weakened the protein network, resulting in the decrease of mechanical strength.     

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.     

Use of xylan,an agricultural by-product,in wheat gluten based biodegradable films: mechanical,solubility and water vapor transfer rate properties

The possibility of using xylan, as an agricultural by-product, for production of composite films in combinations with wheat gluten was investigated. Different levels of xylan (0-40% w/w) were incorporated into wheat gluten to form biodegradable composite films. Films were prepared at pH 4 and 11, and dried at either uncontrolled or controlled conditions. The mechanical properties, solubilities and water vapour transfer rate (WVTR) of the composite films were studied. Films were obtained with added xylan without decreasing film-forming quality. Xylan can be used as an additive, as much as 40% (w/w), in wheat gluten films. Changing pH, wheat gluten/xylan ratio, xylan type and drying conditions affected mechanical and solubility properties, however, WVTR was not affected by xylan additions. Wheat gluten/xylan composite films having different characteristics can be produced depending on xylan type, composition and process conditions.     

Preparation and properties of starch acetate fibers for potential tissue engineering applications

This article reports the development of fibers from starch acetates that have mechanical properties and water stability better than most polysaccharide‐based biomaterials and protein fibers used in tissue engineering. In this research, starch acetates with three different degrees of substitution (DS) have been used to develop fibers for potential use as tissue engineering scaffolds. Varying the DS of starch acetate will provide fibers with different mechanical properties, hydrophilicity, and degradation behavior. Fibers made from DS 2.3 and 2.8 starch acetates have mechanical properties and water stability required for tissue engineering applications. The starch acetate fibers support the adhesion of fibroblasts demonstrating that the fibers would be suitable for tissue engineering and other medical applications. Biotechnol. Bioeng. 2009;103: 1016–1022. © 2009 Wiley Periodicals, Inc.     

Effect of thermal damage and biaxial loading on the optical properties of a collagenous tissue

Thermal denaturation can induce marked changes in the optical and mechanical properties of collagenous tissues. The optical properties are important in both therapeutic and diagnostic applications of lasers in medicine. Although mechanical stress can be caused by collagen shrinkage in laser-based therapies, how the mechanical loading state affects the optical properties is not well understood. We used a new computer-controlled biaxial testing system to subject bovine epicardium to various loading conditions both before and after multiple levels of thermal damage. An integrating sphere technique was used to measure transmittance and diffuse reflectance, from which absorption and scattering coefficients were calculated using a Monte Carlo method. Results showed that the scattering coefficient increased with increasing mechanical load but decreased as the degree of thermal damage increased. There was no significant change in the absorption coefficient due to thermal damage over the ranges studied.     

开花后水分调控对两个筋型冬小麦品种品质与产量的影响

 通过开花后不同水分处理研究了两个不同筋型冬小麦品种(‘豫麦34’和‘洛阳8716’)(Triticum aestivum cv. `Yumai 34' and `Luoyang 8716')的品质及产量变化。结果表明：随着灌水时间推迟,湿面筋含量、沉降值、面团形成时间、稳定时间、评价值和拉伸面积有提高的趋势,但是千粒重和产量下降;随着开花后灌水量的增加,上述品质数值又有减少,产量及千粒重增加;多次灌水处理与开花后灌1次水处理、开花后不灌水处理之间差异显著,开花后21 d和28 d灌水处理的多项品质指标都大于不灌水处理。两品种面团稳定时间（45%和15%）、沉降值（20%和12%）在不同水分处理下变异系数较大,吸水率、湿面筋、蛋白质含量变异系数（<10%和 <5%）较小。     

Tannin-based rigid foams: A survey of chemical and physical properties

Tannin-based rigid foams, prepared from 95% natural material, are suggested for replacing synthetic phenol–formaldehyde foams in various applications. For that purpose, a few physical properties were measured and reported here: resistance to fire and chemicals, absorption of various liquids, permeability, thermal conductivity and mechanical (compressive and tensile) strength. Modifying the composition through the use of boric and/or phosphoric acid allowed substantial increase of fire resistance. The materials were also found to present good resistance to strong acid and bases, and to solvents. High affinity for water, but limited one for organic liquids, was also evidenced. Finally, slightly anisotropic mechanical properties were measured. The materials present a brittle behaviour, whether tested in compression or traction; nevertheless, their strengths, as well as their thermal conductivities, are fully comparable with those of their phenolic counterparts. We show that such materials of vegetable origins can compete with synthetic ones for most of traditional applications.     

The radiation crosslinked films based on PLLA/PDLA stereocomplex after TAIC absorption in supercritical carbon dioxide

The absorption of triallyl isocyanurate (TAIC) to equimolar stereo blends of PLLA and PDLA (sb-PLA samples) with crosslinker (TAIC) was controlled by supercritical carbon dioxide (sc-CO₂) treatment. The well-mixed sb-PLA/TAIC (sc-PLA) samples containing certain ratios of TAIC were obtained after vacuum evaporation. The sc-PLA samples were become much softer by sc-CO₂ treatment. The crosslinked sc-PLA materials with different crosslinking density were prepared by irradiation treatment at different radiation doses. Gel fraction, thermal properties and mechanical properties of crosslinked samples were investigated with different sc-PLA samples irradiated at the same radiation dose of 30 kGy and sc-PLA3 irradiated at different radiation doses. The crosslinking network inhibited crystallization, and enhanced the rigidity as well as lowered brittleness of irradiated samples. Although tensile strength and Young’s modulus of sc-PLA are reduced by sc-CO₂ treatment, they are much improved by radiation crosslinking at a suitable dose and the crosslinked samples become harder and tougher. The typical crosslinked obtained from sc-PLA3 irradiated at 30 kGy reveals the best thermal stability with the improved mechanical properties.