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.
In the present work, we demonstrate the ability to electrospin wheat gluten, a polydisperse plant protein polymer that is currently available at roughly 0.50 dollars/lb. A variety of electrospinning experiments were carried out with wheat gluten from two sources, at different solution concentrations, and with native and denatured wheat gluten to illustrate the interplay between protein structure and the fluid dynamics of the electrospinning process. The presence of both cylindrical and flat fibers was observed in the nonwoven mats, which were characterized using both polarized optical microscopy and field emission scanning electron microscopy. Retardance images obtained by polarized optical microscopy exhibited evidence of molecular orientation at the surface of the fibers. We believe that fiber formation by electrospinning is a result of both chain entanglements and the presence of reversible junctions in the protein, in particular, the breaking and re-forming of disulfide bonds that occur via a thiol/disulfide interchange reaction. The presence of the highest molecular weight glutenin polymer chains in the wheat protein appeared to be responsible for the lower threshold concentration for fiber formation, relative to that of a lower molecular weight fraction of wheat protein devoid of the high molecular weight glutenin component. Denaturation of the wheat protein, however, clearly disrupted this delicate balance of properties in the experimental regimes we investigated, as electrospun fibers from the denatured state were not observed.
As a potential alternative to currently available skin substitutes and wound dressings, we explored the use of bioactive scaffolds made of plant-derived proteins. We hypothesized that 'green' materials, derived from renewable and biodegradable natural sources, may confer bioactive properties to enhance wound healing and tissue regeneration. We optimized and characterized fibrous scaffolds electrospun from soy protein isolate (SPI) with addition of 0.05% poly(ethylene oxide) (PEO) dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol, and from corn zein dissolved in glacial acetic acid. Fibrous mats electrospun from either of these plant proteins remained intact without further cross-linking, possessing a skin-like pliability. Soy-derived scaffolds supported the adhesion and proliferation of cultured primary human dermal fibroblasts. Using targeted PCR arrays and qPCR validation, we found similar gene expression profiles of fibroblasts cultured for 2 and 24 h on SPI substrates and on collagen type I at both time points. On both substrates there was a pronounced time-dependent upregulation of several genes related to ECM deposition remodelling, including MMP-10, MMP-1, collagen VII, integrin-α2 and laminin-β3, indicating that both plant- and animal-derived materials induce similar responses from the cells after initial adhesion, degrading substrate proteins and depositing extracellular matrix in a 'normal' remodelling process. These results suggest that 'green' proteins, such as soy and zein, are promising as a platform for organotypic skin equivalent culture, as well as implantable scaffolds for skin regeneration. Future studies will determine specific mechanisms of their interaction with skin cells and their efficacy in wound-healing applications.
Fluorescence has been demonstrated to be an accurate tool for monitoring resin cure. It is measured using an evanescent wave fiber-optic sensor. An economical optical fiber sensor has been developed with a refractive index greater than 1.6, permitting evanescent wave monitoring of epoxy resins. The fluorescence wavelength-shift, which has been correlated with monomer conversion, is monitored during the liquid molding process. Unidirectional glass fabrics with volume fractions from 40% to 60% were injected with epoxy resin at a variety of driving pressures and cured at several temperatures. Several composite parts were fabricated to test the effects of vacuum pressure, injection rate, cure temperature, and fiber fraction on the performance of the sensor. The sensitivity of the evanescent wave fluorescence sensor to the condition of the resin system was also examined. Two sets of resin/hardener samples were subjected to rigorous chemical analysis to determine the extent of their differences.
A linear variable differential transformer (LVDT) was employed to evaluate CO2‐polymer plasticization. Preliminary results on polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) elastomer are presented. At 22 °C under CO2 pressure, SBS undergoes compression due to hydrostatic pressure. However, sample expansion occurs upon depressurization. At 45 °C, SBS undergoes swelling of 0.7% due to CO2 plasticization, while no post‐pressurization expansion is observed. The contrasting result is explained by change in PS domain mobility and discontinuity in the density‐pressure relationship.
Linear displacement of SBS as a function of time at 56 and 134 bar CO2.magnified imageLinear displacement of SBS as a function of time at 56 and 134 bar CO2.
The resin transfer molding (RTM) technique often utilizes reinforcement with a complex fiber architecture. Several parameters, including the permeability tensor, are necessary to characterize the flow behavior in these intricate fibrous porous media. In this paper, a general procedure for extracting three‐dimensional permeability tensors from data is presented. A general procedure is warranted if the permeability tensor lies out of the material plane. An approximate solution to Darcy's law was employed to relate the components of the permeability tensor to experimental measurements. The procedure requires inverting six nonlinear equations with a robust binary search algorithm. The accuracy of the approximate solution to Darcy's law was checked and found to be in close agreement with a nearly exact solution to Darcy's law obtained by finite element methods.
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