Wheat Gluten Blends with Maleic Anhydride-Functionalized Polyacrylate Cross-Linkers for Improved Properties.

A family of polyacrylate-based cross-linkers was synthesized to maximize the toughness of high Tg, high modulus wheat gluten blends in the glassy state. Mechanical testing and damping measurements were conducted to provide an example where the work of fracture and strength of the blend substantially exceeds polystyrene while maintaining flexure stiffness in excess of 3 GPa. The new rubbery cross-linkers, polymethyl acrylate-co-maleic anhydride and polyethyl acrylate-co-maleic anhydride, improve WG mechanical properties and reduce water absorption simultaneously. MDSC, FTIR, HPLC, and NMR data confirmed the cross-linking reaction with wheat gluten. Flexural, DMA, and water absorption testing were carried out to characterize the property improvements. DMA was conducted to investigate the relationship between energy damping and mechanical property improvement. If the cross-linker damping temperature is close to the testing temperature, the entire sample exhibits high damping, toughness, and strength.

Batch, design optimization, and DNA sequencing study for continuous 1,3-propanediol production from waste glycerol by a soil-based inoculum.

1,3-propanediol (1,3-PD) was produced with a robust fermentation process using waste glycerol feedstock from biodiesel production and a soil-based bacterial inoculum. An iterative inoculation method was developed to achieve independence from soil and selectively breed bacterial populations capable of glycerol metabolism to 1,3-PD. The inoculum showed high resistance to impurities in the feedstock. 1,3-PD selectivity and yield in batch fermentations was optimized by appropriate nutrient compositions and pH control. The batch yield of 1,3-PD was maximized to ~0.7 mol/mol for industrial glycerol which was higher than that for pure glycerin. 16S rDNA sequencing results show a systematic selective enrichment of 1,3-PD producing bacteria with iterative inoculation and subsequent process control. A statistical design of experiments was carried out on industrial glycerol batches to optimize conditions, which were used to run two continuous flow stirred-tank reactor (CSTR) experiments over a period of >500 h each. A detailed analysis of steady states at three dilution rates is presented. Enhanced specific 1,3-PD productivity was observed with faster dilution rates due to lower levels of solvent degeneration. 1,3-PD productivity, specific productivity, and yield of 1.1 g/l hr, 1.5 g/g hr, and 0.6 mol/mol of glycerol were obtained at a dilution rate of 0.1 h(-1)which is bettered only by pure strains in pure glycerin feeds.

Depolymerization of crystalline cellulose catalyzed by acidic ionic liquids grafted onto sponge-like nanoporous polymers.

The acidic ionic liquid (IL) functionalized polymer (PDVB-SO3H-[C3vim][SO3CF3]) possesses abundant nanoporous structures, strong acid strength and unique capability for deconstruction of crystalline cellulose into sugars in ILs. The polymer shows much improved catalytic activities in comparison with mineral acids, homogeneous acidic ionic liquids and the acidic resins such as Amberlyst 15. The enhanced catalytic activity found in the polymer is attributed to synergistic effects between the strongly acidic group and the ILs grafted onto the polymer, which by itself is capable of breaking down the crystalline structures of cellulose. This study may help develop cost-effective and green routes for conversion of biomass to fuels.

Study of in situ 1-butanol pervaporation from A-B-E fermentation using a PDMS composite membrane: validity of solution-diffusion model for pervaporative A-B-E fermentation.

In this study, the application of a new polydimethylsiloxane (PDMS)/dual support composite membrane was investigated by incorporating the pervaporation process into the A-B-E (acetone-butanol-ethanol) fermentation. The performance of the A-B-E fermentation using the integrated pervaporation/fermentation process showed higher biomass concentrations and higher glucose consumption rates than those of the A-B-E fermentation without pervaporation. The performance of the membrane separation was studied during the separation of 1-butanol from three different 1-butanol solutions: binary, model, and fermentation culture solutions. The solution-diffusion model, specifically the mass transfer equation based on Fick's First Law, was shown to be applicable to the undefined A-B-E fermentation culture solutions. A quantitative comparison of 1-butanol separation from the three different solutions was made by calculating overall mass transfer coefficients of 1-butanol. It was found that the overall mass transfer coefficients during the separation of binary, model, and fermentation culture solutions were 1.50, 1.26, and 1.08 mm/h, respectively.

Performance of batch, fed-batch, and continuous A-B-E fermentation with pH-control.

Batch, fed-batch, and continuous A-B-E fermentations were conducted and compared with pH controlled at 4.5, the optimal range for solvent production. While the batch mode provides the highest solvent yield, the continuous mode was preferred in terms of butanol yield and productivity. The highest butanol yield and productivity found in the continuous fermentation at dilution rate of 0.1h(-1) were 0.21 g-butanol/g-glucose and 0.81 g/L/h, respectively. In the continuous and fed-batch fermentation, the time needed for passing acidogenesis to solventogenesis was an intrinsic hindrance to higher butanol productivity. Therefore, a low dilution rate is suggested for the continuous A-B-E fermentation, while the fed-batch mode is not suggested for solvent production. While 3:6:1 ratio of acetone, butanol, and ethanol is commonly observed from A-B-E batch fermentation by Clostridium acetobutylicum when the pH is uncontrolled, up to 94% of the produced solvent was butanol in the chemostat with pH controlled at 4.5.

The feasibility of converting Cannabis sativa L. oil into biodiesel.

Cannabis sativa Linn, known as industrial hemp, was utilized for biodiesel production in this study. Oil from hemp seed was converted to biodiesel through base-catalyzed transesterification. The conversion is greater than 99.5% while the product yield is 97%. Several ASTM tests for biodiesel quality were implemented on the biodiesel product, including acid number, sulfur content, flash point, kinematic viscosity, and free and total glycerin content. In addition, the biodiesel has a low cloud point (-5 degrees C) and kinematic viscosity (3.48mm(2)/s). This may be attributed to the high content of poly-unsaturated fatty acid of hemp seed oil and its unique 3:1 ratio of linoleic to alpha-linolenic acid.

Imaging and thermal studies of wheat gluten/poly(vinyl alcohol) and wheat gluten/thiolated poly(vinyl alcohol) blends.

The morphology of wheat protein (WG) blends with polyvinyl alcohol (PVA) and respectively with thiolated polyvinyl alcohol (TPVA) was investigated by atomic force (AFM) and transmission electron microscopy (TEM) as well as by modulated dynamic scanning calorimetry (MDSC). Thiolated additives based on PVA and other substrates were previously presented as effective means of improving the strength and toughness of compression molded native WG bars via disulfide-sulfhydryl exchange reactions. Consistent with our earlier results, AFM and TEM imaging clearly indicate that the addition of just a few mole percent of thiol to PVA was sufficient to dramatically change its compatibility with wheat protein. Thus, TPVA is much more compatible with WG and phase separates into much smaller domains than in the case of PVA, although there are still two phases in the blend: one WG-rich phase and another TPVA-rich phase. The WG/TPVA blend has phase domains ranging in size from 0.01 to 0.1 microm, which are roughly 10 times smaller than those of the WG/PVA blend. MDSC further illustrates the compatibilization of the protein with TPVA via the dependence of the transition temperatures on composition.

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.

Electrospun fibers from wheat protein: investigation of the interplay between molecular structure and the fluid dynamics of the electrospinning process.

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.

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.

Characterization of sizing layers and buried polymer/sizing/substrate interfacial regions using a localized fluorescent probe.

A novel technique is described to investigate buried polymer/sizing/substrate interfacial regions, in situ, by localizing a fluorescent probe molecule in the sizing layer. Epoxy functional silane coupling agent multilayers were deposited on glass microscope cover slips and doped with small levels of a fluorescently labeled silane coupling agent (FLSCA). The emission of the grafted FLSCA was dependent on the silane layer thickness, showing blue-shifted emission with decreasing thickness. The fluorescent results suggest that thinner layers were more tightly bound to the glass surface. The layers were also characterized by scanning electron microscopy, contact angle, and thermogravimetric analysis (TGA). When the FLSCA-doped silane layers were immersed in epoxy resin, a blue shift in emission occurred during resin cure, indicating the potential to study interfacial chemistry, in situ. Thicker silane layers exhibited smaller fluorescence shifts during cure, suggesting incomplete resin penetration into the thickest silane layers.

Interpreting the signal from a localized fluorescence sensor: a study by angle-resolved XPS and dynamic SIMS.

Angle-resolved X-ray photoelectron spectroscopy (XPS) and dynamic secondary ion mass spectroscopy (DSIMS) experiments were conducted to assess the interactions between a diamine curing agent and a glycidoxysilane-modified glass substrate. This effort was motivated by earlier work, in which a fluorescent probe localized in dilute quantities in the silane layer was used to track the penetration of the resin into the silane layer, as well as the resin cure. XPS and DSIMS experiments were performed on the silane layers immersed only in the resin hardener, providing more detailed information about the concentration profile and structural reorganization within the silane layer due specifically to hardener penetration. Dynamic SIMS spectra reveal the presence of hardener in the layer, as indicated by the strong CN- signal throughout the silane layer thickness. The XPS results indicate the presence of an amine gradient within the top 10 nm of the silane coating, with less amine penetration deeper into the silane layer. The XPS data also suggest some level of anisotropy in the molecular structure of the diamine/glycidoxysilane coating, as revealed by the differences in the relative atomic concentrations and peak positions of the C1s components at two different take-off angles.

Dewetting of unreacted epoxy/amine mixtures on silica.

We employ a direct method, time-of-flight secondary ion mass spectroscopy (ToF-SIMS), to determine experimentally the chemical compositions of the wetted and dewetted regions of an uncured epoxy thin film. Determining the composition of the dewetted region indicated the presence of a very thin sublayer of resin in what was thought to be a region devoid of resin. The capability of ToF-SIMS to probe small 65 x 65 microm(2) areas of the surface has permitted us to directly compare the SIMS spectra of the wetted and dewetted regions to the survey spectra of the reactants. This may indicate the strength of resin/silica interactions, which determine interface formation and properties.