Publications by authors named "Thomas J Schwartz"

This study evaluated the effects of chemical and biological preservatives and ensiling stage on spoilage, ruminal in vitro fermentation, and methane production of wet brewer's grain (WBG) silage. Treatments (TRT) were sodium lignosulfonate at 10 g/kg fresh WBG (NaL1) and 20 g/kg (NaL2), propionic acid at 5 g/kg fresh WBG (PRP, 99%), a combination inoculant (INO; Lactococcus lactis and Lactobacillus buchneri each at 4.9 log cfu per fresh WBG g), and untreated WBG (CON).

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Biocatalysis using molecular oxygen as the electron acceptor has significant potential for selective oxidations at low cost. However, oxygen is poorly soluble in water, and its slow rate of mass transfer in the aqueous phase is a major obstacle, even for laboratory-scale syntheses. Oxygen transfer can be accelerated by vigorous mechanical methods, but these are often incompatible with biological catalysts.

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The characterization of nanometer-scale interactions between carbon-containing substrates and alumina surfaces is of paramount importance to industrial and academic catalysis applications, but it is also very challenging. Here, we demonstrate that dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) allows the unambiguous description of the coordination geometries and conformations of the substrates at the alumina surface through high-resolution measurements of C-Al distances. We apply this new technique to elucidate the molecular-level geometry of C-enriched methionine and natural abundance poly(vinyl alcohol) adsorbed on γ-AlO-supported Pd catalysts, and we support these results with element-specific X-ray absorption near-edge measurements.

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Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach.

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DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticle catalysts. By offering >2500-fold time savings, the technique enabled the observation of (13)C-(13)C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

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The chemisorption and breakdown of methionine (Met) adsorbed on Pd/γ-Al2O3 catalysts were investigated by solid-state NMR. (13)C-enriched Met (ca. 0.

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Conversion of biomass-derived molecules involves catalytic reactions under harsh conditions in the liquid phase (e.g., temperatures of 250 °C and possibly under either acidic or basic conditions).

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It is shown that microenvironments formed around catalytically active sites mitigate catalyst deactivation by biogenic impurities that are present during the production of biorenewable chemicals from biologically derived species. Palladium and ruthenium catalysts are inhibited by the presence of sulfur-containing amino acids; however, these supported metal catalysts are stabilized by overcoating with poly(vinyl alcohol) (PVA), which creates a microenvironment unfavorable for biogenic impurities. Moreover, deactivation of Pd catalysts by carbon deposition from the decomposition of highly reactive species is suppressed by the formation of bimetallic PdAu nanoparticles.

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