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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Enzyme Design From the Bottom Up: An Active Nickel Electrocatalyst with a Structured Peptide Outer Coordination Sphere

Functional, peptide-containing metal complexes with a well-defined peptide structure have the potential to enhance molecular catalysts via an enzyme-like outer coordination sphere. Here, we report the synthesis and characterization of an active, peptide-based metal complex built upon the well characterized hydrogen production catalyst, Ni(PPh2NPh)2. The incorporated peptide maintains its B-hairpin structure when appended to the metal core, and the electrocatalytic activity of the peptide-based metal complex (~100,000 s-1) is fully retained. The combination of an active molecular catalyst with a structured peptide outer coordination sphere provides a scaffold that permits the incorporation of features of an enzyme-like outer-coordination sphere necessary to create molecular electrocatalysts with en-hanced functionality.

bioinspired↗
DOE OSTI2014

Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation

Hydrogenase enzymes provide inspiration for investigations of molecular catalysts utilizing structural and functional mimics of the active site. However, the resulting active site mimics cannot match the combination of high rates and low overpotentials of the enzyme, suggesting that the rest of the protein scaffold, i.e., the outer coordination sphere, is necessary for the efficiency of hydrogenase. Therefore, inclusion of outer coordination sphere elements onto molecular catalysts may enable us to achieve and ultimately surpass the overall enzymatic efficiency. In an effort to identify and include the missing enzymatic features, there has been recent effort to understand the effect of outer coordination sphere elements on molecular catalysts for hydrogen oxidation and production. Our focus has been to utilize amino acid or peptide based scaffolds on an active functional mimic for hydrogen oxidation and production, [Ni(PR2NR’2)2]2+. This bottom-up approach, i.e, building an outer coordination sphere around a functional molecular catalyst, has allowed us to evaluate individual contributions to catalysis, including enhancing proton movement, concentrating substrate and introducing structural features to control reactivity. Collectively, these studies have resulted in catalysts that can operate faster, can operate at lower overpotentials, have enhanced water solubility, and/or can provide more stability to oxygen or extreme conditions such as strongly acidic or basic conditions than their unmodified parent complexes. Common mechanisms have yet to be defined to predictably control these processes but our growing knowledge in this area is essential for the eventual mimicry of enzymes for developing efficient molecular catalysts for practical use. This account reviews previously published work supported by the US DOE Basic Energy Sciences (BES), Physical Bioscience program, the Office of Science Early Career Research Program through the USDOE, BES, the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, Office of Science, Office of BES. Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. DOE’s Office of Biological and Environmental Research program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

bioinspired↗
DOE OSTI2014

A Proton Channel Allows a Hydrogen Oxidation Catalyst to Operate at a Moderate Overpotential with Water Acting as a Base

Proton channels facilitate the movement of protons over large distances and are critical in many reactions, from controlling proton delivery in metalloenzymes[1] to moving protons through PEM fuel cells.[2] Hydrogenases are enzymes that use proton channels to deliver protons to or from the enzyme active site to achieve high rates of hydrogen production and oxidation at low overpotentials.[3] The [Ni(PR2NR’2)2]2+ series of complexes, which are functional mimics of the [FeFe]-hydrogenase active site, utilize pendant amines to move the proton to or from the Ni, resulting in some of the fastest synthetic catalysts for hydrogen production and oxidation reported.[4] While intramolecular proton movement has been shown to be facile,[5] deprotonation of hydrogen oxidation catalysts can be a slow step for catalysis.[6] Additionally, a stable H2 adduct (endo-endo) is formed which, if bypassed, could contribute to an overall enhanced rate (Figure 1). A proton channel may aid in addressing these outstanding issues, and the well-studied nature of these catalysts allows them to serve as a platform to investigate the role of a proton channel in solving these problems. To this end we added a second proton relay to this complex, which we demonstrate serves two purposes: we show that the second proton relay facilitates rapid proton transfer, altering the kinetic products formed following H2 addition, and avoiding the low energy endo-endo intermediate. It also aids in lowering the overpotential at which the catalyst operates using water as a base, demonstrating the multi-functional role of a proton channel in molecular catalysts, and possibly in enzymes. This work was supported by the US Department of Energy, Early Career Research Program, Basic Energy Sciences, Chemical Sciences, Geosciences & Biosciences Division and by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

amino acid catalysts↗
DOE OSTI2011

Application of a new composite cubic-boron nitride gasket assembly for high pressure inelastic x-ray scattering studies of carbon related materials

We have developed a new composite cubic-boron nitride (c-BN) gasket assembly for high pressure diamond anvil cell studies, and applied it to inelastic x-ray scattering (IXS) studies of carbon related materials in order to maintain a larger sample thickness and avoid the interference from the diamond anvils. The gap size between the two diamond anvils remained {approx}80 {micro}m at 48.0 GPa with this new composite c-BN gasket assembly. The sample can be located at the center of the gap, {approx}20 {micro}m away from the surface of both diamond anvils, which provides ample distance to separate the sample signal from the diamond anvils. The high pressure IXS of a solvated C{sub 60} sample was studied up to 48 GPa, and a pressure induced bonding transition from sp{sup 2} to sp{sup 3} was observed at 27 GPa.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Five-dimensional visualization of phase transition in BiNiO 3 under high pressure

Colossal negative thermal expansion was recently discovered in BiNiO 3 associated with a low density to high density phase transition under high pressure. The varying proportion of co-existing phases plays a key role in the macroscopic behavior of this material. Here, we utilize a recently developed X-ray Absorption Near Edge Spectroscopy Tomography method and resolve the mixture of high/low pressure phases as a function of pressure at tens of nanometer resolution taking advantage of the charge transfer during the transition. This five-dimensional (X, Y, Z, energy, and pressure) visualization of the phase boundary provides a high resolution method to study the interface dynamics of high/low pressure phase.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Comparative Genome Structure, Secondary Metabolite, and Effector Coding Capacity across Cochliobolus Pathogens

The genomes of five Cochliobolus heterostrophus strains, two Cochliobolus sativus strains, three additional Cochliobolus species (Cochliobolus victoriae, Cochliobolus carbonum, Cochliobolus miyabeanus), and closely related Setosphaeria turcica were sequenced at the Joint Genome Institute (JGI). The datasets were used to identify SNPs between strains and species, unique genomic regions, core secondary metabolism genes, and small secreted protein (SSP) candidate effector encoding genes with a view towards pinpointing structural elements and gene content associated with specificity of these closely related fungi to different cereal hosts. Whole-genome alignment shows that three to five of each genome differs between strains of the same species, while a quarter of each genome differs between species. On average, SNP counts among field isolates of the same C. heterostrophus species are more than 25 higher than those between inbred lines and 50 lower than SNPs between Cochliobolus species. The suites of nonribosomal peptide synthetase (NRPS), polyketide synthase (PKS), and SSP encoding genes are astoundingly diverse among species but remarkably conserved among isolates of the same species, whether inbred or field strains, except for defining examples that map to unique genomic regions. Functional analysis of several strain-unique PKSs and NRPSs reveal a strong correlation with a role in virulence.

59 BASIC BIOLOGICAL SCIENCES↗