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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 1,603 records · Page 89
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Application of functional genomics for domestication of novel non-model microbes

Abstract With the expansion of domesticated microbes producing biomaterials and chemicals to support a growing circular bioeconomy, the variety of waste and sustainable substrates that can support microbial growth and production will also continue to expand. The diversity of these microbes also requires a range of compatible genetic tools to engineer improved robustness and economic viability. As we still do not fully understand the function of many genes in even highly studied model microbes, engineering improved microbial performance requires introducing genome-scale genetic modifications followed by screening or selecting mutants that enhance growth under prohibitive conditions encountered during production. These approaches include adaptive laboratory evolution, random or directed mutagenesis, transposon-mediated gene disruption, or CRISPR interference (CRISPRi). Although any of these approaches may be applicable for identifying engineering targets, here we focus on using CRISPRi to reduce the time required to engineer more robust microbes for industrial applications. One-Sentence Summary The development of genome scale CRISPR-based libraries in new microbes enables discovery of genetic factors linked to desired traits for engineering more robust microbial systems.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1980

Microwave integrated circuit for Josephson voltage standards

A microwave integrated circuit comprised of one or more Josephson junctions and short sections of microstrip or stripline transmission line is fabricated from thin layers of superconducting metal on a dielectric substrate. The short sections of transmission are combined to form the elements of the circuit and particularly, two microwave resonators. The Josephson junctions are located between the resonators and the impedance of the Josephson junctions forms part of the circuitry that couples the two resonators. The microwave integrated circuit has an application in Josephson voltage standards. In this application, the device is asymmetrically driven at a selected frequency (approximately equal to the resonance frequency of the resonators), and a d.c. bias is applied to the junction. By observing the current voltage characteristic of the junction, a precise voltage, proportional to the frequency of the microwave drive signal, is obtained.

Holdeman, L. B.↗
NASA NTRS2001

The sugar model: catalytic flow reactor dynamics of pyruvaldehyde synthesis from triose catalyzed by poly-l-lysine contained in a dialyzer

The formation of pyruvaldehyde from triose sugars was catalyzed by poly-l-lysine contained in a small dialyzer with a 100 molecular weight cut off (100 MWCO) suspended in a much larger triose substrate reservoir at pH 5.5 and 40 degrees C. The polylysine confined in the dialyzer functioned as a catalytic flow reactor that constantly brought in triose from the substrate reservoir by diffusion to offset the drop in triose concentration within the reactor caused by its conversion to pyruvaldehyde. The catalytic polylysine solution (400 mM, 0.35 mL) within the dialyzer generated pyruvaldehyde with a synthetic intensity (rate/volume) that was 3400 times greater than that of the triose substrate solution (12 mM, 120 mL) outside the dialyzer. Under the given conditions the final yield of pyruvaldehyde was greater than twice the weight of the polylysine catalyst. During the reaction the polylysine catalyst was poisoned presumably by reaction of its amino groups with aldehyde reactants and products. Similar results were obtained using a dialyzer with a 500 MWCO. The dialyzer method of catalyst containment was selected because it provides a simple and easily manipulated experimental system for studying the dynamics and evolutionary development of confined autocatalytic processes related to the origin of life under anaerobic conditions.

Biogenesis↗
NASA NTRS2012

Rhombohedral cubic semiconductor materials on trigonal substrate with single crystal properties and devices based on such materials

Growth conditions are developed, based on a temperature-dependent alignment model, to enable formation of cubic group IV, group II-V and group II-VI crystals in the [111] orientation on the basal (0001) plane of trigonal crystal substrates, controlled such that the volume percentage of primary twin crystal is reduced from about 40% to about 0.3%, compared to the majority single crystal. The control of stacking faults in this and other embodiments can yield single crystalline semiconductors based on these materials that are substantially without defects, or improved thermoelectric materials with twinned crystals for phonon scattering while maintaining electrical integrity. These methods can selectively yield a cubic-on-trigonal epitaxial semiconductor material in which the cubic layer is substantially either directly aligned, or 60 degrees-rotated from, the underlying trigonal material.

Park, Yeonjoon↗
DOE OSTI2021

Patient mutations in human ATP:cob(I)alamin adenosyltransferase differentially affect its catalytic versus chaperone functions

Human ATP:cob(I)alamin adenosyltransferase (ATR) is a mitochondrial enzyme that catalyzes an adenosyl transfer to cob(I)alamin, synthesizing 5'-deoxyadenosylcobalamin (AdoCbl) or coenzyme B 12 . ATR is also a chaperone that escorts AdoCbl, transferring it to methylmalonyl-CoA mutase, which is important in propionate metabolism. Mutations in ATR lead to methylmalonic aciduria type B, an inborn error of B12 metabolism. Our previous studies have furnished insights into how ATR protein dynamics influence redox-linked cobalt coordination chemistry, controlling its catalytic versus chaperone functions. In this study, we have characterized three patient mutations at two conserved active site residues in human ATR, R190C/H, and E193K and obtained crystal structures of R190C and E193K variants, which display only subtle structural changes. All three mutations were found to weaken affinities for the cob(II)alamin substrate and the AdoCbl product and increase K M(ATP) . 31 P NMR studies show that binding of the triphosphate product, formed during the adenosylation reaction, is also weakened. However, although the k cat of this reaction is significantly diminished for the R190C/H mutants, it is comparable with the WT enzyme for the E193K variant, revealing the catalytic importance of Arg-190. Furthermore, although the E193K mutation selectively impairs the chaperone function by promoting product release into solution, its catalytic function might be unaffected at physiological ATP concentrations. In contrast, the R190C/H mutations affect both the catalytic and chaperoning activities of ATR. Because the E193K mutation spares the catalytic activity of ATR, our data suggest that the patients carrying this mutation are more likely to be responsive to cobalamin therapy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods

Electrochemical reduction of furfural (ECRFF) emerges as an efficient and sustainable means to obtain high-value chemicals and biofuels with the activity and product selectivity being sensitive to cathode materials. In this work, elementary steps describing furfuryl alcohol (FA) and 2-methylfuran (MF) production routes in ECRFF are studied by using periodic density functional theory on Ag, Pb, and Ni, as alternative cathode materials. The established Brønsted–Evans–Polanyi (BEP) relationship has been proven to be reliable to estimate energy barriers of C–O bond cleavage. The intrinsic characters of Ag, Pb, and Ni are then summarized in free energy diagrams to reflect the FA and MF production trends as future guidelines to evaluate ECRFF activity and selectivity on these metals. On all metal surfaces, at both terrace and stepped sites, the first C–H or O–H hydrogenation step, producing respective mh6 or mh7 intermediates, influences overall FA production. On Ag and Pb, pathways involving the mh6 intermediate are thermodynamically and kinetically favored, whereas on Ni, both mh6 and mh7 routes are competitive due to strong interactions between the furan ring and the substrate. In addition, these partially hydrogenated intermediates can also undergo C–O bond cleavage with reduced energy barriers (compared to direct C–O bond cleavage in furfural), which opens potential paths for parallel MF production. Conversion of FA into MF catalyzed by these metallic cathodes was considered as well, although the high C–O bond cleavage energy barrier is likely to hinder this process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structures of monomeric and dimeric PRC2:EZH1 reveal flexible modules involved in chromatin compaction

Polycomb repressive complex 2 (PRC2) is a histone methyltransferase critical for maintaining gene silencing during eukaryotic development. In mammals, PRC2 activity is regulated in part by the selective incorporation of one of two paralogs of the catalytic subunit, EZH1 or EZH2. Each of these enzymes has specialized biological functions that may be partially explained by differences in the multivalent interactions they mediate with chromatin. Here, we present two cryo-EM structures of PRC2:EZH1, one as a monomer and a second one as a dimer bound to a nucleosome. When bound to nucleosome substrate, the PRC2:EZH1 dimer undergoes a dramatic conformational change. We demonstrate that mutation of a divergent EZH1/2 loop abrogates the nucleosome-binding and methyltransferase activities of PRC2:EZH1. Finally, we show that PRC2:EZH1 dimers are more effective than monomers at promoting chromatin compaction, and the divergent EZH1/2 loop is essential for this function, thereby tying together the methyltransferase, nucleosome-binding, and chromatin-compaction activities of PRC2:EZH1. We speculate that the conformational flexibility and the ability to dimerize enable PRC2 to act on the varied chromatin substrates it encounters in the cell.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Indication of non-thermal contribution to visible femtosecond laser-induced CO oxidation on Ru(0001)

We studied CO oxidation on Ru(0001) induced by 400 nm and 800 nm femtosecond laser pulses where we find a branching ratio between CO oxidation and desorption of 1:9 and 1:31, respectively, showing higher selectivity towards CO oxidation for the shorter wavelength excitation. Activation energies computed with density functional theory show discrepancies with values extracted from the experiments, indicating both a mixture between different adsorbed phases and importance of non-adiabatic effects on the effective barrier for oxidation. We simulated the reactions using kinetic modeling based on the two-temperature model of laser-induced energy transfer in the substrate combined with a friction model for the coupling to adsorbate vibrations. This model gives an overall good agreement with experiment except for the substantial difference in yield ratio between CO oxidation and desorption at 400 nm and 800 nm. However, including also the initial, non-thermal effect of electrons transiently excited into antibonding states of the O-Ru bond yielded good agreement with all experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

How Large Should the QM Region Be in QM/MM Calculations? The Case of Catechol O -Methyltransferase

Hybrid quantum mechanical–molecular mechanical (QM/MM) simulations are widely used in studies of enzymatic catalysis. Until recently, it has been cost prohibitive to determine the asymptotic limit of key energetic and structural properties with respect to increasingly large QM regions. Here, leveraging recent advances in electronic structure efficiency and accuracy, we investigate catalytic properties in catechol O-methyltransferase, a prototypical methyltransferase critical to human health. Using QM regions ranging in size from reactants-only (64 atoms) to nearly one-third of the entire protein (940 atoms), we show that properties such as the activation energy approach within chemical accuracy of the large-QM asymptotic limits rather slowly, requiring approximately 500–600 atoms if the QM residues are chosen simply by distance from the substrate. This slow approach to asymptotic limit is due to charge transfer from protein residues to the reacting substrates. Our large QM/MM calculations enable identification of charge separation for fragments in the transition state as a key component of enzymatic methyl transfer rate enhancement. We introduce charge shift analysis that reveals the minimum number of protein residues (approximately 11–16 residues or 200–300 atoms for COMT) needed for quantitative agreement with large-QM simulations. The identified residues are not those that would be typically selected using criteria such as chemical intuition or proximity. These results provide a recipe for a more careful determination of QM region sizes in future QM/MM studies of enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Photocatalytic Transfer Hydrogenation in Water: Insight into Mechanism and Catalyst Speciation

Organometallic catalysts with strong metal-to-ligand charge-transfer (MLCT) optical transitions and reactive metal-hydride bonds provide opportunities for new excited-state reactivity. Toward this end, we have investigated photoinduced transfer hydrogenation reactions for a series of Cp*IrH complexes with functionalized bipyridyl ligands. Overcoming the baseline reactivity of this class of catalyst toward hydrogen evolution in aqueous media presents a major challenge for focusing this photochemical reactivity into desired transformations of more complex organic substrates. In this work, a photochemically induced aqueous ketone reduction catalyzed by [Cp*Ir(bpy)H][Cl] is reported and benchmarked to the competing hydrogen evolution reaction (HER). A detailed mechanistic study is conducted of the reduction of cyclohexanone with sodium formate delivering the reducing equivalent. Examining the kinetic profile of the cyclohexanone reduction revealed an unexpected induction period, suggesting a more complex underlying reaction mechanism where product selectivity was not simply a function of direct competition from a common excited-state reactive intermediate. The reaction kinetics were analyzed by variable time normalization analysis (VTNA), and the catalyst resting state was interrogated through operando light-emitting diode (LED) illumination H-1 NMR spectroscopy. Overall, these and other mechanistic studies provide insight into a photochemical reaction pathway to ketone reduction that is distinct from that previously reported for HER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synchrotron x-ray diffraction study of micro-patterns obtained by spatially selective hydrogenation of GaAsN

We report a comparative synchrotron radiation x-ray diffraction study of GaAs{sub 1−y}N{sub y} micro-structures obtained by two different patterning methods: spatially selective H incorporation achieved by using H-opaque masks and spatially selective H removal attained by laser writing. These methods are emerging as original routes for fabrication of micro- and nano-structures with in-plane modulation of the bandgap energy. By measuring the out-of-plane and in-plane lattice parameters, we find that for both patterning approaches the largest part of the micro-structure volume remains tensile-strained and pseudomorphic to the substrate, regardless of the compressive-strained hydrogenated barriers. However, a larger lattice disorder is probed in the laser-written micro-structures and attributed to partial removal of H and/or strain changes at the micro-structure boundaries. This larger lattice disorder is confirmed by photoluminescence studies.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Ultra-Sensitive Magnetoresistive Displacement Sensing Device

An ultrasensitive displacement sensing device for use in accelerometers, pressure gauges, temperature transducers, and the like, comprises a sputter deposited, multilayer, magnetoresistive field sensor with a variable electrical resistance based on an imposed magnetic field. The device detects displacement by sensing changes in the local magnetic field about the magnetoresistive field sensor caused by the displacement of a hard magnetic film on a movable microstructure. The microstructure, which may be a cantilever, membrane, bridge, or other microelement, moves under the influence of an acceleration a known displacement predicted by the configuration and materials selected, and the resulting change in the electrical resistance of the MR sensor can be used to calculate the displacement. Using a micromachining approach, very thin silicon and silicon nitride membranes are fabricated in one preferred embodiment by means of anisotropic etching of silicon wafers. Other approaches include reactive ion etching of silicon on insulator (SOI), or Low Pressure Chemical Vapor Deposition of silicon nitride films over silicon substrates. The device is found to be improved with the use of giant magnetoresistive elements to detect changes in the local magnetic field.

Olivas, John D.↗
DOE OSTI2020

Article with transparent conductive oxide coating

A solar cell includes a first substrate having a first surface and a second surface. An underlayer is located over the second surface. A first conductive layer is located over the underlayer. An overlayer is located over the first conductive layer. A semiconductor layer is located over the conductive oxide layer. A second conductive layer is located over the semiconductor layer. The first conductive layer includes a conductive oxide and at least one dopant selected from the group consisting of tungsten, molybdenum, niobium, and/or fluorine.

14 SOLAR ENERGY↗
DOE OSTI2025

Toward Efficient Entropic Recycling by Mastering Ring–Chain Kinetics

Traditional chemical recycling approaches for condensation polymers suffer compounding energy losses and CO 2 emissions across multiple polymerization and depolymerization cycles. Entropic recycling can address these energy losses by entrapping free energy within the deconstruction products. Entropic recycling involves depolymerization to macrocyclic monomers, but such processes have not been feasible due to the high dilutions typically required to generate macrocyclic compounds. Here, we leverage selective catalysis to allow entropic recycling at concentrations 20–2000× higher than typical for macrocyclization reactions. We find that Ru-based olefin metathesis catalysts containing bulky iodine ligands significantly bias the ring–chain kinetic product distribution during ring-closing metathesis (RCM) toward the formation of oligomeric cycloalkenes. Further improvements in reaction concentration and macrocycle yield are obtained by using high catalyst loadings and by predisposing the alkene substrates to undergo favorable macrocyclization. These RCM optimizations translate effectively to cyclodepolymerization (CDP) of an olefin-containing polymer, with RCM and CDP affording similar macrocycle product distributions under identical reaction conditions. Macrocycle polymerization by entropy-driven ring-opening metathesis provides much higher molecular weight polymers than condensation polymerization of linear analogues, reducing the time to achieve high molecular weight from hours to minutes and enabling polymerization at room temperature. Finally, our findings re-emphasize the importance of energy consumption during a polymer’s lifecycle and provide a framework for the design of efficient entropic recycling systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbons with Renewable Feedstock

One of the grand challenges for national energy security is the establishment of sustainable chemical transformations. The chemical industry relies on naphtha feedstock from nonrenewable crude oil, and uses energy intense processes to make useful building block molecules such as ethylene through steam cracking, which generates significant greenhouse carbon dioxide emissions. Sustainable chemistry through selective catalysis should enable chemical transformations that use renewable feedstock such as nonfood biomass, minimize energy consumption, and do not emit greenhouse gases or other waste byproducts. In this research, we studied fundamental chemistry that couples the removal of oxygen atoms from nonfood biomass derived polyols and diols with oxidative dehydrogenation (ODH) of petroleum based alcohols. Heterobimetallic Re-Ir complexes were constructed and their reaction chemistry established. Typical substrates are glycerol, sugar alcohols and pentane to produce allyl alcohol, pentene, and water. The reaction mechanism of a recyclable rhenium nano-particle catalyst was established for deoxydehydration of sugar alcohols without the use of organic solvents.

09 BIOMASS FUELS↗
NASA NTRS2004

Performance Trade-Offs for MBG Using Different Bandgap Pairs

Present GAInP2/GAAs cell grown on Ge (or GaAs) substrates have demonstrates high efficiency, However, the individual bandgaps (1.85 eV, 1.42 eV respectively) are not the optimum match to convert the AM0 spectrum efficiently, although by reducing the thickness of the GaInP2 cell, good efficiencies have been achieved. Within the III-V alloys, modeling shows that several dual junction cells, comprising different bandgap pairs, could give higher efficiency. This paper outlines the modeling used, the bandgap pairs selected, and projections for the AM0 efficiency assuming that the effects of lattice mismatch associated with the bandgap can be reduced. We also present preliminary data on I-V performance for the selected top and bottom cells and for some full cascade cells. We have included some characterization results to check the bandgaps and lattice strain, to check how closely the fabricated cells conform to the model,

Iles, P. A.↗
NASA NTRS2014

A Cryogenic Infrared Calibration Target

A compact cryogenic calibration target is presented that has a peak diffuse reflectance, R < or = 0.003, from 800 to 4800/cm (12 − 2 microns ). Upon expanding the spectral range under consideration to 400-10,000/ cm−1 (25 − 1 microns) the observed performance gracefully degrades to R < or = 0.02 at the band edges. In the implementation described, a high-thermal-conductivity metallic substrate is textured with a pyramidal tiling and subsequently coated with a thin lossy dielectric coating that enables high absorption and thermal uniformity across the target. The resulting target assembly is lightweight, has a low-geometric profile, and has survived repeated thermal cycling from room temperature to approx.4 K. Basic design considerations, governing equations, and test data for realizing the structure described are provided. The optical properties of selected absorptive materials-Acktar Fractal Black, Aeroglaze Z306, and Stycast 2850 FT epoxy loaded with stainless steel powder-are characterized and presented

dielectric coating↗