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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Human cytochrome P450 17A1 structures with metabolites of prostate cancer drug abiraterone reveal substrate-binding plasticity and a second binding site

Abiraterone acetate is a first-line therapy for castration-resistant prostate cancer. This prodrug is deacetylated in vivo to abiraterone, which is a potent and specific inhibitor of cytochrome P450 17A1 (CYP17A1). CYP17A1 performs two sequential steps that are required for the biosynthesis of androgens that drive prostate cancer proliferation, analogous to estrogens in breast cancer. Abiraterone can be further metabolized in vivo on the steroid A ring to multiple metabolites that also inhibit CYP17A1. Despite its design as an active-site-directed substrate analog, abiraterone and its metabolites demonstrate mixed competitive/noncompetitive inhibition. To understand their binding, we solved the X-ray structures of CYP17A1 with three primary abiraterone metabolites. Despite different conformations of the steroid A ring and substituents, all three bound in the CYP17A1 active site with the steroid core packed against the I helix and the A ring C3 keto or hydroxyl oxygen forming a hydrogen bond with N202 similar to abiraterone itself. The structure of CYP17A1 with 3-keto, 5α-abiraterone was solved to 2.0 Å, the highest resolution to date for a CYP17A1 complex. This structure had additional electron density near the F/G loop, which is likely a second molecule of the inhibitor and which may explain the noncompetitive inhibition. Mutation of the adjacent Asn52 to Tyr positions its side chain in this space, maintains enzyme activity, and prevents binding of the peripheral ligand. Collectively, our findings provide further insight into abiraterone metabolite binding and CYP17A1 function.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

X-ray topography characterization of gallium nitride substrates for power device development

Gallium nitride substrates grown by the hydride vapor phase epitaxy (HVPE) method using a patterned growth process have been characterized by synchrotron monochromatic beam X-ray topography in the grazing incidence geometry. Images reveal a starkly heterogeneous distribution of dislocations with areas as large as 0 3 mm 2 containing threading dislocation densities below 10 3 cm -2 in between a grid of strain centers with higher threading dislocation densities (> 10 4 cm -2 ). Basal plane dislocation densities in these areas are as low as 104 cm -2 . By comparing the recorded images of dislocations with ray tracing simulations of expected dislocations in GaN, the Burgers vectors of the dislocations have been determined. The distribution of threading screw/mixed dislocations (TSDs/TMDs), threading edge dislocations (TEDs) and basal plane dislocations (BPDs) is discussed with implications for fabrication of power devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Stress-dominated growth of two-dimensional materials on nonplanar substrates

Curved features are ubiquitous on solid surfaces, but the effect of surface curvatures on growth of two-dimensional (2D) materials has not yet been established. Using a newly developed method based on the Metropolis algorithm and taking graphene as a prototype, we find that a curved feature on substrates can result in a variety of topological defects in 2D materials. As the feature's size increases by just nanometers, the defects can vary from adatoms, dislocation pairs, and grain boundary scars to long-range grain boundaries, in contrast to previously reported defect-free modes of rigid colloidal crystals growing on spheres. We identify an important role of curvature-induced lattice stress in lowering the growth rate over the curved features and driving a plastic instability in the materials. When the feature's size increases to several nanometers, the stress effect is compromised by an enhanced effect of geodesic curvature, yielding long-range grain boundaries as a result of increased local growth rate on the feature with respect to that on flat regions. Here we further provide a ‘phase diagram’ of defects that helps to guide a rational choice of geometrical parameters of features towards the growth of high-quality 2D materials as well as controllable creation of topological defects.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Bump-and-Hole Engineering Identifies Specific Substrates of Glycosyltransferases in Living Cells

Studying posttranslational modifications classically relies on experimental strategies that oversimplify the complex biosynthetic machineries of living cells. Protein glycosylation contributes to essential biological processes, but correlating glycan structure, underlying protein, and disease-relevant biosynthetic regulation is currently elusive. Here, we engineer living cells to tag glycans with editable chemical functionalities while providing information on biosynthesis, physiological context, and glycan fine structure. We introduce a non-natural substrate biosynthetic pathway and use engineered glycosyltransferases to incorporate chemically tagged sugars into the cell surface glycome of the living cell. We apply the strategy to a particularly redundant yet disease-relevant human glycosyltransferase family, the polypeptide N-acetylgalactosaminyl transferases. This approach bestows a gain-of-chemical-functionality modification on cells, where the products of individual glycosyltransferases can be selectively characterized or manipulated to understand glycan contribution to major physiological processes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Influence of substrate composition on size and chemical state of ion beam synthesised Co nanoparticles – Towards fabrication of electrodes for energy devices

A one-step approach to synthesize ultrafine transition metal particles (size < 5 nm) in carbon substrates is highly desirable for fabricating electrodes for energy devices. Herein, cobalt ion implantation into amorphous carbon films (a:C) and hydrogenated amorphous carbon films (a:CH) was explored, with the aim of synthesizing ultrafine metallic cobalt nanoparticles at room temperature. Co ions of 30 keV energy were implanted into the carbon films to achieve a Co areal density of 1.0 ± 0.1 × 10 17 atoms cm -2 . Rutherford backscattering measurements revealed that hydrogenated amorphous carbon films gave a broader Co depth distribution compared to the amorphous carbon films. Further, cross-sectional TEM analysis revealed that hydrogenated carbon films suppressed metallic Co nanoparticle aggregation, leading to the creation of ultrafine Co nanoparticles (size < 5 nm). Co L-edge X-ray absorption spectroscopy measurements confirmed the formation of predominantly metallic Co nanoparticles by ion implantation. Results conclusively demonstrate that the presence of hydrogen (~ 28 at%) in the carbon matrix facilitates the synthesis of ultrafine metallic Co nanoparticles during Co ion implantation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insertion reactions and structural studies of [(NHC)CuH] 2 with nitrogen-based substrates

The stoichiometric and catalytic reactions of Cu-H dimers supported by N-heterocyclic carbenes (NHCs) have mainly focused on the insertions of aldehydes, ketones, CO 2 , and unsaturated hydrocarbons. Here we investigated the stoichiometric reactions of dimeric [(NHC)CuH] 2 (NHC = IPr*, 6Dipp) with unsaturated nitrogen-based substrates of PhN=NPh, N 3 Ad, pyrazine, and N 2 O. The spectroscopic and structural chacterizations of the resulting monomeric, two-coordinate Cu(I) complexes containing diphenyl hydrazido, triazenido, pyrazinyl, and hydroxide ligands are discussed. The hydrazido complex of (IPr*)Cu(NPh-NHPh) and triazenido complex of (IPr*)Cu(HNNNAd) are resistant to N—N bond cleavage and loss of N 2 , respectively, to form the corresponding amido complexes even when heated at 80 °C over several hours.

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

CreA-mediated repression of gene expression occurs at low monosaccharide levels during fungal plant biomass conversion in a time and substrate dependent manner

Carbon catabolite repression enables fungi to utilize the most favourable carbon source in the environment, and is mediated by a key regulator, CreA, in most fungi. CreA-mediated regulation has mainly been studied at high monosaccharide concentrations, an uncommon situation in most natural biotopes. In nature, many fungi rely on plant biomass as their major carbon source by producing enzymes to degrade plant cell wall polysaccharides into metabolizable sugars. To determine the role of CreA when fungi grow in more natural conditions and in particular with respect to degradation and conversion of plant cell walls, we compared transcriptomes of a creA deletion and reference strain of the ascomycete Aspergillus niger during growth on sugar beet pulp and wheat bran. Transcriptomics, extracellular sugar concentrations and growth profiling of A. niger on a variety of carbon sources, revealed that also under conditions with low concentrations of free monosaccharides, CreA has a major effect on gene expression in a strong time and substrate composition dependent manner. In addition, we compared the CreA regulon from five fungi during their growth on crude plant biomass or cellulose. It showed that CreA commonly regulated genes related to carbon metabolism, sugar transport and plant cell wall degrading enzymes across different species. We therefore conclude that CreA has a crucial role for fungi also in adapting to low sugar concentrations as occurring in their natural biotopes, which is supported by the presence of CreA orthologs in nearly all fungi.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Effect of substrate temperature on the growth of Nb 3 Sn film on Nb by multilayer sputtering

Here, we report on the fabrication of niobium tin (Nb 3 Sn) films by multilayer sequential sputtering on niobium at substrate temperatures ranging from room temperature to 250 °C. The multilayers were then annealed inside a separate vacuum furnace at 950 °C for 3 h. The material properties of the films were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and transmission electron microscopy. The superconducting properties of the films were studied by four-point probe resistivity measurements from room temperature to below the superconducting critical temperature T c . The highest film T c was 17.76 K, obtained when the multilayers were deposited at room temperature. When the deposition temperature was raised to 250 °C, a significant reduction in voids was achieved while the film's T c was 17.58 K.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enhanced 2'-Fucosyllactose production by engineered Saccharomyces cerevisiae using xylose as a co-substrate

2'-Fucosyllactose (2'-FL), a human milk oligosaccharide with confirmed benefits for infant health, is a promising infant formula ingredient. Although Escherichia coli, Saccharomyces cerevisiae, Corynebacterium glutamicum, and Bacillus subtilis have been engineered to produce 2'-FL, their titers and productivities need be improved for economic production. Glucose along with lactose have been used as substrates for producing 2'-FL, but accu- mulation of by-products due to overflow metabolism of glucose hampered efficient production of 2' -FL regardless of a host strain. To circumvent this problem, we used xylose, which is the second most abundant sugar in plant cell wall hydrolysates and is metabolized through oxidative metabolism, for the production of 2'-FL by engi- neered yeast. Specifically, we modified an engineered S. cerevisiae strain capable of assimilating xylose to pro- duce 2' -FL from a mixture of xylose and lactose. First, a lactose transporter (Lac12) from Kluyveromyces lactis was introduced. Second, a heterologous 2'-FL biosynthetic pathway consisting of enzymes Gmd, WcaG, and WbgL from Escherichia coli was introduced. Third, we adjusted expression levels of the heterologous genes to maximize 2'-FL production. The resulting engineered yeast produced 25.5 g/L of 2'-FL with a volumetric productivity of 0.35 g/L∙h in a fed-batch fermentation with lactose and xylose feeding to mitigate the glucose repression. Interestingly, the major location of produced 2'-FL by the engineered yeast can be changed using different culture media. While 72% of the produced 2'-FL was secreted when a complex medium was used, 82% of the produced 2'-FL remained inside the cells when a minimal medium was used. In conclusion, as yeast extract is already used as food and animal feed ingredients, 2'-FL enriched yeast extract can be produced cost-effectively using the 2'-FL-accumu- lating yeast cells.

2′ -fucosyllactose↗
DOE OSTI2020

Two-Electron–Two-Proton Transfer from Colloidal ZnO and TiO 2 Nanoparticles to Molecular Substrates

Transfers of multiple electrons and protons are challenging yet central to many energy-conversion processes and other chemical and biochemical reactions. Semiconducting oxides can hold multiple redox equivalents. This study describes the 2e – /2H + transfer reactivity of photo-reduced ZnO and TiO 2 nanoparticle (NP) colloids with molecular 2e – /2H + acceptors, to form new O-H, N-H, and C-H bonds. The reaction stoichi-ometries were monitored by NMR and optical spectroscopies. Faster 2e – /2H + transfer rates were observed for substrates forming O-H or N-H bonds, presumably due to initial hydrogen bonding at the oxide surface. Chemically reduced ZnO NPs stabilized by Na + or Ca 2+ also engage in 2e – /2H + transfer reactivity, showing that protons transferred in these processes are inherent to the oxide nanoparticles and do not exclusively stem from photoreduction. Furthermore, these results highlight the potential of ZnO and TiO 2 for multiple proton-coupled electron transfer (PCET) reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Pseudomonas aeruginosa Adhesion and Biofilm Formation on Poly(l-lysine)-Tethered Hydrogels: Synergistic Effect of Substrate Stiffness and Positive Charge Density

Infections associated with antibacterial-resistant Pseudomonas aeruginosa (P. aeruginosa) are the major cause of morbidity and mortality of patients, presenting one of the greatest therapeutic challenges for treatment of community-acquired and nosocomial infections. To develop antimicrobial hydrogel coatings to control the adhesion and subsequent biofilm formation of P. aeruginosa, we have used photo-cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels with varied cross-linking densities and covalently grafted poly(l-lysine) (PLL) at different weight compositions (ϕ PLL ). Both surface stiffness and positive charge density of the hydrogels were efficiently tuned over a broad range to investigate their effects on two main strains of P. aeruginosa, PA01 and PA14. We found that both number and viability of attached cells were positively correlated with the hydrogel stiffness, leading to thicker and larger coverage of cell colonies at 72 h postseeding on the stiffer substrates. The dependence of both PA01 and PA14 strains on ϕ PLL , however, was nonmonotonic. Positive charges from dissociated amine groups in the grafted PLL chains significantly promoted initial adhesion and proliferation of both strains at low ϕ PLL and developed into the thickest biofilms on the stiffest hydrogels grafted with ϕ PLL of 1–2%. Nevertheless, on the softest hydrogels grafted with PLL at high ϕ PLL of 7–10%, the bacteria no longer attached or survived. These results not only improved our fundamental understanding of bacteria-material interactions but also provided a series of PLL-grafted PEGDA hydrogels with controlled stiffness and positive charge density as ideal surface coating materials to prevent bacterial infections.

bacteria↗
DOE OSTI2026

Molecular Dynamics Investigation of Oil Wetting on Synthetic Polymer Substrates

Understanding the interaction of polymer surfaces with nonpolar, low surface tension liquids, or whether a substrate is oleophobic versus oleophilic, is critical for applications ranging from antifingerprint coatings to oil–water separation membranes and oil spill remediation. Despite its technological importance, the molecular mechanisms underpinning polymer–oil wetting are not well characterized. Here, we employ molecular dynamics simulations to investigate the behavior of n-hexadecane in contact with chemically distinct polymer surfaces, spanning eight constitutional unit chemistries as well as amorphous and crystalline morphologies. This permits a critical examination of both thermodynamic and dynamic descriptors of oleophobicity, including oil contact angle, dewetting free energy, interfacial diffusivity, and a proposed “ghost probe energy,” which does not require explicit simulation of oil–polymer interactions. We find that the oil contact angle does not reliably distinguish oleophobic behavior across polymer chemistries, whereas other metrics provide clearer and more consistent differentiation. Analysis of the results reveals that polymer–oil wetting behavior is primarily governed by interfacial van der Waals interactions and modulated by surface flexibility and morphology. Collectively, this work establishes a computational framework for characterizing oil wetting and provides additional insight into what molecular-level factors dictate trends in oleophobicity.

lipids↗
DOE OSTI2019

Hydrogen Uptake Kinetics of 1,4-Bis(phenylethynyl)benzene (DEB) Rubberized Coating on Silicone Foam Substrate

The hydrogen uptake kinetics of 1,4-bis(phenylethynyl)benzene, or DEB, mixed with palladium (Pd) on activated carbon in a rubber matrix coating on top of a porous silicone foam substrate are investigated. First, isothermal isobaric hydrogenation experiments were performed under different temperatures and H 2 pressures to extract the uptake kinetics. The H 2 uptake models based on the measured kinetic parameters were then employed to investigate/simulate the performance of the getter under dynamic application environments. The actual hydrogenation characteristics in this type of getter is multifaceted and involve actual H 2 concentration in the getter matrix, micrometer scale diffusion of atomic hydrogen away from Pd sites, precipitation of hydrogenated DEB crystals at the coating surfaces, and mobility of fresh DEB molecules. The kinetic analysis/modeling methodology described in this report can serve as a template for other gas-solid reactions as well. Aside from possessing a good hydrogen capacity and excellent performance, this type of rubberized getter also offers some unique advantages over traditional solid getter: flexible structure and protection of Pd catalyst from exposure to the environment.

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

Directly Linking Low-Angle Grain Boundary Misorientation to Device Functionality for GaAs Grown on Flexible Metal Substrates

A new growth method to make highly oriented GaAs thin films on flexible metal substrates has been developed, enabling roll-to-roll manufacturing of flexible semiconductor devices. The grains are oriented in the <001> direction with <1 degree misorientations between them, and they have a comparable mobility to single-crystalline GaAs at high doping concentrations. At the moment, the role of low-angle grain boundaries (LAGBs) on device performance is unknown. A series of electron backscatter diffraction (EBSD) and cathodoluminesence (CL) studies reveal that increased doping concentrations decrease the grain size and increase the LAGB misorientation. Cross-sectional scanning transmission electron microscopy (STEM) reveals the complex dislocation structures within LAGBs. Most importantly, a correlative EBSD/electron beam-induced current (EBIC) experiment reveals that LAGBs are carrier recombination centers and that the magnitude of recombination is dependent on the degree of misorientation. The presented results directly link increased LAGB misorientation to degraded device performance, and therefore, strategies to reduce LAGB misorientations and densities would improve highly oriented semiconductor devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Liquid Crystal Films as Active Substrates for Nanoparticle Control

Organizing nanoparticles in a controlled way allows us to monitor their optical properties. It is particularly interesting to organize them on top of liquid crystal films to take advantage, in a second step, of the easy actuation of liquid crystals with external parameters such as temperature, electric fields, and so forth. We show that despite their fluidity, nematic and smectic films allow the formation of well-ordered hexagonal domains of gold spherical nanoparticles (AuNPs) at their surface, but we also show that both nematic films and AuNP domains impact each other. Using optical microscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectrophotometry, we compare nematic, polymer-stabilized nematic, and smectic films with AuNP domains made of NPs of diameter 6 nm. On the liquid crystal films, depressions are revealed below the AuNP domains, whereas the AuNP domains appear well-organized but with a hexagonal period shortened with respect to AuNP monolayers formed on hard substrates. We interpret these features by the anchoring tilt imposed by the AuNP domains on the liquid crystal molecules. The smectic-A layers characteristic of the nematic surface transform into smecticC layers, which induce the formation of depression. Here, the energy penalty associated with the local smectic-A/smectic-C transition induces the shortening of the AuNP domain period in order to decrease the AuNP domain surface. The observed large depth of the polymer-stabilized nematic depressions below AuNP domains may be explained either by an increased size of the polymer-stabilized smectic layers close to the surface or by an increased number of polymer-stabilized smectic liquid crystal smectic layers close to the surface with respect to pure nematic films.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Illuminating the Role of Alcohol Substrate in Nickel Photoredox Catalysis via Ground State and Transient Absorption Spectroscopy

Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activity has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.

alcohol↗
DOE OSTI2021

Substrate Partitioning into Protein Macromolecular Frameworks for Enhanced Catalytic Turnover

Spatial partitioning of chemical processes is an important attribute of many biological systems, the effect of which is reflected in the high efficiency of enzymes found within otherwise chaotic cellular environments. Barriers, often provided through the formation of compartments or phase segregation, gate the access of macromolecules and small molecules within the cell and provide an added level of metabolic control. Taking inspiration from nature, we have designed virus-like particles (VLPs) as nanoreactor compartments that sequester enzyme catalysts and have used these as building blocks to construct 3D protein macromolecular framework (PMF) materials, which are structurally characterized using small-angle X-ray scattering (SAXS). Additionally, the highly charged PMFs form a separate phase in suspension, and by tuning the ionic strength, we show positively charged molecules preferentially partition into the PMF, while negatively charged molecules are excluded. This molecular partitioning was exploited to tune the catalytic activity of enzymes enclosed within the individual particles in the PMF, the results of which showed that positively charged substrates had turnover rates that were 8500× faster than their negatively charged counterparts. Moreover, the catalytic PMF led to cooperative behavior resulting in charge dependent trends opposite to those observed with individual P22 nanoreactor particles.

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

Insight into the Catalytic Mechanism of GH11 Xylanase: Computational Analysis of Substrate Distortion Based on a Neutron Structure

The reaction mechanism of biomass decomposition by xylanases remains the subject of debate. Here, to clarify the mechanism, we investigated the glycosylation step of GH11 xylanase, an enzyme that catalyzes the hydrolysis of lignocellulosic hemicellulose (xylan). Making use of a recent neutron crystal structure, which revealed the protonation states of relevant residues, we used ab initio quantum mechanics/molecular mechanics (QM/MM) calculations to determine the detailed reaction mechanism of the glycosylation step. In particular, our focus is on the controversial question of whether or not an oxocarbenium ion intermediate is formed on the reaction pathway. The calculations support the validity of a basic retaining mechanism within a double-displacement scheme. The estimated free energy barrier of this reaction is ~18 kcal/mol with QM/MM-CCSD(T)/6-31(+)G**//MP2/6-31+G**/AMBER calculations, and the rate-determining step of the glycosylation is scission of the glycosidic bond after proton transfer from the acidic Glu177. The estimated lifetime of the oxocarbenium ion intermediate (on the order of tens of ps) and the secondary kinetic isotope effect suggest that there is no accumulation of this intermediate on the reaction path, although the intermediate can be transiently formed. In the enzyme–substrate (ES) complex, the carbohydrate structure of the xylose residue at the -1 subsite has a rather distorted (skewed) geometry, and this xylose unit at the active site has an apparent half-chair conformation when the oxocarbenium ion intermediate is formed. The major catalytic role of the protein environment is to orient residues that take part in the initial proton transfer. Because of a fine alignment of catalytic residues, the enzyme can accelerate the glycosylation reaction without paying a reorganization energy penalty.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗