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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 199 records · Page 11

Robust and tunable oxide nanoscrolls for solar-driven H 2 generation and storage

Hydrogen gas is a promising alternative to fossil fuels due to its high energy output and environmentally safe byproducts. Various morphologies of photocatalytic materials have been explored for high-efficiency H 2 production, for instance, quasi-1D nanoscroll structures that provide a larger surface-to-volume ratio. Recently, we predicted layer-by-layer formation of stable oxide nanoscrolls directly from dichalcogenide precursors, eliminating the need for costly formation of two-dimensional oxides for a roll-up synthesis of nanoscrolls. Here, in this study, we evaluate the suitability of those oxide nanoscroll materials—MoO 3 , WO 3 , PdO 2 , HfO 2 , and GeO 2 —for solar-driven photocatalytic H 2 production and storage. Using excited state theory coupled with Bethe–Salpeter equation simulations, we discern their electronic and optical properties as a function of interlayer scroll spacing and find them to be highly conducive for solar-driven photocatalysis. Additionally, using ab initio molecular dynamics simulations, we show that they are also suitable for H 2 storage as the nanoscrolls exhibit an effective trapping of hydrogen, even in the presence of defects and vacancies in the oxides. This work thus demonstrates the discovery of robust and tunable oxide nanoscrolls as materials for advancing solar-driven hydrogen technologies.

Chemical compounds↗

Structure and assembly of the diiron cofactor in the heme-oxygenase–like domain of the N-nitrosourea–producing enzyme SznF

In biosynthesis of the pancreatic cancer drug streptozotocin, the tridomain nonheme-iron oxygenase SznF hydroxylates N δ and N ω ' of N ω -methyl- L -arginine before oxidatively rearranging the triply modified guanidine to the N-methyl-N-nitrosourea pharmacophore. A previously published structure visualized the monoiron cofactor in the enzyme’s C-terminal cupin domain, which promotes the final rearrangement, but exhibited disorder and minimal metal occupancy in the site of the proposed diiron cofactor in the N-hydroxylating heme-oxygenase–like (HO-like) central domain. We leveraged our recent observation that the N-oxygenating µ-peroxodiiron(III/III) intermediate can form in the HO-like domain after the apo protein self-assembles its diiron(II/II) cofactor to solve structures of SznF with both of its iron cofactors bound. These structures of a biochemically validated member of the emerging heme-oxygenase–like diiron oxidase and oxygenase (HDO) superfamily with intact diiron cofactor reveal both the large-scale conformational change required to assemble the O 2 -reactive Fe 2 (II/II) complex and the structural basis for cofactor instability—a trait shared by the other validated HDOs. During cofactor (dis)assembly, a ligand-harboring core helix dynamically (un)folds. The diiron cofactor also coordinates an unanticipated Glu ligand contributed by an auxiliary helix implicated in substrate binding by docking and molecular dynamics simulations. The additional carboxylate ligand is conserved in another N-oxygenating HDO but not in two HDOs that cleave carbon–hydrogen and carbon–carbon bonds to install olefins. Among ~9,600 sequences identified bioinformatically as members of the emerging HDO superfamily, ~25% conserve this additional carboxylate residue and are thus tentatively assigned as N-oxygenases.

59 BASIC BIOLOGICAL SCIENCES↗

Electronic structures of a diagonally striped lattice: Multiple ( N - 1 ) -fold degenerate flat bands

We investigate the electronic structure of an interesting two-dimensional (2D) diagonally striped lattice (DSL). It consists of arrays of N different types of “atoms” or “molecules” with a fixed sequence in both horizontal and vertical directions. Using a tight-binding model, we show that the DSL (N>2) has the symmetry group Amm2 and Pmm2, and exhibits an oscillatory metallic and insulating phases for the odd- and even- N number, respectively. Some conventional 2D lattices, such as the Lieb lattice, can be related to the derivative DSL via vacancy formation by removing one type of atom in every other (N-1) row of the original DSL. Interestingly, there are multiple (N-1)-fold degenerate flat bands in one group of the derivative DSLs, which affords a unique platform for studying many-body physics. In addition to atomic and molecular lattices, we suggest other artificial DSLs, such as photonic and phononic, to be also constructed with possibly interesting properties.

36 MATERIALS SCIENCE↗

Argon equation of state data to 1 TPa: Shock compression experiments and simulations

Argon is the most abundant noble gas on Earth and its noble, atomic fluid nature makes it an excellent candidate for comparison of experiment and theory at extreme conditions. For this study, we performed a combined computational and experimental study on shock compressed cryogenic liquid argon. Using Sandia's Z machine, we shock compressed liquid argon to 600 GPa and reshock states up to 950 GPa. Laser shock experiments at the Omega Laser facility extend the principal Hugoniot to 1000 GPa and provided temperature data along the principal Hugoniot. The plate impact experiments and laser shock experiments used well-characterized impedance matching standards and demonstrate consistent results between the two platforms over a common range. Density functional theory based molecular dynamics simulations provided additional data on the Hugoniot to 600 GPa. The combined experimental data and simulation results provide constraints on the development of new equation of state models at extreme conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantifying molecular deformation in polymer melts by a generalized Zimm plot approach

The Zimm plot has been widely used to characterize the molecular dimensions of polymers from small-angle scattering experiments, where the reciprocal intensity is analyzed as a function of the square of the magnitude of the scattering wavevector Q. Here, this work explores the benefits of analyzing the reciprocal scattering intensity from deformed polymers, extending the original Zimm plot to anisotropic materials. In the small-angle limit, a tensorial extension of the Guinier law is found for the gyration tensor and the reciprocal single-chain structure factor. In the high-Q limit, application of the spherical harmonic expansion technique to the reciprocal structure factor permits direct model-independent analysis of spatially dependent molecular deformation of polymers. Additionally, the contributions from high-order spherical harmonics become insignificant in the reciprocal-intensity representation. The proposed generalized Zimm plot approach is demonstrated computationally with the affine deformation model and the Rouse model, and experimentally with small-angle neutron scattering measurements of deformed polystyrene melts.

36 MATERIALS SCIENCE↗

The conserved AAA ATPase PCH-2 distributes its regulation of meiotic prophase events through multiple meiotic HORMADs in C. elegans

During meiotic prophase, the essential events of homolog pairing, synapsis, and recombination are coordinated with meiotic progression to promote fidelity and prevent aneuploidy. The conserved AAA+ ATPase PCH-2 coordinates these events to guarantee crossover assurance and accurate chromosome segregation. How PCH-2 accomplishes this coordination is poorly understood. Here, we provide evidence that PCH-2 decelerates pairing, synapsis and recombination in C. elegans by remodeling meiotic HORMADs. We propose that PCH-2 converts the closed versions of these proteins, which drive these meiotic prophase events, to unbuckled conformations, destabilizing interhomolog interactions and delaying meiotic progression. Further, we find that PCH-2 distributes this regulation among three essential meiotic HORMADs in C. elegans: PCH-2 acts through HTP-3 to regulate pairing and synapsis, HIM-3 to promote crossover assurance, and HTP-1 to control meiotic progression. In addition to identifying a molecular mechanism for how PCH-2 regulates interhomolog interactions, our results provide a possible explanation for the expansion of the meiotic HORMAD family as a conserved evolutionary feature of meiosis. Taken together, our work demonstrates that PCH-2’s remodeling of meiotic HORMADs has functional consequences for the rate and fidelity of homolog pairing, synapsis, recombination and meiotic progression, ensuring accurate meiotic chromosome segregation.

59 BASIC BIOLOGICAL SCIENCES↗

Mimicking Natural Photosynthesis: Designing Ultrafast Photosensitized Electron Transfer into Multiheme Cytochrome Protein Nanowires

Efficient nanomaterials for artificial photosynthesis require fast and robust unidirectional electron transfer (ET) from photosensitizers through charge-separation and accumulation units to redox-active catalytic sites. We explored the ultrafast time-scale limits of photo-induced charge transfer between a Ru(II)tris(bipyridine) derivative photosensitizer and PpcA, a 3-heme c-type cytochrome serving as a nanoscale biological wire. Four covalent attachment sites (K28C, K29C, K52C, and G53C) were engineered in PpcA enabling site-specific covalent labeling with expected donor-acceptor (DA) distances of 4–8 Å. X-ray scattering results demonstrated that mutations and chemical labeling did not disrupt the structure of the proteins. Time-resolved spectroscopy revealed three orders of magnitude difference in charge transfer rates for the systems with otherwise similar DA distances and the same number of covalent bonds separating donors and acceptors. All-atom molecular dynamics simulations provided additional insight into the structure-function requirements for ultrafast charge transfer and the requirement of van der Waals contact between aromatic atoms of photosensitizers and hemes in order to observe sub-nanosecond ET. This work demonstrates opportunities to utilize multi-heme c-cytochromes as frameworks for designing ultrafast light-driven ET into charge-accumulating biohybrid model systems, and ultimately for mimicking the photosynthetic paradigm of efficiently coupling ultrafast, light-driven electron transfer chemistry to multi-step catalysis within small, experimentally versatile photosynthetic biohybrid assemblies.

36 MATERIALS SCIENCE↗

Characterization of Kariya ( Hildegardia barteri (Mast.) Kosterm) Seed Oil Fatty Acid Methyl Ester Prepared from Basic Catalytic Transesterification

The rising global energy demand, alongside concerns regarding environmental deterioration due to the use of fossil fuels, has spurred extensive investigation into renewable energy alternatives. Biomass-derived biodiesel, especially from lesser-known oil sources, emerges as a promising option. This research focuses on analyzing the fatty acid methyl esters (FAMEs) derived from Kariya (Hildegardia barteri (Mast.) Kosterm) seed oil through basic catalytic transesterification using gas chromatography–flame ionization detector (GC–FID) analysis, assessing its potential as a biodiesel feedstock. Oil extraction from Kariya seeds was carried out using three solvents (n-hexane, ethanol, and a 1:1 blend of hexane and ethanol), followed by transesterification with methanol. Gas chromatography–mass spectrometry (GC–MS) and GC–FID analyses were utilized to identify and quantify FAMEs in the resulting biodiesel. The results revealed various FAMEs, including methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, and methyl linolenate. Significant differences in FAME composition were observed among the samples, with hexane–ethanol Kariya oil biodiesel (HE-KOB) showing the highest FAME content (76.1%). This combination of solvents exhibited synergistic effects on the composition of HE-KOB, suggesting potential optimization strategies for biodiesel production. Fourier transform infrared spectroscopy (FTIR) provided additional insights into the molecular composition of the biodiesel samples, confirming their biodiesel nature through the identified functional groups such as methyl, methylene, hydrocarbon, ester, aldehyde, and alkene. Thermogravimetric analysis (TGA) for thermal decomposition also gave an insight into FAME composition and its contribution to the degree of conversion of biodiesel to energy. These findings highlight the feasibility of utilizing Kariya seed oil as a biodiesel feedstock, emphasizing the importance of solvent selection and transesterification conditions in optimizing FAME yield and composition. This research contributes to the exploration of underutilized oil sources for sustainable biodiesel production, aligning with the global shift towards cleaner and renewable energy sources.

09 BIOMASS FUELS↗

Polyfunctional epoxies. I - Rubber-toughened brominated and nonbrominated formulations for graphite composites. II - Nonrubber versus rubber-toughened brominated formulations for graphite composites

A new trifunctional epoxy resin, Tris-(hydroxyphenyl) methane triglycidyl ether, is compared to a state-of-the-art tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM), in graphite composites. Rubber-toughened brominated formulations of the epoxy resin are compared to nonbrominated ones in terms of their mechanical performance, environmental stability, thermochemical behavior, and flame retardancy. It is shown that the new resin performs almost the same way as the TGDDM does, but has improved glass transition temperature and environmental properties. Brominated polymeric additives (BPA) of different molecular weights are tested as a Br source to flame retardant graphite epoxy composites. The optimal molecular weight of the BPA and its polymeric backbone length are derived and compared with a 10 percent rubber-toughened formulation of the epoxy resin. Results indicate that when the Br content in the graphite composite is increased without the use of rubber, the mechanical properties improved. The use of BPAs as tougheners for graphite composites is also considered.

Nir, Z.↗

Submillimetre molecular line observations of M17: The interaction of an ionisation front and molecular clouds

An area of about 9 by 10 arc minutes in the M17 molecular cloud has been mapped in the J=3-2 transition of CO. The strongest CO emission is observed to come from the two bars to the north and southwest, which lie just outside the area of ionized gas seen in the radio continuum studies. We are viewing the boundary between the ionized and molecular gas almost edge on. The most intense CO emission is from the area around the dense molecular cloud core M17SW in the southwest bar. To the east of M17SW there are signs of recent or continuing star formation including H2O masers and an ultra-compact HII region. The CO J=3-2 spectra observed are complex with considerable variation in line shapes occuring over distances of less than one arc minute. We interpret the velocity structure of this region as arising from an ensemble of molecular cloud fragments in addition to extended emission. We have identified several cloud components at different velocities within both the northern and southwest bars of CO emission. A simple kinematic model of the cloud components in the southwest bar in which they are considered to be clumps of post-shock gas lying close to the edge of the expanding HII region, with the shock being driven by Kleinmann's star, gives a velocity of approx. 10.8 km s(-1) for the expansion velocity of the HII region, which is currently at a distance of approx. 2.4 pc from Kleinmann's star. The resulting shock is thought to be preceding the ionisation front and appears to have led to the fragmentation of the original cloud.

Rainey, R.↗

Interstellar polycyclic aromatic hydrocarbons and carbon in interplanetary dust particles and meteorites

Raman spectra of interplanetary dust particles (IDPs) and meteorites containing material similar to polycyclic aromatic hydrocarbons (PAHs) show features that are similar in position and relative strength to interstellar IR emission features attributable to vibrational transitions in free molecular-sized PAHs. In addition, these spectra sometimes show red photoluminescence that has elsewhere been attributed to PAHs, and a part of the carbonaceous phase in IDPs and meteorites contain a degree of deuterium enrichment anticipated in small, free PAHs that are exposed to ISM UV radiation. These observations suggest that some of the IDPs' carbonaceous material may have been produced in circumstellar dust shells, and only slightly modified in interstellar space.

Allamandola, L. J.↗

Ballistic electron emission microscopy and spectroscopy of Au/GaAs interfaces

This paper presents the first Schottky barrier results for the Au/GaAs(100) interface prepared completely in situ on GaAs grown by molecular-beam epitaxy. The resulting interface displays unexpected properties which can be interpreted in terms of enhanced electrode interdiffusion. In addition, the capability of molecular-beam epitaxy for in situ processing enables the stabilization of this interface against diffusion and allows the formation of a Au/GaAs system with nearly ideal properties. Newly developed ballistic electron spectroscopy and imaging techniques demonstrate that the heterogeneity present at the interface of Au/GaAs(100) fabricated on chemically treated GaAs substrates is removed.

Kaiser, W. J.↗

Spherical Perfluoropolyethers

Four fluorocarbon compounds of generic class C(CF2OR)4 {where R = CF3, C(CF3)3, CF2CF3, or CF2CF2CF3} synthesized by direct fluorination of corresponding hydrocarbons. Molecules of these compounds approximately spherical and act as "molecular ball bearings." In addition to potential utility as lubricants, compounds expected thermally stable and useful as heat-transfer fluids or even vapor-phase-soldering fluids.

Lagow, Richard J.↗

HALOE Science Investigation

This cooperative agreement has investigated a number of spectroscopic problems of interest to the Halogen Occultation Experiment (HALOE). The types of studies performed are in two parts, namely, those that involve the testing and characterization of correlation spectrometers and those that provide basic molecular spectroscopic information. In addition, some solar studies were performed with the calibration data returned by HALOE from orbit. In order to accomplish this a software package was written as part of this cooperative agreement. The HALOE spectroscopic instrument package was used in various tests of the HALOE flight instrument. These included the spectral response test, the early stages of the gas response test and various spectral response tests of the detectors and optical elements of the instruments. Considerable effort was also expended upon the proper laboratory setup for many of the prelaunch tests of the HALOE flight instrument, including the spectral response test and the gas response test. These tests provided the calibration and the assurance that the calibration was performed correctly.

Benner, D. Chris↗

SNC Meteorites, Organic Matter and a New Look at Viking

Recently, evidence has begun to grow supporting the possibility that the Viking GC-MS would not have detected certain carboxylate salts that could have been present as metastable oxidation products of high molecular weight organic species. Additionally, despite the instrument's high sensitivity, the possibility had remained that very low levels of organic matter, below the instrument's detection limit, could have been present. In fact, a recent study indicates that the degradation products of several million microorganisms per gram of soil on Mars would not have been detected by the Viking GC-MS. Since the strength of the GC-MS findings was considered enough to dismiss the biology packet, particularly the LR results, any subsequent evidence suggesting that organic molecules may in fact be present on the Martian surface necessitates a re-evaluation of the Viking LR data. In addition to an advanced mass spectrometer to look for isotopic signatures of biogenic processes, future lander missions will include the ability to detect methane produced by methanogenic bacteria, as well as techniques based on biotechnology. Meanwhile, the identification of Mars samples already present on Earth in the form of the SNC meteorites has provided us with the ability to study samples of the Martian upper crust a decade or more in advance of any planned sample return missions. While contamination issues are of serious concern, the presence of indigenous organic matter in the form of polycyclic aromatic hydrocarbons has been detected in the Martian meteorites ALH84001 and Nakhla, while there is circumstantial evidence for carbonaceous material in Chassigny. The radiochronological ages of these meteorites are 4.5 Ga, 1.3 Ga, and 165 Ma respectively representing a span of time in Earth history from the earliest single-celled organisms to the present day. Given this perspective on organic material, a biological interpretation to the Viking LR results can no longer be ruled out. In the LR experiment, a solution containing C-14 labeled organic compounds was injected into soil samples. The detection of radioactivity in the overhead space would indicate that one or more of the substrates had been chemically converted into a carbon-containing gas. To serve as a control, some samples were heated enough to destroy most known terrestrial microbes so that an indication for life would be a positive response from unheated samples and a negative response from heated samples. On Mars, the LR results had met minimum criteria for a biological interpretation but due to the GC-MS results, the LR responses were later attributed to putative soil inorganic oxidants. Since the time of Viking, studies have been carried out with the objective of determining an oxidant or combination of oxidants that might exist on Mars and have produced the observed kinetics of the LR response. To date, no such agent has been found that produces all aspects of the LR results on Mars. While the above considerations in no way imply the existence of life forms at the two Viking landing sites, inorganic and biological explanations for the Viking LR data should now be considered equally plausible until more complete studies of the Martian surface are carried out. Therefore, in light of the SNC meteorites data and their implications for the possibility of organic matter near or on the Martian surface the Viking biology experiments should thus be seen, not as failures for their inability to provide unambiguous evidence for or against Martian life, but as a foundation for the development of future life-detection instruments. Additional information is contained in the original extended abstract.

Warmflash, David M.↗

Modeling the effects of hydrogen and dose rate sensitivity in CMOS and bipolar technologies

Low dose rate (LDR) and high dose rate (HDR) experiments on field-oxide-field-effect-transistors (FOXFETs) and gated lateral pnp (GLPNP) bipolar transistors indicate that there is a dose rate enhancement factor (EF) associated with radiation-induced degradation. This EF is also affect by the presence of hydrogen in the oxide. In this work, we developed a one dimensional (1-D) numerical calculations code to investigate the key mechanisms that describe the dose rate sensitivity and the effect of hydrogen on dose rate effects. We used a finite-difference methodology for the numerical calculations that allow for computing solutions for the densities of the mobile species as well as for the electrostatic potential at nodes contained within a mesh superimposed on the solution domain. Results from calculations of damage EF indicate that oxide thickness, distribution of hole traps and hole capture cross-section affect dose rate sensitivity. In addition, calculations show that molecular hydrogen cracking at positively charged defects may be a key reaction relating hydrogen and dose rate response. Comparison to experimental data on bipolar and CMOS devices results in good agreement with the dose rate calculations of interface trap buildup

Barnaby, Hugh↗

Analysis of Nonlinear Shrinkage for the Bound Metal Deposition Manufacturing using Multi-scale Approach

We consider problem of nonlinear shrinkage of the metal part during bound metal deposition manufacturing on the ground and in zero-G. To analyze this problem we developed multi-scale physics-based approach that spans atomistic dynamics at the scale of nanoseconds and the full part shrinkage at the time scale of hours. Using this approach we estimated the key parameters of the problem including grain boundary width, coefficient of surface diffusion, initial redistribution of particles during debinding stage, micro-structure evolution from round particles to densely packed grains and corresponding change of the total and chemical free energy, and sintering stress. The introduced method was used to predict shrinkage at the level of two particles, filament cross-section, sub-model, and the whole green, brown, and metal parts. To further improve accuracy and reliability of the shrinkage predictions we propose concept of intelligent additive manufacturing of metal powders in space that combines the strengths of both physics-based and data-driven methods of analysis of AM.

bound metal deposition↗

Transforming any Facility for Meeting Strict Cleanliness Requirements

Over the life of the James Webb Space Telescope (JWST), Integration & Test (I&T) has taken place in areas that needed considerable work to make the facility itself and/or the protocols used while working in the rooms suitable to meet JWST percent area coverage (PAC) and molecular accumulation requirements. In addition to normal particulate matter, JWST had a uniquely significant challenge: fibers! Fibers not only cause much higher PAC levels, but they also risk damaging the angstrom sized Near Infrared Spectrometer (NIRSpec) microshutter array (MSA), which is critical to NIRSpec instrument performance. The primary emphasis of this paper is to address particulate and fiber contamination. The success of the JWST mission required effective cleanrooms, protocols, and mitigations in non-cleanroom areas that were pressed into service to house contamination-sensitive optics and scientific instruments. Some presented profound challenges. These included: NASA’s 60-year-old Johnson Space Center (JSC) Chamber A, which had never been used for anything contamination-sensitive, and the European tropical launch facilities, which were designed to meet International Standard Organization (ISO) Class 8 processing for communication satellites. The final challenge for JWST, as if to stare us in the face and say, “I dare you to try and make me clean enough,” was preparing the 4 areas in the Centre Spatial Guyanais (CSG) Final Assembly Building (BAF) located in French Guiana, a building in which one entire side opens for Ariane 5 rocket ingress and egress. This paper will describe our initial evaluation processes and the actual work undertaken to transform even the most challenging areas into first class cleanrooms that met JWST particulate and fiber requirements.

James Webb Space Telescope↗