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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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Abstract not provided
The new uranyl aqua sulfate compound [({CH_3}{sub 3}N{sub 2}C{sub 3}H{sub 3}{CH_2COOH})(H{sub 3}O)] [(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]·1.5H{sub 2}O was synthesized and the crystal structure determined. The two-dimensional uranyl-aqua sulfate compound exhibits a previously reported anionic structural unit topology, but features an interstitial complex incorporating hydronium in the form of a disorder Zundel cation and the cation moiety from the ionic liquid 1-carboxymethyl 3-methylimidazolium bistriflimide [HBetMIm][Tf{sub 2}N], which forms hydrogen bonding dimer pairs. An analysis of similar uranyl sulfate complexes from the literature is conducted to explore the relative importance and role of structure directing factors in alkylammonium charge-balanced two-dimensional uranyl sulfates. A correlation is observed between structural unit charge density and interlayer spacing, with a concomitant direction of structural and orientational geometric isomerism of the anionic structural unit. We discuss the role of synthetic conditions and molecular cation properties in directing structural unit formation through charge density matching and hydrogen bonding.
Abstract not provided.
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Oxidation of hydrogen (H₂) to protons and electrons for energy production in fuel cells is catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton delivery and removal is critical in hydrogenase enzymes in nature that catalyze H₂ oxidation using earth-abundant metals (iron and nickel). Here we report a synthetic iron complex, (Cp C 5 F 4 N )Fe(P Et N (CH 2 ) 3 NMe 2 PEt)(Cl), that serves as a precatalyst for the oxidation of H₂, with turnover frequencies of 290 s⁻¹ in fluorobenzene, under 1 atm of H₂ using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the exogenous base. The cooperative effect of the primary, secondary and outer coordination spheres for moving protons in this remarkably fast catalyst emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.
Using a classical model that treats translational and spin degrees of freedom on an equal footing, we study phonon-magnon interactions in BCC iron with combined molecular and spin dynamics methods. The atomic interactions are modeled via an empirical many-body potential while spin dependent interactions are established through a Hamiltonian of the Heisenberg form with a distance dependent magnetic exchange interaction obtained from first principles electronic structure calculations. The temporal evolution of translational and spin degrees of freedom was determined by numerically solving the coupled equations of motion, using an algorithm based on the second order Suzuki-Trotter decomposition of the exponential operators. By calculating Fourier transforms of space- and time-displaced correlation functions, we demonstrate that the the presence of lattice vibrations leads to noticeable softening and damping of spin wave modes. As a result of the interplay between lattice and spin subsystems, we also observe additional longitudinal spin wave excitations, with frequencies which coincide with that of the longitudinal lattice vibrations.
Avena sativa oat is a cereal widely used as human food and livestock feed. However, the low metabolized energy and the rapid rumen degradations of protein and starch have limited the use of A. sativa oat grains. To overcome this disadvantage, new A. sativa oat varieties have been developed. Additionally, heat-related processing has been performed to decrease the degradation rate and improve the absorption of amino acids in the small intestine. The nutritive value is reflected by both chemical composition and inherent molecular structure conformation. However, the traditional wet chemical analysis is not able to detect the inherent molecular structures within an intact tissue. The advanced synchrotron-radiation and globar-based molecular microspectroscopy have been developed recently and applied to study internal molecular structures and the processing induced structure changes in A. sativa oats and reveal how molecular structure changes in relation to nutrient availability. This review aimed to obtain the recent information regarding physiochemical properties, molecular structures, metabolic characteristics of protein, and the heat-induced changes in new A. sativa oat varieties. The use of the advanced vibrational molecular spectroscopy was emphasized, synchrotron- and globar-based (micro)spectroscopy, to reveal the inherent structure of A. sativa oats at cellular and molecular levels and to reveal the heat processing effect on the degradation characteristics and the protein molecular structure in A. sativa oats. The relationship between nutrient availability and protein molecular inherent structure was also presented. Information described in this review gives better insight in the physiochemical properties, molecular structure, and the heat-induced changes in A. sativa oat detected with advanced molecular spectroscopic techniques in combinination with conventional nutrition study techniques.
Molecular representation is a critical element in our understanding of the physical world and the foundation for modern molecular machine learning. Previous molecular machine learning models have used strings, fingerprints, global features and simple molecular graphs that are inherently information-sparse representations. However, as the complexity of prediction tasks increases, the molecular representation needs to encode higher fidelity information. This work introduces a new approach to infusing quantum-chemical-rich information into molecular graphs via stereoelectronic effects, enhancing expressivity and interpretability. Learning to predict the stereoelectronics-infused representation with a tailored double graph neural network workflow enables its application to any downstream molecular machine learning task without expensive quantum-chemical calculations. We show that the explicit addition of stereoelectronic information substantially improves the performance of message-passing two-dimensional machine learning models for molecular property prediction. We show that the learned representations trained on small molecules can accurately extrapolate to much larger molecular structures, yielding chemical insight into orbital interactions for previously intractable systems, such as entire proteins, opening new avenues of molecular design. Finally, we have developed a web application (simg.cheme.cmu.edu) where users can rapidly explore stereoelectronic information for their own molecular systems.
Based on the interest in, as well as exciting outlook for, nitride semiconductor based structures with regard to electronic, optoelectronic, and spintronic applications, it is compelling to investigate these systems using the powerful technique of spin-polarized scanning tunneling microscopy (STM), a technique capable of achieving magnetic resolution down to the atomic scale. However, the delicate surfaces of these materials are easily corrupted by in-air transfers, making it unfeasible to study them in stand-alone ultra-high vacuum STM facilities. Therefore, we have carried out the development of a hybrid system including a nitrogen plasma assisted molecular beam epitaxy/pulsed laser epitaxy facility for sample growth combined with a low-temperature, spin-polarized scanning tunneling microscope system. The custom-designed molecular beam epitaxy growth system supports up to eight sources, including up to seven effusion cells plus a radio frequency nitrogen plasma source, for epitaxially growing a variety of materials, such as nitride semiconductors, magnetic materials, and their hetero-structures, and also incorporating in situ reflection high energy electron diffraction. The growth system also enables integration of pulsed laser epitaxy. The STM unit has a modular design, consisting of an upper body and a lower body. The upper body contains the coarse approach mechanism and the scanner unit, while the lower body accepts molecular beam epitaxy grown samples using compression springs and sample skis. The design of the system employs two stages of vibration isolation as well as a layer of acoustic noise isolation in order to reduce noise during STM measurements. This isolation allows the system to effectively acquire STM data in a typical lab space, which during its construction had no special and highly costly elements included, (such as isolated slabs) which would lower the environmental noise. The design further enables tip exchange and tip coating without breaking vacuum, and convenient visual access to the sample and tip inside a superconducting magnet cryostat. A sample/tip handling system is optimized for both the molecular beam epitaxy growth system and the scanning tunneling microscope system. The sample/tip handing system enables in situ STM studies on epitaxially grown samples, and tip exchange in the superconducting magnet cryostat. The hybrid molecular beam epitaxy and low temperature scanning tunneling microscopy system is capable of growing semiconductor-based hetero-structures with controlled accuracy down to a single atomic-layer and imaging them down to atomic resolution.
We report an analysis of the interstellar {gamma}-ray emission from the Chamaeleon, R Coronae Australis (R CrA), and Cepheus and Polaris flare regions with the Fermi Large Area Telescope. They are among the nearest molecular cloud complexes, within {approx}300 pc from the solar system. The {gamma}-ray emission produced by interactions of cosmic rays (CRs) and interstellar gas in those molecular clouds is useful to study the CR densities and distributions of molecular gas close to the solar system. The obtained {gamma}-ray emissivities above 250 MeV are (5.9 {+-} 0.1{sub stat}{sup +0.9}{sub -1.0sys}) Multiplication-Sign 10{sup -27} photons s{sup -1} sr{sup -1} H-atom{sup -1}, (10.2 {+-} 0.4{sub stat}{sup +1.2}{sub -1.7sys}) Multiplication-Sign 10{sup -27} photons s{sup -1} sr{sup -1} H-atom{sup -1}, and (9.1 {+-} 0.3{sub stat}{sup +1.5}{sub -0.6sys}) Multiplication-Sign 10{sup -27} photons s{sup -1} sr{sup -1} H-atom{sup -1} for the Chamaeleon, R CrA, and Cepheus and Polaris flare regions, respectively. Whereas the energy dependences of the emissivities agree well with that predicted from direct CR observations at the Earth, the measured emissivities from 250 MeV to 10 GeV indicate a variation of the CR density by {approx}20% in the neighborhood of the solar system, even if we consider systematic uncertainties. The molecular mass calibrating ratio, X{sub CO} = N(H{sub 2})/W{sub CO}, is found to be (0.96 {+-} 0.06{sub stat}{sup +0.15}{sub -0.12sys}) Multiplication-Sign 10{sup 20} H{sub 2}-molecule cm{sup -2} (K km s{sup -1}){sup -1}, (0.99 {+-} 0.08{sub stat}{sup +0.18}{sub -0.10sys}) Multiplication-Sign 10{sup 20} H{sub 2}-molecule cm{sup -2} (K km s{sup -1}){sup -1}, and (0.63 {+-} 0.02{sub stat}{sup +0.09}{sub -0.07sys}) Multiplication-Sign 10{sup 20} H{sub 2}-molecule cm{sup -2} (K km s{sup -1}){sup -1} for the Chamaeleon, R CrA, and Cepheus and Polaris flare regions, respectively, suggesting a variation of X{sub CO} in the vicinity of the solar system. From the obtained values of X{sub CO}, the masses of molecular gas traced by W{sub CO} in the Chamaeleon, R CrA, and Cepheus and Polaris flare regions are estimated to be {approx}5 Multiplication-Sign 10{sup 3} M{sub Sun }, {approx}10{sup 3} M{sub Sun }, and {approx}3.3 Multiplication-Sign 10{sup 4} M{sub Sun }, respectively. A comparable amount of gas not traced well by standard H I and CO surveys is found in the regions investigated.
We report new ALMA observations of the CO(3-2) line emission from the $2.1\pm0.3\times10^{10}\rm\thinspace M_{\odot}$ molecular gas reservoir in the central galaxy of the Phoenix cluster. The cold molecular gas is fuelling a vigorous starburst at a rate of $500-800\rm\thinspace M_{\odot}\rm\; yr^{-1}$ and powerful black hole activity in the form of both intense quasar radiation and radio jets. The radio jets have inflated huge bubbles filled with relativistic plasma into the hot, X-ray atmospheres surrounding the host galaxy. The ALMA observations show that extended filaments of molecular gas, each $10-20\rm\; kpc$ long with a mass of several billion solar masses, are located along the peripheries of the radio bubbles. The smooth velocity gradients and narrow line widths along each filament reveal massive, ordered molecular gas flows around each bubble, which are inconsistent with gravitational free-fall. The molecular clouds have been lifted directly by the radio bubbles, or formed via thermal instabilities induced in low entropy gas lifted in the updraft of the bubbles. These new data provide compelling evidence for close coupling between the radio bubbles and the cold gas, which is essential to explain the self-regulation of feedback. As a result, the very feedback mechanism that heats hot atmospheres and suppresses star formation may also paradoxically stimulate production of the cold gas required to sustain feedback in massive galaxies.
One critical aspect of mass spectrometry imaging (MSI) is the need to con?dently identify detected analytes. While orthogonal tandem MS (e.g., LC-MS2) experiments from sample extracts can assist in annotating ions, the spatial information about these molecules is lost. Accordingly, this could cause mislead conclusions, especially in cases where isobaric species exhibit di?erent distributions within a sample. In this Technical Note, we employed a multimodal imaging approach, using matrix assisted laser desorption/ionization (MALDI)-MSI and liquid extraction surface analysis (LESA)-MS2I, to con?dently annotate and One critical aspect of mass spectrometry imaging (MSI) is the need to con?dently identify detected analytes. While orthogonal tandem MS (e.g., LC-MS2) experiments from sample extracts can assist in annotating ions, the spatial information about these molecules is lost. Accordingly, this could cause mislead conclusions, especially in cases where isobaric species exhibit di?erent distributions within a sample. In this Technical Note, we employed a multimodal imaging approach, using matrix assisted laser desorption/ionization (MALDI)-MSI and liquid extraction surface analysis (LESA)-MS2I, to con?dently annotate and localize a broad range of metabolites involved in a tripartite symbiosis system of moss, cyanobacteria, and fungus. We found that the combination of these two imaging modalities generated very congruent ion images, providing the link between highly accurate structural information onfered by LESA and high spatial resolution attainable by MALDI. These results demonstrate how this combined methodology could be very useful in di?erentiating metabolite routes in complex systems.
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Here a previously presented Monte Carlo method for estimating local plasma conditions in 2D based on intensity ratios of deuterium Balmer D α , D γ and D ε lines was amended to consider also the D α and D γ emission contributions arising from molecular processes. The obtained estimates were used to infer the molecular divertor density with the help of the molecular databases of EIRENE. The method was benchmarked against EDGE2D-EIRENE simulations and observed to reproduce the molecularly induced emission fractions and the molecular divertor densities primarily within 25% of the references. Experimental analysis of a JET L-mode density scan suggested molecularly induced D α and D γ contributions of up to 60–70% and 20%, respectively, during the process of detachment. The independent estimates of the molecular divertor density inferred from the obtained molecularly induced D α and D γ intensities agree within uncertainties with each other. Both estimates show the molecular density increasing up to approximately 1.0–2.0 x 10 20 m -3 at the outer strike point in deep detachment with its ratio to the local electron density agreeing with EDGE2D-EIRENE predictions within the scatter of the experimental data.