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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Pendant Group Modifications Provide Graft Copolymer Silicones with Exceptionally Broad Thermomechanical Properties

Graft copolymers offer a versatile platform for the design of self-assembling materials; however, simple strategies for precisely and independently controlling the thermomechanical and morphological properties of graft copolymers remain elusive. Here, using a library of 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, we discover a versatile backbone-pendant sequence-control strategy that addresses this challenge. Small structural variations of pendant groups, e.g., cyclohexyl versus n-hexyl, of small-molecule comonomers have dramatic impacts on order-to-disorder transitions, glass transitions, mechanical properties, and morphologies of statistical and block silicone-based graft copolymers, providing an exceptionally broad palette of designable materials properties. For example, statistical graft copolymers with high PDMS volume fractions yielded unbridged body-centered cubic morphologies that behaved as soft plastic crystals. By contrast, lamellae-forming graft copolymers provided robust, yet reprocessable silicone thermoplastics (TPs) with transition temperatures spanning over 160 °C and elastic moduli as high as 150 MPa despite being both unentangled and un-cross-linked. Altogether, this study reveals a new pendant-group-mediated self-assembly strategy that simplifies graft copolymer synthesis and enables access to a diverse family of silicone-based materials, setting the stage for the broader development of self-assembling materials with tailored performance specifications.

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

Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes

High-valent nonheme Fe IV –oxido species are key intermediates in biological oxidation, and their properties are proposed to be influenced by the unique microenvironments present in protein active sites. Microenvironments are regulated by noncovalent interactions, such as hydrogen bonds (H-bonds) and electrostatic interactions; however, there is little quantitative information about how these interactions affect crucial properties of high valent metal–oxido complexes. To address this knowledge gap, we introduced a series of Fe IV –oxido complexes that have the same S = 2 spin ground state as those found in nature and then systematically probed the effects of noncovalent interactions on their electronic, structural, and vibrational properties. The key design feature that provides access to these complexes is the new tripodal ligand [poat] 3– , which contains phosphinic amido groups. An important structural aspect of [Fe IV poat(O)] - is the inclusion of an auxiliary site capable of binding a Lewis acid (LA II ); we used this unique feature to further modulate the electrostatic environment around the Fe–oxido unit. Experimentally, studies confirmed that H-bonds and LA II s can interact directly with the oxido ligand in Fe IV –oxido complexes, which weakens the Fe=O bond and has an impact on the electronic structure. Additionally, we found that relatively large vibrational changes in the Fe–oxido unit correlate with small structural changes that could be difficult to measure, especially within a protein active site. Our work demonstrates the important role of noncovalent interactions on the properties of metal complexes, and that these interactions need to be considered when developing effective oxidants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

High Strength and Deformation Mechanisms of A l0.3 CoCrFeNi High-Entropy Alloy Thin Films Fabricated by Magnetron Sputtering

Recently, high-entropy alloy thin films (HEATFs) with nanocrystalline structures and high hardness were developed by magnetron sputtering technique and have exciting potential to make small structure devices and precision instruments with sizes ranging from nanometers to micrometers. However, the strength and deformation mechanisms are still unclear. In this work, nanocrystalline Al0.3CoCrFeNi HEATFs with a thickness of ~4 μm were prepared. The microstructures of the thin films were comprehensively characterized, and the mechanical properties were systematically studied. It was found that the thin film was smooth, with a roughness of less than 5 nm. The chemical composition of the high entropy alloy thin film was homogeneous with a main single face-centered cubic (FCC) structure. Furthermore, it was observed that the hardness and the yield strength of the high-entropy alloy thin film was about three times that of the bulk samples, and the plastic deformation was inhomogeneous. Our results could provide an in-depth understanding of the mechanics and deformation mechanism for future design of nanocrystalline HEATFs with desired properties.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

Complexes with weakly coordinating ligands are often formed in chemical reactions and can play key roles in determining the reactivity, particularly in catalytic reactions. Using time-resolved X-ray absorption fine structure (XAFS) spectroscopy in combination with time-resolved IR (TRIR) spectroscopy and tungsten hexacarbonyl, W(CO) 6 , we are able to structurally characterize the formation of an organometallic alkane complex, determine the W–C distances, and monitor the reactivity with silane to form an organometallic silane complex. Experiments in perfluorosolvents doped with xenon afford initially the corresponding solvated complex, which is sufficiently reactive in the presence of Xe that we can then observe the coordination of Xe to the metal center, providing a unique insight into the metal–xenon bonding. These results offer a step toward elucidating the structure, bonding, and chemical reactivity of transient species by X-ray absorption spectroscopy, which has sensitivity to small structural changes. The XAFS results indicate that the bond lengths of metal–alkane (W–H–C) bond in W(CO) 5 (heptane) as 3.07 (±0.06) Å, which is longer than the calculated W–C (2.86 Å) for binding of the primary C–H, but shorter than the calculated W–C (3.12 Å) for the secondary C–H. Here, a statistical average of the calculated W–C alkane bond lengths is 3.02 Å, and comparison of this value indicates that the value derived from the XAFS measurements is averaged over coordination of all C–H bonds consistent with alkane chain walking. Photolysis of W(CO) 6 in the presence of HSiBu 3 allows the conversion of W(CO) 5 (heptane) to W(CO) 5 (HSiBu 3 ) with an estimated W–Si distance of 3.20 (±0.03) Å. Time-resolved TRIR and XAFS experiments following photolysis of W(CO) 6 in perfluoromethylcyclohexane (PFMCH) allows the characterization of W(CO) 5 (PFMCH) with a W–F distance of 2.65 (±0.06) Å, and doping PFMCH with Xe allows the characterization of W(CO) 5 Xe with a W–Xe bond length of 3.10 (±0.02) Å.

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

Fragment-based determination of a proteinase K structure from MicroED data using ARCIMBOLDO_SHREDDER

Structure determination of novel biological macromolecules by X-ray crystallography can be facilitated by the use of small structural fragments, some of only a few residues in length, as effective search models for molecular replacement to overcome the phase problem. Independence from the need for a complete pre-existing model with sequence similarity to the crystallized molecule is the primary appeal of ARCIMBOLDO , a suite of programs which employs this ab initio algorithm for phase determination. Here, the use of ARCIMBOLDO is investigated to overcome the phase problem with the electron cryomicroscopy (cryoEM) method known as microcrystal electron diffraction (MicroED). The results support the use of the ARCIMBOLDO_SHREDDER pipeline to provide phasing solutions for a structure of proteinase K from 1.6 Å resolution data using model fragments derived from the structures of proteins sharing a sequence identity of as low as 20%. ARCIMBOLDO_SHREDDER identified the most accurate polyalanine fragments from a set of distantly related sequence homologues. Alternatively, such templates were extracted in spherical volumes and given internal degrees of freedom to refine towards the target structure. Both modes relied on the rotation function in Phaser to identify or refine fragment models and its translation function to place them. Model completion from the placed fragments proceeded through phase combination of partial solutions and/or density modification and main-chain autotracing using SHELXE . The combined set of fragments was sufficient to arrive at a solution that resembled that determined by conventional molecular replacement using the known target structure as a search model. This approach obviates the need for a single, complete and highly accurate search model when phasing MicroED data, and permits the evaluation of large fragment libraries for this purpose.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Selective deuteration of an RNA:RNA complex for structural analysis using small-angle scattering

The structures of RNA:RNA complexes regulate many biological processes. Despite their importance, protein-free RNA:RNA complexes represent a tiny fraction of experimentally determined structures. Here, we describe a joint small-angle X-ray and neutron scattering (SAXS/SANS) approach to structurally interrogate conformational changes in a model RNA:RNA complex. Using SAXS, we measured the solution structures of the individual RNAs and of the overall RNA:RNA complex. With SANS, we demonstrate, as a proof of principle, that isotope labeling and contrast matching (CM) can be combined to probe the bound state structure of an RNA within a selectively deuterated RNA:RNA complex. Furthermore, we show that experimental scattering data can validate and improve predicted AlphaFold 3 RNA:RNA complex structures to reflect its solution structure. In conclusion, our work demonstrates that in silico modeling, SAXS, and CM-SANS can be used in concert to directly analyze conformational changes within RNAs when in complex, enhancing our understanding of RNA structure in functional assemblies.

HIV-1 dimerization initiation site↗
DOE OSTI2018

Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy

The dynamically flexible lattices in lead-halide perovskites may play important roles in extending carrier recombination lifetime in 3D perovskite solar-cell absorbers and in exciton self-trapping in 2D perovskite white-light phosphors. Here, two-dimensional infrared (2D IR) spectroscopy was applied to study a recently reported Pb-I-SCN layered perovskite. The Pb-ISCN perovskite was spin-coated on a SiO 2 surface as a thin film, with a thickness of ~100 nm, where the S 12 CN – anions were isotopically diluted with the ratio of S 12 CN:S 13 CN=5:95 or 1:99 to avoid vibrational coupling and excitation transfer between adjacent SCN – anions. The minor S 12 CN – component was the principal vibrational probe that reported on the structural evolution through 2D IR spectroscopy. Spectral diffusion was observed with a time constant of 4.1 ± 0.3 ps. Spectral diffusion arises from small structural changes that result in sampling of frequencies within the distribution of frequencies that comprise the inhomogeneously broadened absorption spectrum of the in the Pb-I-SCN layered perovskite. These transitions among discrete local structures are distinct from oscillatory phonon motions of the lattice. To accurately evaluate the structural dynamics through measurement of spectral diffusion, the vibrational coupling between adjacent SCN – anions had to be carefully treated. Although the inorganic layers of typical 2D perovskites are structurally isolated from each other, the 2D IR data demonstrated that the layers of the Pb-I-SCN perovskite are vibrationally coupled. When both S 12 CN – and S 13 CN – were pumped simultaneously, cross-peaks between S 12 CN and S 13 CN vibrations and an oscillating 2D band shape of the S 12 CN – vibration were observed. Both observables demonstrate vibrational coupling between the closest SCN – anions, which reside in different inorganic layers. The thin films and the isotopic dilution produced exceedingly small vibrational echo signal fields; measurements were made possible using the near-Brewster’s angle reflection pump-probe geometry.

14 SOLAR ENERGY↗
DOE OSTI2014

Dynamics of compressional Mach cones in a strongly coupled complex plasma

Using a Generalised-Hydrodynamic (GH) fluid model, we study the influence of strong coupling induced modification of the fluid compressibility on the dynamics of compressional Mach cones in a dusty plasma medium. A significant structural change of lateral wakes for a given Mach number and Epstein drag force is found in the strongly coupled regime. With the increase of fluid compressibility, the peak amplitude of the normalised perturbed dust density first increases and then decreases monotonically after reaching its maximum value. It is also noticed that the opening angle of the cone structure decreases with the increase of the compressibility of the medium and the arm of the Mach cone breaks up into small structures in the velocity vector profile when the coupling between the dust particles increases.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

HIERARCHICAL STAR FORMATION IN NEARBY LEGUS GALAXIES

Hierarchical structure in ultraviolet images of 12 late-type LEGUS galaxies is studied by determining the numbers and fluxes of nested regions as a function of size from ∼1 to ∼200 pc, and the number as a function of flux. Two starburst dwarfs, NGC 1705 and NGC 5253, have steeper number-size and flux-size distributions than the others, indicating high fractions of the projected areas filled with star formation. Nine subregions in seven galaxies have similarly steep number-size slopes, even when the whole galaxies have shallower slopes. The results suggest that hierarchically structured star-forming regions several hundred parsecs or larger represent common unit structures. Small galaxies dominated by only a few of these units tend to be starbursts. The self-similarity of young stellar structures down to parsec scales suggests that star clusters form in the densest parts of a turbulent medium that also forms loose stellar groupings on larger scales. The presence of super star clusters in two of our starburst dwarfs would follow from the observed structure if cloud and stellar subregions more readily coalesce when self-gravity in the unit cell contributes more to the total gravitational potential.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

X-ray crystal structure and small-angle X-ray scattering of sheep liver sorbitol dehydrogenase

The X-ray crystal structure and a small-angle X-ray scattering solution structure of sheep liver sorbitol dehydrogenase have been determined. The details of the interactions that enable the tetramer scaffold to be the functional biological unit have been analyzed. The X-ray crystal structure of sheep liver sorbitol dehydrogenase (slSDH) has been determined using the crystal structure of human sorbitol dehydrogenase (hSDH) as a molecular-replacement model. slSDH crystallized in space group I222 with one monomer in the asymmetric unit. A conserved tetramer that superposes well with that seen in hSDH (despite belonging to a different space group) and obeying the 222 crystal symmetry is seen in slSDH. An acetate molecule is bound in the active site, coordinating to the active-site zinc through a water molecule. Glycerol, a substrate of slSDH, also occupies the substrate-binding pocket together with the acetate designed by nature to fit large polyol substrates. The substrate-binding pocket is seen to be in close proximity to the tetramer interface, which explains the need for the structural integrity of the tetramer for enzyme activity. Small-angle X-ray scattering was also used to identify the quaternary structure of the tetramer of slSDH in solution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Adsorption and oligomerization of 1,3-phenylene diisocyanide on Au(111)

The adsorption and self-assembly of 1,3-phenylene diisocyanide (1,3-PDI) are studied on Au(111) using reflection–adsorption infrared spectroscopy (RAIRS), scanning tunneling microscopy (STM), and temperature-programmed desorption (TPD) supplemented by density functional theory (DFT) calculations and the results compared with the structures formed from 1,4-PDI where it assembled to form –(Au–PDI)– oligomer chains that incorporate gold adatoms. The infrared spectra display a single isocyanide feature consistent with the isocyanide binding to gold adatoms, while DFT calculations confirm that isocyanide binding to gold adatoms is more energetically favorable than binding to the surface. STM images show that 1,3-PDI forms zigzag chains containing hairpin bends that cause the chains to double back on each other, consistent with the 120° angle between the isocyanide groups. Hexagonal structural motifs are also observed that are proposed to be due to the self-assembly of three isocyanides as well as small structures that are assigned to 1,3-PDI dimers. Furthermore, the results suggest that the formation of gold-containing oligomers from isocyanide-containing molecules is a general phenomenon.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Enhancing Plastic Recycling Through Nano-Scale Structure Analysis in Custom Block Copolymer Filaments (Rev.1)

As plastic production continues to increase, new methods to combat plastic waste are needed. This paper explores upcycling, a way to increase the utility or value of waste plastic. This can be done using block copolymers as compatibilizers. Block copolymers are made of two immiscible polymer blocks that phase separate on the nanoscale, forming small structures. The orientation of these nano-scale structures influences mechanical properties, and we show that orientation can be controlled by directional 3D (three dimensional) printing. Using small-angle X-ray scattering (SAXS), we analyze block copolymer filaments extruded at varying speeds. The SAXS data provide a baseline understanding of nano-scale structure in these unique filaments for future use in 3D printing experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Study on the heat removal for fuel debris using heat pipes

Simple method to retrieve fuel debris by meta-stabilizing: Heat removal system is needed. Heat removal using heat pipes: Cover fuel debris with geopolymer. What is a heat pipe: Heat transport medium with cycles of evaporation and condensation. It consists of the container, working fluid, and the wick. Advantage: Internal vacuum structure, small amount of working fluid, Massive heat transfer due to high-speed movement of hydraulic fluid. Cycle of hydraulic fluid with capillary structure. Because the cycle works independently of gravity, we can set heat pipes at free angle. We evaluated the availability of heat pipes within PCV. Investigation of hydrogen and oxygen concentration of internal gas collected by water replacement method: Non-condensable gas was confirmed inside the heat pipe irradiated by gamma rays. The heat removal effect by the heat pipe greatly descends to the extent close to the copper pipe by Gamma ray irradiation. The above reason was presumed to be that non-condensable gas was generated by radiolysis and the active length of the condensation part of the heat pipe decreased. Counter measures to decrease the amount of non-condensable gas is necessary for using heat pipes under radiation environment. We are doing the experiments to check changes in non-condensable gas generation by using catalysts or other kinds of liquids under Gamma ray irradiation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Insight into small molecule binding to the neonatal Fc receptor by X-ray crystallography and 100 kHz magic-angle-spinning NMR

Aiming at the design of an allosteric modulator of the neonatal Fc receptor (FcRn)–Immunoglobulin G (IgG) interaction, we developed a new methodology including NMR fragment screening, X-ray crystallography, and magic-angle-spinning (MAS) NMR at 100 kHz after sedimentation, exploiting very fast spinning of the nondeuterated soluble 42 kDa receptor construct to obtain resolved proton-detected 2D and 3D NMR spectra. FcRn plays a crucial role in regulation of IgG and serum albumin catabolism. It is a clinically validated drug target for the treatment of autoimmune diseases caused by pathogenic antibodies via the inhibition of its interaction with IgG. We herein present the discovery of a small molecule that binds into a conserved cavity of the heterodimeric, extracellular domain composed of an α-chain and β2-microglobulin (β2m) (FcRnECD, 373 residues). X-ray crystallography was used alongside NMR at 100 kHz MAS with sedimented soluble protein to explore possibilities for refining the compound as an allosteric modulator. Proton-detected MAS NMR experiments on fully protonated [ 13 C, 15 N]-labeled FcRnECD yielded ligand-induced chemical-shift perturbations (CSPs) for residues in the binding pocket and allosteric changes close to the interface of the two receptor heterodimers present in the asymmetric unit as well as potentially in the albumin interaction site. X-ray structures with and without ligand suggest the need for an optimized ligand to displace the α-chain with respect to β2m, both of which participate in the FcRn ECD –IgG interaction site. Our investigation establishes a method to characterize structurally small molecule binding to nondeuterated large proteins by NMR, even in their glycosylated form, which may prove highly valuable for structure-based drug discovery campaigns.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

High Performance Pseudocapacitor Based on 2D Layered Metal Chalcogenide Nanocrystals

Single-layer and few-layer transition metal dichalcogenides have been extensively studied for their electronic properties, but their energy-storage potential has not been well explored. This paper describes the structural and electrochemical properties of few-layer TiS 2 nanocrystals. Here, the two-dimensional morphology leads to very different behavior, compared to corresponding bulk materials. Only small structural changes occur during lithiation/delithiation and charge storage characteristics are consistent with intercalation pseudocapacitance, leading to materials that exhibit both high energy and power density.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cryo-EM structure determination of small therapeutic protein targets at 3 Å-resolution using a rigid imaging scaffold

Cryoelectron microscopy (Cryo-EM) has enabled structural determination of proteins larger than about 50 kDa, including many intractable by any other method, but it has largely failed for smaller proteins. Here, we obtain structures of small proteins by binding them to a rigid molecular scaffold based on a designed protein cage, revealing atomic details at resolutions reaching 2.9 Å. We apply this system to the key cancer signaling protein KRAS (19 kDa in size), obtaining four structures of oncogenic mutational variants by cryo-EM. Importantly, a structure for the key G12C mutant bound to an inhibitor drug (AMG510) reveals significant conformational differences compared to prior data in the crystalline state. The findings highlight the promise of cryo-EM scaffolds for advancing the design of drug molecules against small therapeutic protein targets in cancer and other human diseases.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

In situ resistivity of endotaxial FeSi{sub 2} nanowires on Si(110)

We present in situ ultra-high vacuum measurements of the resistivity ρ of self-assembled endotaxial FeSi{sub 2} nanowires (NWs) on Si(110) using a variable-spacing two-point method with a moveable scanning tunneling microscope tip and fixed contact pad. The resistivity at room temperature was found to be nearly constant down to NW width W = 4 nm, but rose sharply to nearly double the bulk value at W = 3 nm. These data are not well-fit by a simple Fuch-Sondheimer model for boundary scattering, suggesting that other factors, possibly quantum effects, may be significant at the smallest dimensions. For a NW width of 4 nm, partial oxidation increased ρ by approximately 50%, while cooling from 300 K to 150 K decreased ρ by approximately 10%. The relative insensitivity of ρ to NW size or oxidation or cooling is attributed to a high concentration of vacancies in the FeSi{sub 2} structure, with a correspondingly short length for inelastic electron scattering, which obscures boundary scattering except in the smallest NWs. It is remarkable that the vacancy concentration persists in very small structures.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Disruption of Z-Disc Function Promotes Mechanical Dysfunction in Human Myocardium: Evidence for a Dual Myofilament Modulatory Role by Alpha-Actinin 2

The ACTN2 gene encodes α-actinin 2, located in the Z-disc of the sarcomeres in striated muscle. In this study, we sought to investigate the effects of an ACTN2 missense variant of unknown significance (p.A868T) on cardiac muscle structure and function. Left ventricular free wall samples were obtained at the time of cardiac transplantation from a heart failure patient with the ACTN2 A868T heterozygous variant. This variant is in the EF 3–4 domain known to interact with titin and α-actinin. At the ultrastructural level, ACTN2 A868T cardiac samples presented small structural changes in cardiomyocytes when compared to healthy donor samples. However, contractile mechanics of permeabilized ACTN2 A868T variant cardiac tissue displayed higher myofilament Ca 2+ sensitivity of isometric force, reduced sinusoidal stiffness, and faster rates of tension redevelopment at all Ca 2+ levels. Small-angle X-ray diffraction indicated increased separation between thick and thin filaments, possibly contributing to changes in muscle kinetics. Molecular dynamics simulations indicated that while the mutation does not significantly impact the structure of α-actinin on its own, it likely alters the conformation associated with titin binding. Our results can be explained by two Z-disc mediated communication pathways: one pathway that involves α-actinin’s interaction with actin, affecting thin filament regulation, and the other pathway that involves α-actinin’s interaction with titin, affecting thick filament activation. This work establishes the role of α-actinin 2 in modulating cross-bridge kinetics and force development in the human myocardium as well as how it can be involved in the development of cardiac disease.

59 BASIC BIOLOGICAL SCIENCES↗