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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Antiferromagnetic ordering and possible lattice response to dynamic uranium valence in U 3 O 8

Determining the correct electronic structure of U 3 O 8 remains a formidable experimental and theoretical challenge. In the low-temperature phase, two crystallographic U sites are separated into a distinct 2U(V)+1U(VI) oxidation configuration. At low temperatures, the U(V) sites form a distorted honeycomb lattice, but the U(VI) sit on a triangular sublattice, suggesting potential for magnetic frustration effects. The spin configuration of the unpaired f electrons on the U(V) sites is likely antiferromagnetic (AFM) from susceptibility measurements, but this has not been confirmed. Here in this paper, we present a neutron scattering investigation of the structure and dynamics of U 3 O 8 from 1.7 to 600 K. We confirm static AFM ordering onset at between 22 and 25 K, which is present down to at least 1.7 K with AFM peaks corresponding to [0.5 1 1] and [0.5 2 2] in the orthorhombic phase. These measurements rule out static AFM order along the a axis of the Amm2 phase, a configuration previously suggested by theory. Above 100 K a quasielastic scattering channel opens that we speculate arises from a lattice relaxation response to thermally activated electron hopping. This term does not conform to a magnetic form factor, so it is not related to spin relaxations. If correct, this mechanism stabilizes a continuous valence transition from 2U(V)+1U(VI) in the low-temperature (T<600 K) orthorhombic phase to the hexagonal phase that contains only one degenerate U site, wherein the U valence can be dynamically stabilized between U(V)↔U(VI) by phonon-assisted electron hopping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Visualizing Anisotropic Oxygen Diffusion in Ceria under Activated Conditions

Oxygen reactivity plays a key role in the performance of ceria-based catalysts. Aberration-corrected transmission electron microscopy and molecular dynamics simulations were used to study the oxygen atom diffusion in ceria under activated conditions. Reactive oxygen atom and its real-time diffusion were visualized. Additionally, the interplay between cerium and oxygen atoms originating from a Coulomb interaction was revealed by the out-of-plane buckling of cerium atoms associated with oxygen transport. Anisotropic oxygen atom diffusion that depends on crystal orientations was discovered, demonstrating a preferential [001] crystallographic diffusion pathway. These findings reveal prospects for applications of anisotropic orientation-relevant fluorite-structured oxides.

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

Powder Diffraction Crystallography : 98 Years as Plan B?

A historical essay written in 2014 to accompany a talk in the Transactions Symposium "100 Years of Crystallography" at the 2014 American Crystallographic Association Annual Meeting (talk at https://history.amercrystalassn.org/h-brian-toby-videos). Abstract: Powder diffraction patterns were used for structure solution almost contemporaneously with the Bragg’s initial single-crystal determinations. Structures have continued to be determined from powders, in the subsequent century. There has been a nearly explosive growth in this technique since the 1970’s. This was initially driven by neutron diffraction, which prompted the invention of Rietveld analysis, but synchrotrons have gone on to have at least as large an impact. There is no apparent upper limit to the scale of systems that can be structurally studied with powder diffraction; novel protein structures have been determined. When short-range ordering or disordered regions of a material are of interest, the Fourier transform of a powder diffraction pattern, the pair distribution function can be modeled.

Toby, Brian H.↗
NASA NTRS1989

The low cycle fatigue deformation response of a single-crystal superalloy at 650 C

The cyclic stress-strain response and the associated deformation structure of the single crystal nickel-base superalloy PWA 1480 were investigated. Specimens of various crystallographic orientations were tested in low-cycle fatigue (LCF) at 650 C, resulting in a significant tension-compression anisotropy in initial yield strength associated with the shearing of gamma-prime precipitates by dislocation pairs, and a LCF cyclic hardening of the crystals associated with dislocation interactions occurring in the gamma phase. In specimens deforming by slip on a single slip system, dislocations of the primary slip system accumulated in the gamma matrix and formed seesile entanglements. In specimens deforming by slip on several slip systems, the dislocations of the different operative slip systems intersected in the gamma matrix and formed sessile arrangements.

Gabb, T. P.↗
DOE OSTI2021

Structures of two novel crystal forms of Aspergillus oryzae alpha amylase (taka-amylase)

The structures of Aspergillus oryzae α-amylase were determined in a tetragonal crystal, having one molecule as asymmetric unit, and a monoclinic crystal with two molecules as asymmetric unit. Both crystal forms were obtained from trace contaminants of an old commercial lipase preparation. Structures were determined and refined to 1.65 Å and 1.43 Å resolution respectively. The latter crystal has a non-crystallographic (NCS) twofold axis within the asymmetric unit. Glycosylation at Asn197 is evident, and in the tetragonal crystal can be seen to include three, partially disordered sugar residues following the initial N-acetyl glucosamine (NAG). Superposition of the tetragonal crystal model on the α-amylases from Bacillus subtilis (PDB:1BAG), pig pancreas (PDB:3L2L), and barley (PDB:1AMY), show a high degree of coincidence, particularly for the (β/α)8-barrel domains, and especially within the active site. Using this structural agreement between amylases, we extrapolated the binding model of a six residue, limit dextrin found in pig pancreas α-amylase to the A. oryzae enzyme model, which predicts substrate interacting amino acid residues.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Crystallographic evidence of Watson–Crick connectivity in the base pair of anionic adenine with thymine

Utilizing an ionic liquid strategy, we report crystal structures of salts of free anionic nucleobases and base pairs previously studied only computationally and in the gas phase. Reaction of tetrabutylammonium ([N 4444 ] + ) or tetrabutylphosphonium ([P 4444 ] + ) hydroxide with adenine (HAd) and thymine (HThy) led to hydrated salts of deprotonated adenine, [N 4444 ][Ad]·2H 2 O, and thymine, [P 4444 ][Thy]·2H 2 O, as well as the double salt cocrystal, [P 4444 ] 2 [Ad][Thy]·3H 2 O·2HThy. The cocrystal includes the anionic [Ad-(HThy)] base pair which is a stable formation in the solid state that has previously not even been suggested. It exhibits Watson–Crick connectivity as found in DNA but which is unusual for the free neutral base pairs. The stability of the observed anionic bases and their supramolecular formations and hydrates has also been examined by electronic structure calculations, contributing to more insight into how base pairs can bind when a proton is removed and highlighting mechanisms of stabilization or chemical transformation in the DNA chains.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1991

Three-dimensional structure of human serum albumin

The binding locations to human serum albumin (HSA) of several drug molecules were determined at low resolution using crystallographic methods. The principal binding sites are located within subdomains IIA and IIIA. Preliminary studies suggest that an approach to increasing the in vivo efficacy of drugs which are rendered less effective or ineffective by virtue of their interaction with HSA, would be the use of competitive displacement in drug therapies and/or the development of a general inhibitor to the site within subdomain IIIA. These findings also suggest that the facilitated transfer of various ligands across organ/circulatory interfaces such as liver, kidney, and brain may be associated with binding to the IIIA subdomain.

Carter, Daniel C.↗
NASA NTRS1992

Structure of a human monoclonal antibody Fab fragment against gp41 of human immunodeficiency virus type

The three-dimensional structure of a human monoclonal antibody (Fab), which binds specifically to a major epitope of the transmembrane protein gp41 of the human immunodeficiency virus type 1, has been determined by crystallographic methods to a resolution of 2.7 A. It has been previously determined that this antibody recognizes the epitope SGKLICTTAVPWNAS, belongs to the subclass IgG1 (kappa), and exhibits antibody-dependent cellular cytotoxicity. The quaternary structure of the Fab is in an extended conformation with an elbow bend angle between the constant and variable domains of 175 degrees. Structurally, four of the hypervariable loops can be classified according to previously recognized canonical structures. The third hypervariable loops of the heavy (H3) and light chain (L3) are structurally distinct. Hypervariable loop H3, residues 102H-109H, is unusually extended from the surface. The complementarity-determining region forms a hydrophobic binding pocket that is created primarily from hypervariable loops L3, H3, and H2.

He, X. M.↗
NASA NTRS1992

Structure of a human monoclonal antibody Fab fragment against gp41 of human immunodeficiency virus type 1

The three-dimensional structure of a human monoclonal antibody (Fab), which binds specifically to a major epitope of the transmembrane protein gp41 of the human immunodeficiency virus type 1, has been determined by crystallographic methods to a resolution of 2.7 A. It has been previously determined that this antibody recognizes the epitope SGKLICTTAVPWNAS, belongs to the subclass IgG1 (kappa), and exhibits antibody-dependent cellular cytotoxicity. The quaternary structure of the Fab is in an extended conformation with an elbow bend angle between the constant and variable domains of 175 deg. Structurally, four of the hypervariable loops can be classified according to previously recognized canonical structures. The third hypervariable loops of the heavy (H3) and light chain (L3) are structurally distinct. Hypervariable loop H3, residues 102H-109H, is unusually extended from the surface. The complementarity-determining region forms a hydrophobic binding pocket that is created primarily from hypervariable loops L3, H3, and H2.

He, Xiao M.↗
DOE OSTI2021

Persistence of crystal orientations across sub-micron-scale "super-grains" in self-organized Cu-W nanocomposites

We use precession electron diffraction to investigate the crystallographic character of copper (Cu)-tungsten (W) nanocomposites fabricated via physical vapor co-deposition at 400 oC. We observe sub-micron-scale regions, where apparently disconnected Cu and W grains have near identical crystallographic orientations. This persistence of grain orientations suggests Cu and W grains within these regions are interconnected in 3-D when they first form and may be considered as intercalated, sub-micron-scale "super-grains". Indeed, atom probe tomography provides direct evidence of 3-D interconnectivity of W domains. Our findings shed light on the structure and self organization mechanisms of nanocomposites formed by spontaneous phase separation of co-deposited metals.

Yadav, Digvijay↗
DOE OSTI2021

PDB ‐101: Educational resources supporting molecular explorations through biology and medicine

Abstract The Protein Data Bank (PDB) archive is a rich source of information in the form of atomic‐level three‐dimensional (3D) structures of biomolecules experimentally determined using macromolecular crystallography, nuclear magnetic resonance (NMR) spectroscopy, and electron microscopy (3DEM). Originally established in 1971 as a resource for protein crystallographers to freely exchange data, today PDB data drive research and education across scientific disciplines. In 2011, the online portal PDB‐101 was launched to support teachers, students, and the general public in PDB archive exploration ( pdb101.rcsb.org ). Maintained by the Research Collaboratory for Structural Bioinformatics PDB, PDB‐101 aims to help train the next generation of PDB users and to promote the overall importance of structural biology and protein science to nonexperts. Regularly published features include the highly popular Molecule of the Month series, 3D model activities, molecular animation videos, and educational curricula. Materials are organized into various categories (Health and Disease, Molecules of Life, Biotech and Nanotech, and Structures and Structure Determination) and searchable by keyword. A biennial health focus frames new resource creation and provides topics for annual video challenges for high school students. Web analytics document that PDB‐101 materials relating to fundamental topics (e.g., hemoglobin, catalase) are highly accessed year‐on‐year. In addition, PDB‐101 materials created in response to topical health matters (e.g., Zika, measles, coronavirus) are well received. PDB‐101 shows how learning about the diverse shapes and functions of PDB structures promotes understanding of all aspects of biology, from the central dogma of biology to health and disease to biological energy.

Zardecki, Christine↗
NASA NTRS1980

Defect structure of EFG silicon ribbon

The defect structure of EFG ribbons was studied using EBIC, TEM and HVEM. By imaging the same areas in EBIC and HVEM, a direct correlation between the crystallographic nature of defects and their electrical properties was obtained. (1) Partial dislocations at coherent twin boundaries may or may not be electrically active. Since no microprecipitates were observed at these dislocations it is likely that the different electrical activity is a consequence of the different dislocation core structures. (2) 2nd order twin joins were observed which followed the same direction as the coherent first order twins normally associated with EFG ribbons. These 2nd order twin joins are in all cases strongly electrically active. EFG ribbons contain high concentrations of carbon. Since no evidence of precipitation was found with TEM it is suggested that the carbon may be incorporated into the higher order twin boundaries now known to exist in EFG ribbons.

Strunk, H.↗
DOE OSTI2023

Crystal structure of calcium-ferrite type NaAlSiO4 up to 45 GPa

Abstract Alkali-rich aluminous high-pressure phases including calcium-ferrite (CF) type NaAlSiO4 are thought to constitute ~20% by volume of subducted mid-ocean ridge basalt (MORB) under lower mantle conditions. As a potentially significant host for incompatible elements in the deep mantle, knowledge of the crystal structure and physical properties of CF-type phases is therefore important to understanding the crystal chemistry of alkali storage and recycling in the Earth’s mantle. We determined the evolution of the crystal structure of pure CF-NaAlSiO4 and Fe-bearing CF-NaAlSiO4 at pressures up to ~45 GPa using synchrotron-based, single-crystal X-ray diffraction. Using the high-pressure lattice parameters, we also determined a third-order Birch-Murnaghan equation of state, with V0 = 241.6(1) Å3, KT0 = 220(4) GPa, and KT0′ = 2.6(3) for Fe-free CF, and V0 = 244.2(2) Å3, KT0 = 211(6) GPa, and KT0′ = 2.6(3) for Fe-bearing CF. The addition of Fe into CF-NaAlSiO4 resulted in a 10 ± 5% decrease in the stiffest direction of linear compressibility along the c-axis, leading to stronger elastic anisotropy compared with the Fe-free CF phase. The NaO8 polyhedra volume is 2.6 times larger and about 60% more compressible than the octahedral (Al,Si)O6 sites, with K0NaO8 = 127 GPa and K0(Al,Si)O6 ~304 GPa. Raman spectra of the pure CF-type NaAlSiO4 sample shows that the pressure coefficient of the mean vibrational mode, 1.60(7) cm–1/GPa, is slightly higher than 1.36(6) cm−1/GPa obtained for the Fe-bearing CF-NaAlSiO4 sample. The ability of CF-type phases to contain incompatible elements such as Na beyond the stability field of jadeite requires larger and less-compressible NaO8 polyhedra. Detailed high-pressure crystallographic information for the CF phases provides knowledge on how large alkali metals are hosted in alumina framework structures with stability well into the lowermost mantle.

Geochemistry & Geophysics↗
DOE OSTI2022

X-ray nano-imaging of defects in thin film catalysts via cluster analysis

Functional properties of transition-metal oxides strongly depend on crystallographic defects; crystallographic lattice deviations can affect ionic diffusion and adsorbate binding energies. Scanning x-ray nanodiffraction enables imaging of local structural distortions across an extended spatial region of thin samples. Yet, localized lattice distortions remain challenging to detect and localize using nanodiffraction, due to their weak diffuse scattering. Here, in this study, we apply an unsupervised machine learning clustering algorithm to isolate the low-intensity diffuse scattering in as-grown and alkaline-treated thin epitaxially strained SrIrO 3 films. We pinpoint the defect locations, find additional strain variation in the morphology of electrochemically cycled SrIrO 3 , and interpret the defect type by analyzing the diffraction profile through clustering. Our findings demonstrate the use of a machine learning clustering algorithm for identifying and characterizing hard-to-find crystallographic defects in thin films of electrocatalysts and highlight the potential to study electrochemical reactions at defect sites in operando experiments.

42 ENGINEERING↗
DOE OSTI2021

IrRep: Symmetry eigenvalues and irreducible representations of ab initio band structures

Here, we present IrRep – a Python code that calculates the symmetry eigenvalues of electronic Bloch states in crystalline solids and the irreducible representations under which they transform. As input it receives bandstructures computed with state-of-the-art Density Functional Theory codes such as VASP, Quantum Espresso, or Abinit, as well as any other code that has an interface to Wannier90. Our code is applicable to materials in any of the 230 space groups and double groups preserving time-reversal symmetry with or without spin-orbit coupling included, for primitive or conventional unit cells. This makes IrRep a powerful tool to systematically analyze the connectivity and topological classification of bands, as well as to detect insulators with non-trivial topology, following the Topological Quantum Chemistry formalism: IrRep can generate the input files needed to calculate the (physical) elementary band representations and the symmetry-based indicators using the [CheckTopologicalMat: https://www.cryst.ehu.es/cgi-bin/cryst/programs/magnetictopo.pl] routine of the Bilbao Crystallographic Server. It is also particularly suitable for interfaces with other plane-waves based codes, due to its flexible structure.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Zero-Dimensional Hybrid Organic–Inorganic Indium Bromide with Blue Emission

Low-dimensional hybrid organic–inorganic metal halides have received increased attention because of their outstanding optical and electronic properties. However, the most studied hybrid compounds contain lead and have long-term stability issues, which must be addressed for their use in practical applications. In this work, we report a new zero-dimensional hybrid organic–inorganic halide, RInBr 4 , featuring photoemissive trimethyl(4-stilbenyl)methylammonium (R + ) cations and nonemissive InBr 4 – tetrahedral anions. The crystal structure of RInBr 4 is composed of alternating layers of inorganic anions and organic cations along the crystallographic a axis. The resultant hybrid demonstrates bright-blue emission with Commission Internationale de l’Eclairage color coordinates of (0.19, 0.20) and a high photoluminescence quantum yield (PLQY) of 16.36% at room temperature, a 2-fold increase compared to the PLQY of 8.15% measured for the precursor organic salt RBr. On the basis of our optical spectroscopy and computational work, the organic component is responsible for the observed blue emission of the hybrid material. In addition to the enhanced light emission efficiency, the novel hybrid indium bromide demonstrates significantly improved environmental stability. These findings may pave the way for the consideration of hybrid organic In(III) halides for light emission applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

c -axis transport in UTe 2 : Evidence of three-dimensional conductivity component

Here we study the temperature dependence of electrical resistivity for currents directed along all crystallographic axes of the spin-triplet superconductor UTe 2 . We focus particularly on an accurate determination of the resistivity along the c axis (ρ c ) by using a generalized Montgomery technique that allows extraction of crystallographic resistivity components from a single sample. In contrast to expectations from the observed highly anisotropic band structure, our measurement of the absolute values of resistivities in all current directions reveals a surprisingly nearly isotropic transport behavior at temperatures above Kondo coherence, with ρ c ~ ρ b ~ 2 ρ a , that evolves to reveal qualitatively distinct behaviors on cooling. The temperature dependence of ρ c exhibits a peak at a temperature much lower than the onset of Kondo coherence observed in ρ a and ρ b , consistent with features in magnetotransport and magnetization that point to a magnetic origin. A comparison to the temperature-dependent evolution of the scattering rate observed in angle-resolved photoemission spectroscopy experiments provides important insights into the underlying electronic structure necessary for building a microscopic model of superconductivity in UTe 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Helimagnetism in MnBi 2 Se 4 Driven by Spin-Frustrating Interactions Between Antiferromagnetic Chains

We report the magnetic properties and magnetic structure determination for a linear-chain antiferromagnet, MnBi 2 Se 4 . The crystal structure of this material contains chains of edge-sharing MnSe 6 octahedra separated by Bi atoms. The magnetic behavior is dominated by intrachain antiferromagnetic (AFM) interactions, as demonstrated by the negative Weiss constant of –74 K obtained by the Curie–Weiss fit of the paramagnetic susceptibility measured along the easy-axis magnetization direction. The relative shift of adjacent chains by one-half of the chain period causes spin frustration due to interchain AFM coupling, which leads to AFM ordering at TN = 15 K. Neutron diffraction studies reveal that the AFM ordered state exhibits an incommensurate helimagnetic structure with the propagation vector k = (0, 0.356, 0). The Mn moments are arranged perpendicular to the chain propagation direction (the crystallographic b axis), and the turn angle around the helix is 128°. The magnetic properties of MnBi2Se4 are discussed in comparison to other linear-chain antiferromagnets based on ternary mixed-metal halides and chalcogenides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗