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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

The Electronic Structure of the Metal Active Site Determines the Geometric Structure and Function of the Metalloregulator NikR

NikR is a nickel-responsive metalloregulator protein that controls the level of Ni 2+ ions in living cells. Previous studies have shown that NikR can bind a series of first-row transition metal ions but binds to DNA with high affinity only as a Ni 2+ complex. To understand this metal selectivity, S K-edge X-ray absorption spectroscopy of NikR bound to different metal ions was used to evaluate the different electronic structures. The experimental results are coupled with density functional theory calculations on relevant models. This study shows that both the Z eff of the metal ion and the donor nature of the ligands determine the electronic structure of the metal site. This impacts the geometric structure of the metal site and thus the conformation of the protein. Furthermore, this contribution of electronic structure to geometric structure can be extended to other metal selective metalloregulators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17): Site-Selective Substitution, Electronic Structure, Chemical Bonding, and Structural Transformation

CoSn-type intermetallic compounds have emerged as a model platform for Kagome-derived flat-band physics, where subtle chemical perturbations can strongly influence electronic structure and phase stability. Here, we present a combined experimental and theoretical study of Sb-substitution in CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17) to elucidate the interplay between site selectivity, solubility limit, chemical bonding, and electronic structure. Rietveld refinements on Neutron powder diffraction data confirmed the selective Sb-substitution at the electron-rich In2 (2d) site forming the honeycomb substructure, while the In1 (1a) site within the Kagome layer remains exclusively occupied by In. Density functional theory (DFT) calculations revealed that pristine CoSn-type NiIn hosts Ni 3d-dominated flat bands near the Fermi level (EF), originating from the Kagome-like Ni substructure. Partial replacement of In by Sb within the honeycomb layer alters these flat-band features below EF, reducing the density of states and suppressing the flat-band topology near the Fermi level. Orbital-resolved electronic structure and chemical-bonding analyses show that Sb-substitution enhances Ni-p-block (In/Sb) covalency and optimizes charge compensation, stabilizing the CoSn-type structure up to the solubility limit x ≈ 0.17. Beyond the limit, the higher-Sb compositions show satellite reflections consistent with an incommensurately modulated phase. These results establish a link between site-selective chemical substitution, bonding optimization, and flat-band electronic structure evolution, providing fundamental insights into how chemical substitution influences the electronic properties of Kagome-based intermetallic compounds.

Roy, Nilanjan [National Institute of Technology Si↗
DOE OSTI2019

Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite

Abstract Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (Na 0.27 MnO 2 ) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g −1 after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material. Particularly, the co-deintercalation of the hydrated water and sodium-ion during the high potential charging process results in the shrinkage of interlayer distance and thus stabilizes the layered structure. Our results provide a genuine insight into how structural disordering and structural water improve sodium-ion storage in a layered electrode and open up an exciting direction for improving aqueous batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Extended experimental inferential structure determination method in determining the structural ensembles of disordered protein states

Proteins with intrinsic or unfolded state disorder comprise a new frontier in structural biology, requiring the characterization of diverse and dynamic structural ensembles. Here we introduce a comprehensive Bayesian framework, the Extended Experimental Inferential Structure Determination (X-EISD) method, which calculates the maximum log-likelihood of a disordered protein ensemble. X-EISD accounts for the uncertainties of a range of experimental data and back-calculation models from structures, including NMR chemical shifts, J-couplings, Nuclear Overhauser Effects (NOEs), paramagnetic relaxation enhancements (PREs), residual dipolar couplings (RDCs), hydrodynamic radii (R h ), single molecule fluorescence Förster resonance energy transfer (smFRET) and small angle X-ray scattering (SAXS). We apply X-EISD to the joint optimization against experimental data for the unfolded drkN SH3 domain and find that combining a local data type, such as chemical shifts or J-couplings, paired with long-ranged restraints such as NOEs, PREs or smFRET, yields structural ensembles in good agreement with all other data types if combined with representative IDP conformers.

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

Synthesis and structural characterization of the new Zintl phases Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12

Two new ternary compounds, Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 , were synthesized and structurally characterized. The synthesis was achieved either through reactions in sealed niobium tubes or in alumina crucibles by combining the elements in excess molten Sb. Their structures were elucidated using single-crystal X-ray diffraction, and they were determined to crystallize in the orthorhombic space group Cmmm (no. 65) with the Eu 10 Cd 6 Bi 12 structure type. Akin to the archetype phase, both Mn and Zn sites contain about 25% of vacancies. Furthermore, the anionic substructure of the title phases can be described as [M 6 Pn 12 ] (M = Zn, Mn; Pn = Sb, Bi) double layers composed of the corner and edge-sharing [MPn 4 ] tetrahedra, linked by [Pn 2 ] 4– dumbbells. Eu 2+ /Yb 2+ cations fill the space between the layers, with the valence electron counts adhering closely to the Zintl–Klemm rules, i.e., both Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 are expected to be valence-precise compounds. Analysis of the electronic structure and transport properties of Yb 10 Zn 6 Sb 12 indicate semimetallic behavior with relatively low Seebeck coefficient and resistivity that slightly decreases as a function of temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural transitions of 4:1 methanol–ethanol mixture and silicone oil under high pressure

A 4:1 (volume ratio) methanol–ethanol (ME) mixture and silicone oil are two of the most widely used liquid pressure-transmitting media (PTM) in high-pressure studies. Their hydrostatic limits have been extensively studied using various methods; however, the evolution of the atomic structures associated with their emerging nonhydrostaticity remains unclear. Here, we monitor their structures as functions of pressure up to ∼30 GPa at room temperature using in situ high-pressure synchrotron x-ray diffraction (XRD), optical micro-Raman spectroscopy, and ruby fluorescence spectroscopy in a diamond anvil cell. No crystallization is observed for either PTM. The pressure dependence of the principal diffraction peak position and width indicates the existence of a glass transition in the 4:1 ME mixture at ∼12 GPa and in the silicone oil at ∼3 GPa, beyond which a pressure gradient emerges and grows quickly with pressure. There may be another liquid-to-liquid transition in the 4:1 ME mixture at ∼5 GPa and two more glass-to-glass transitions in the silicone oil at ∼10 GPa and ∼16 GPa. By contrast, Raman signals only show peak weakening and broadening for typical structural disordering, and Raman spectroscopy seems to be less sensitive than XRD in catching these structural transitions related to hydrostaticity variations in both PTM. These results uncover rich pressure-induced transitions in the two PTM and clarify their effects on hydrostaticity with direct structural evidence. The high-pressure XRD and Raman data on the two PTM obtained in this work could also be helpful in distinguishing between signals from samples and those from PTM in future high-pressure experiments.

Chen, Xiehang (ORCID:0000000168541506)↗
DOE OSTI2021

Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries

Electrolyte is very critical to the performance of the high-voltage lithium (Li) metal battery (LMB), which is one of the most attractive candidates for the next generation high-density energy storage systems. Electrolyte formulation and structure determine the physical properties of the electrolytes and their interfacial chemistries on the electrode surfaces. Localized high-concentration electrolytes (LHCEs) outperform state-of-the-art carbonate electrolytes in many aspects in LMBs due to their unique solvation structure. Types of fluorinated co-solvents used in LHCEs are investigated here in searching for the most suitable diluent for high concentration electrolytes (HCEs). Non-solvating solvents (including fluorinated ethers, fluorinated borate and fluorinated orthoformate) added in HCEs enable the formation of LHCEs with high-concentration solvation structures. However, low solvating fluorinated carbonate will coordinate with Li+ ions and form a second solvation shell or a pseudo-LHCE which diminishes the benefits of LHCE. In addition, it is evident that the diluent has significant influence on the electrode/electrolyte interphases (EEIs) beyond retaining the high-concentration solvation structures. Diluent molecules surrounding the high-concentration clusters could accelerate or decelerate the anion decomposition through co-participation of diluent decomposition in the EEI formation. The varied interphase features lead to significantly different battery-performance. This study points out the importance of diluents and their synergetic effects with the conductive salt and the solvating solvent in designing LHCEs. These systematic comparisons and fundamental insights into LHCEs using different types of fluorinated solvents can guide further development of advanced electrolytes for high-voltage LMBs.

Cao, Xia↗
DOE OSTI2022

High pressure structural phase transitions in Dysprosium to 202 GPa

High pressure structural phase transitions in heavy lanthanide metal Dysprosium (Dy) have been studied to 202 GPa (Volume Compression V/V 0 = 0.36) in a diamond anvil cell employing copper as an internal x-ray pressure standard. The previously assigned monoclinic (C2/m) phase above 72 GPa has been reexamined and assigned to an orthorhombic phase with sixteen atoms per cell (oF16) based on structural refinements. The equation of state is presented to 202 GPa and indicates a volume change of 2.3% during the structural phase transition from distorted face-centered cubic (hR24) phase to oF16 phase at 72 GPa. The oF16 phase can be regarded as a pseudo-orthorhombic eight-layered structure with (b/c) ratio decreasing from an ideal value of $\sqrt{3}$ with increasing pressure to 202 GPa. The ultrahigh pressure structural phases of Dy are compared with other members of the lanthanide series.

36 MATERIALS SCIENCE↗
DOE OSTI2022

RCSB Protein Data Bank (RCSB.org): delivery of experimentally-determined PDB structures alongside one million computed structure models of proteins from artificial intelligence/machine learning

Abstract The Research Collaboratory for Structural Bioinformatics Protein Data Bank (RCSB PDB), founding member of the Worldwide Protein Data Bank (wwPDB), is the US data center for the open-access PDB archive. As wwPDB-designated Archive Keeper, RCSB PDB is also responsible for PDB data security. Annually, RCSB PDB serves >10 000 depositors of three-dimensional (3D) biostructures working on all permanently inhabited continents. RCSB PDB delivers data from its research-focused RCSB.org web portal to many millions of PDB data consumers based in virtually every United Nations-recognized country, territory, etc. This Database Issue contribution describes upgrades to the research-focused RCSB.org web portal that created a one-stop-shop for open access to ∼200 000 experimentally-determined PDB structures of biological macromolecules alongside >1 000 000 incorporated Computed Structure Models (CSMs) predicted using artificial intelligence/machine learning methods. RCSB.org is a ‘living data resource.’ Every PDB structure and CSM is integrated weekly with related functional annotations from external biodata resources, providing up-to-date information for the entire corpus of 3D biostructure data freely available from RCSB.org with no usage limitations. Within RCSB.org, PDB structures and the CSMs are clearly identified as to their provenance and reliability. Both are fully searchable, and can be analyzed and visualized using the full complement of RCSB.org web portal capabilities.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

In situ analysis of the structural transformation of glassy carbon under compression at room temperature

Room temperature compression of graphitic materials leads to interesting superhard sp 3 rich phases which are sometimes transparent. In the case of graphite itself, the sp 3 rich phase is proposed to be monoclinic M-carbon; however, for disordered materials such as glassy carbon the nature of the transformation is unknown. We compress glassy carbon at room temperature in a diamond anvil cell, examine the structure in situ using x-ray diffraction, and interpret the findings with molecular dynamics modeling. Experiment and modeling both predict a two-stage transformation. First, the isotropic glassy carbon undergoes a reversible transformation to an oriented compressed graphitic structure. This is followed by a phase transformation at ~35 GPa to an unstable, disordered sp 3 rich structure that reverts on decompression to an oriented graphitic structure. Analysis of the simulated sp 3 rich material formed at high pressure reveals a noncrystalline structure with two different sp 3 bond lengths.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Disentangling transient charge order from structural dynamics contributions during coherent atomic motion studied by ultrafast resonant x-ray diffraction [Disentangling charge and structural contributions during coherent atomic motions studied by ultrafast resonant x-ray diffraction]

We report on the ultrafast dynamics of charge order and structural response during the photoinduced suppression of charge and orbital order in a mixed-valence manganite. Employing femtosecond time-resolved resonant x-ray diffraction below and at the Mn K absorption edge, we present a method to disentangle the transient charge order and structural dynamics in thin films of Pr 0.5 Ca 0.5 MnO 3 . Based on the static resonant scattering spectra, we extract the dispersion correction of charge-ordered Mn 3+ and Mn 4+ ions, allowing us to separate the transient contributions of purely charge order from structural contributions to the scattering amplitude after optical excitation. Furthermore, our finding of a coherent structural mode at around 2.3THz, which primarily modulates the lattice but does not strongly affect the charge order, supports the picture of the charge order being the driving force of the combined charge, orbital, and structural transition.

36 MATERIALS SCIENCE↗