Search NASA⌕ Search

SEARCH · Search NASA

Results for “structural disorder”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Li 0.625 Al 0.125 H 0.25 Cl 0.75 O 0.25 Superionic Conductor with Disordered Rock-Salt Structure

Solid-state Li-ion conductors are of broad interest in electrochemical energy storage, especially in solid-state Li batteries that serve as a promising alternative for the next-generation safe and high-energy-density batteries. Exploring solid-state superionic conductors is significant for the development of solid-state Li batteries with high performance. Herein, we report a disordered rock-salt (A 1 B 1 )-structured solid electrolyte (Li 0.625 Al 0.125 H 0.25 )(Cl 0.75 O 0.25 ) (abbr. LAHCO) that was synthesized using Li 2 OHCl and LiAlCl 4 as precursors. Neutron diffraction reveals that Li, Al, and H atoms occupy the A sites and O and Cl atoms occupy the B sites in the A 1 B 1 structure for pure LAHCO. The LAHCO compound with excess LiAlCl 4 shows the highest Li + ionic conductivity of ~10 –4 S cm –1 at room temperature due to the disordering induced by configurational entropy as well as the entropy of mixing. Moreover, LAHCO–LiAlCl 4 solid electrolyte exhibits a stable polarization voltage under a current density of 5–50 μA cm –2 in Li symmetric cells. Furthermore, this work not only explicates the importance of Li-ion conductors with a rock-salt structure but also contributes toward the development of solid-state Li-ion conductors for broad applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Structural studies of intrinsically disordered MLL -fusion protein AF9 in complex with peptidomimetic inhibitors

AF9 (MLLT3) and its paralog ENL(MLLT1) are members of the YEATS family of proteins with important role in transcriptional and epigenetic regulatory complexes. These proteins are two common MLL fusion partners in MLL -rearranged leukemias. The oncofusion proteins MLL-AF9/ENL recruit multiple binding partners, including the histone methyltransferase DOT1L, leading to aberrant transcriptional activation and enhancing the expression of a characteristic set of genes that drive leukemogenesis. The interaction between AF9 and DOT1L is mediated by an intrinsically disordered C-terminal ANC1 homology domain (AHD) in AF9, which undergoes folding upon binding of DOT1L and other partner proteins. We have recently reported peptidomimetics that disrupt the recruitment of DOT1L by AF9 and ENL, providing a proof-of-concept for targeting AHD and assessing its druggability. Intrinsically disordered proteins, such as AF9 AHD, are difficult to study and characterize experimentally on a structural level. In this study, we present a successful protein engineering strategy to facilitate structural investigation of the intrinsically disordered AF9 AHD domain in complex with peptidomimetic inhibitors by using maltose binding protein (MBP) as a crystallization chaperone connected with linkers of varying flexibility and length. The strategic incorporation of disulfide bonds provided diffraction-quality crystals of the two disulfide-bridged MBP–AF9 AHD fusion proteins in complex with the peptidomimetics. These successfully determined first series of 2.1–2.6 Å crystal complex structures provide high-resolution insights into the interactions between AHD and its inhibitors, shedding light on the role of AHD in recruiting various binding partner proteins. We show that the overall complex structures closely resemble the reported NMR structure of AF9 AHD/DOT1L with notable difference in the conformation of the β-hairpin region, stabilized through conserved hydrogen bonds network. These first series of AF9 AHD/peptidomimetics complex structures are providing insights of the protein–inhibitor interactions and will facilitate further development of novel inhibitors targeting the AF9/ENL AHD domain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Functional in vitro diversity of an intrinsically disordered plant protein during freeze–thawing is encoded by its structural plasticity

Intrinsically disordered late embryogenesis abundant (LEA) proteins play a central role in the tolerance of plants and other organisms to dehydration brought upon, for example, by freezing temperatures, high salt concentration, drought or desiccation, and many LEA proteins have been found to stabilize dehydration-sensitive cellular structures. Their conformational ensembles are highly sensitive to the environment, allowing them to undergo conformational changes and adopt ordered secondary and quaternary structures and to participate in formation of membraneless organelles. In an interdisciplinary approach, we discovered how the functional diversity of the Arabidopsis thaliana LEA protein COR15A found in vitro is encoded in its structural repertoire, with the stabilization of membranes being achieved at the level of secondary structure and the stabilization of enzymes accomplished by the formation of oligomeric complexes. We provide molecular details on intra- and inter-monomeric helix–helix interactions, demonstrate how oligomerization is driven by an α-helical molecular recognition feature (α-MoRF) and provide a rationale that the formation of noncanonical, loosely packed, right-handed coiled-coils might be a recurring theme for homo- and hetero-oligomerization of LEA proteins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Structural origin of disorder-induced ion conduction in NaFePO 4 cathode materials

Diffusion in NaFePO 4 can be enhanced through amorphization. Based on computations using DFT and machine learning potentials, we ascribe this phenomenon to the formation of less constrained Na-ion environments upon disordering. Most modern battery technologies depend on solid-state crystalline cathode materials. However, some of these materials are constrained by the low ionic conductivity of their most stable phases. An example of this is maricite (NaFePO 4 ). Interestingly, experiments have shown that maricite can improve its rate capability through disordering (amorphization). However, experimental characterization of amorphous cathode materials remains a major challenge, hindering a clear understanding of the structural origin of the disorder-induced improvement in sodium-ion mobility. To address this, we here employ molecular dynamics simulations by first training a machine learning potential for NaFePO 4 based on the atomic cluster expansion approach and a batch active learning potential parameterization scheme. This potential is then applied to explore the structural and dynamical properties of NaFePO 4 glasses as cathode materials. Specifically, we investigate the effect of glass structure on sodium-ion diffusion, revealing the relative influences of short-range and medium-range order features. We find significant heterogeneity in sodium-ion diffusivity in the glass, with fast-conducting ions residing in less constrained atomic environments with fewer P and Fe neighbors. These more mobile ions are also surrounded by larger ring-type structures. Overall, the results and developed approach present promising avenues for developing high-performance glassy cathodes for next-generation batteries.

Christensen, Rasmus↗
DOE OSTI2020

Structure analysis of supported disordered molybdenum oxides using pair distribution function analysis and automated cluster modelling

Molybdenum oxides and sulfides on various low-cost high-surface-area supports are excellent catalysts for several industrially relevant reactions. The surface layer structure of these materials is, however, difficult to characterize due to small and disordered MoO x domains. Here, it is shown how X-ray total scattering can be applied to gain insights into the structure through differential pair distribution function (d-PDF) analysis, where the scattering signal from the support material is subtracted to obtain structural information on the supported structure. MoO x catalysts supported on alumina nanoparticles and on zeolites are investigated, and it is shown that the structure of the hydrated molybdenum oxide layer is closely related to that of disordered and polydisperse polyoxometalates. By analysing the PDFs with a large number of automatically generated cluster structures, which are constructed in an iterative manner from known polyoxometalate clusters, information is derived on the structural motifs in supported MoO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Completing the Ba–As Compositional Space: Synthesis and Characterization of Three New Binary Zintl Arsenides, Ba3As4, Ba5As4, and Ba16As11

Three novel binary barium arsenides, Ba3As4, Ba5As4, and Ba16As11, were synthesized and their crystal and electronic structures were investigated. Structural data collected via the single-crystal X-ray diffraction method indicate that the anionic substructures of all three novel compounds are composed of structural motifs based on the homoatomic As–As contacts, with [As2]4− dimers found in Ba5As4 and Ba16As11, and an [As4]6− tetramer found in Ba3As4. Ba3As4 and Ba5As4 crystallize in the orthorhombic crystal system—with the non-centrosymmetric space group Fdd2 (a = 15.3680(20) Å, b = 18.7550(30) Å, c = 6.2816(10) Å) for the former, and the centrosymmetric space group Cmce (a = 16.8820(30) Å, b = 8.5391(16) Å, and c = 8.6127(16) Å) for the latter—adopting Eu3As4 and Eu5As4 structure types, respectively. The heavily disordered Ba16As11 structure was solved in the tetragonal crystal system with the space group P4¯21m (a = 12.8944(12) Å and c = 11.8141(17) Å). The Zintl concept can be applied to each of these materials as follows: Ba3As4 = (Ba2+)3[As4]6−, Ba5As4 = (Ba2+)5(As3−)2[As2]4−, and 2 × Ba16As11 = (Ba2+)32(As3−) ≈ 20[As2]4− ≈ 1, pointing to the charge-balanced nature of these compounds. Electronic structure calculations indicate narrow bandgap semiconducting behavior, with calculated bandgaps of 0.47 eV for Ba3As4, 0.34 eV for Ba5As4, and 0.33 eV for Ba16As11.

Crystallography↗
DOE OSTI2025

Linking structural and rheological memory in disordered soft materials

Linking the macroscopic flow properties and nanoscopic structure is a fundamental challenge to understanding, predicting, and designing disordered soft materials. Under small stresses, these materials are soft solids, while larger loads can lead to yielding and the acquisition of plastic strain, which adds complexity to the task. In this work, we connect the transient structure and rheological memory of a colloidal gel under cyclic shearing across a range of amplitudes via a generalized memory function using rheo-X-ray photon correlation spectroscopy (rheo-XPCS). Our rheo-XPCS data show that the nanometer scale aggregate-level structure recorrelates whenever the change in recoverable strain over some interval is zero. The macroscopic recoverable strain is therefore a measure of the nano-scale structural memory. We further show that yielding in disordered colloidal materials is strongly heterogeneous and that memories of prior deformation can exist even after the material has been subjected to flow.

Kamani, Krutarth M. [Univ. of Illinois at Urbana-C↗
DOE OSTI2022

Optically Induced Anisotropy in Time-Resolved Scattering: Imaging Molecular-Scale Structure and Dynamics in Disordered Media with Experiment and Theory

Time-resolved scattering experiments enable imaging of materials at the molecular scale with femtosecond time resolution. However, in disordered media they provide access to just one radial dimension thus limiting the study of orientational structure and dynamics. Here we introduce a rigorous and practical theoretical framework for predicting and interpreting experiments combining optically induced anisotropy and time-resolved scattering. Using impulsive nuclear Raman and ultrafast x-ray scattering experiments of chloroform and simulations, we demonstrate that this framework can accurately predict and elucidate both the spatial and temporal features of these experiments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Role of structural defects in mediating disordering processes at irradiated epitaxial Fe 3 O 4 / Cr 2 O 3 interfaces

Disordering processes in oxide materials are complicated by the presence of interfaces, which can serve as either point defect sinks or accumulation sites; the response depends on factors such as interfacial structure, chemistry, and termination. Here, we have characterized the disordering of epitaxial Fe 3 O 4 (111) / Cr 2 O 3 (0001) thin film heterostructures after 400 keV Ar 2+ radiation at room temperature. The density of misfit dislocations in both the Fe 3 O 4 overlayer and Cr 2 O 3 buffer layer is varied by changing the thickness of Cr 2 O 3 to be pseudomorphically strained to the Al 2 O 3 (0001) substrate (5 nm thick) or partially relaxed (20 nm thick), as confirmed by Bragg filtering analysis of scanning transmission electron microscopy images. In both cases, irradiation leads to damage accumulation on the Fe 3 O 4 side of the heterointerface, as shown by Rutherford backscattering spectrometry measurements in the channeling geometry. However, the interface with more misfit dislocations exhibits disordering at a faster rate than the less-defective interface. Likewise, layer-resolved electron energy loss spectroscopy reveals interfacial reduction of Fe after irradiation at the more defective interface. Intermixing of Cr across the interface is observed by atom probe tomography, which is likely facilitated by the generation of Cr interstitials in Cr 2 O 3 under irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Unprecedented non-hysteretic superelasticity of [001]-oriented NiCoFeGa single crystals

Superelasticity associated with the martensitic transformation has found a broad range of engineering applications. However, the intrinsic hysteresis and temperature sensitivity of the first-order phase transformation significantly hinder the usage of smart metallic components in many critical areas. In this paper, we report a large superelasticity up to 15.2% strain in [001]-oriented NiCoFeGa single crystals, exhibiting non-hysteretic mechanical responses, a small temperature dependence and high-energy-storage capability and cyclic stability over a wide temperature and composition range. In situ synchrotron X-ray diffraction measurements show that the superelasticity is correlated with a stress-induced continuous variation of lattice parameter accompanied by structural fluctuation. Neutron diffraction and electron microscopy observations reveal an unprecedented microstructure consisting of atomic-level entanglement of ordered and disordered crystal structures, which can be manipulated to tune the superelasticity. The discovery of the large elasticity related to the entangled structure paves the way for exploiting elastic strain engineering and development of related functional materials. NiCoFeGa single crystals exhibit large non-hysteretic superelasticity over broad temperature and composition ranges. It is attributed to the continuous phase transition with applied stress, which is related to the fluctuation of entangled ordered and disordered crystal structures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mass spectrometry structural analysis of intrinsically disordered phosphoproteins

Phosphorylation is a ubiquitous protein modification that is known to play important roles in many biological phenomena including cell signaling, the opening and closing of membrane protein channels, and even triggering of amyloid protein aggregation. Despite the effects phosphorylation has on protein function, the impact phosphorylation has on the structure of proteins is not well understood. Here, to determine how phosphorylation affects the structure of proteins, top-down mass spectrometry (TD-MS) and ion mobility-mass spectrometry (IM-MS) were performed on various phosphorylated proteins and their dephosphorylated proteoforms. TD-MS with collision- and electron-based fragmentation techniques was utilized to locate phosphorylation sites on the intrinsically disordered amyloid proteins β-casein and α-synuclein. TD-MS also provided evidence that alkaline phosphatase dephosphorylates β-casein from the N-terminus to the C-terminus. Furthermore, IM-MS of common phosphorylated proteins such as β-casein, α-casein, ovalbumin, and phosvitin indicates that phosphorylation promotes compaction of protein structure in denaturing as well as native conditions. Increases in abundance of more compact conformers are also observed when the disease related amyloid protein α-synuclein is phosphorylated at serine 129. We interpret the increased abundance of more compact conformers when proteins are phosphorylated as evidence that salt bridges form between negatively charged phosphates and positively charged residues, which alters protein structure. Salt bridge formation due to phosphorylation could be a mechanism for regulating protein function and be responsible for many of the phenomena observed in nature.

Amyloid proteins↗
DOE OSTI2023

Experimental observation of spin glass state in the highly disordered quaternary Heusler alloy FeRuMnGa

The realization of the spin-glass (SG) state in Heusler alloys is very rare despite the presence of inherent structural and elemental disorder in those compounds. Although a few half- and full-Heusler alloys are known to exhibit the SG state, there is hardly any manifestation of the same in cases of quaternary Heusler compounds. Here we report the observation of a SG state in a highly disordered equiatomic quaternary Heusler compound: FeRuMnGa where the SG state is in between the canonical SG and the cluster glass. Different intricate features of the SG state including nonequilibrium magnetic dynamics at low temperatures in the compound are unveiled through our comprehensive magnetic, heat capacity, and neutron-diffraction studies. Further the structural disorder in the sample is neither conventional A2 - nor B2 -type whereas those two types are commonly observed for Heusler compounds. The presence of disorder also plays a significant role in electron transport properties of the alloy, which is reflected in its exhibition of semimetallic behavior and anomalous Hall effect at low temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Accurate prediction of short-range order and its effect on thermodynamic, structural, and electronic properties of disordered alloys: exemplified in archetypical Cu 3 Au

Electronic-structure methods based on density-functional theory (DFT) were used to quantify the effect of chemical short-range order (SRO) on thermodynamic, structural, and electronic properties of archetypal face-centered-cubic (fcc) Cu3Au alloy. We showed that SRO can be tuned to alter bonding and lattice dynamics (i.e., phonons) and detail how these properties are changed with SRO. Thermodynamically favorable SRO significantly improved the phase stability of fcc Cu3Au from -0.0343 eV-atom -1 to –0.0682 eV-atom -1 . We used our DFT-based linear-response theory to predict SRO and its electronic origin, and accurately estimate the observed transition temperature, ordering instability (L1 2 ), and Warren-Cowley SRO parameters, in agreement with experiments. The accurate prediction of real-space SRO gives an edge over computationally and resource intensive approaches such as monte-carlo methods or experiments, which will enable large scale molecular dynamic simulations by providing supercells with optimized SRO. Here we also analyzed phonon dispersion and estimated the vibrational entropy change (from 9kB at 300 K to 6kB at 100 K) in fcc Cu3Au. We established from SRO analysis that exclusion of chemical interactions may lead to a skewed view of true properties in chemically complex alloys. The first-principles methods described in this work are generally applicable to any arbitrary solid-solution alloys, including multi-principal-element alloys, therefore, holds promise for designing technologically useful materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Transient local secondary structure in the intrinsically disordered C‐term of the Albino3 insertase

Albino3 (Alb3) is an integral membrane protein fundamental to the targeting and insertion of light‐harvesting complex (LHC) proteins into the thylakoid membrane. Alb3 contains a stroma‐exposed C‐terminus (Alb3‐Cterm) that is responsible for binding the LHC‐loaded transit complex before LHC membrane insertion. Alb3‐Cterm has been reported to be intrinsically disordered, but precise mechanistic details underlying how it recognizes and binds to the transit complex are lacking, and the functional roles of its four different motifs have been debated. Using a novel combination of experimental and computational techniques such as single‐molecule fluorescence resonance energy transfer, circular dichroism with deconvolution analysis, site‐directed mutagenesis, trypsin digestion assays, and all‐atom molecular dynamics simulations in conjunction with enhanced sampling techniques, we show that Alb3‐Cterm contains transient secondary structure in motifs I and II. The excellent agreement between the experimental and computational data provides a quantitatively consistent picture and allows us to identify a heterogeneous structural ensemble that highlights the local and transient nature of the secondary structure. This structural ensemble was used to predict both the inter‐residue distance distributions of single molecules and the apparent unfolding free energy of the transient secondary structure, which were both in excellent agreement with those determined experimentally. We hypothesize that this transient local secondary structure may play an important role in the recognition of Alb3‐Cterm for the LHC‐loaded transit complex, and these results should provide a framework to better understand protein targeting by the Alb3‐Oxa1‐YidC family of insertases.

Okoto, Patience S.↗
DOE OSTI2021

Bayesian force fields from active learning for simulation of inter-dimensional transformation of stanene

Abstract We present a way to dramatically accelerate Gaussian process models for interatomic force fields based on many-body kernels by mapping both forces and uncertainties onto functions of low-dimensional features. This allows for automated active learning of models combining near-quantum accuracy, built-in uncertainty, and constant cost of evaluation that is comparable to classical analytical models, capable of simulating millions of atoms. Using this approach, we perform large-scale molecular dynamics simulations of the stability of the stanene monolayer. We discover an unusual phase transformation mechanism of 2D stanene, where ripples lead to nucleation of bilayer defects, densification into a disordered multilayer structure, followed by formation of bulk liquid at high temperature or nucleation and growth of the 3D bcc crystal at low temperature. The presented method opens possibilities for rapid development of fast accurate uncertainty-aware models for simulating long-time large-scale dynamics of complex materials.

Chemistry↗
DOE OSTI2021

Full structural ensembles of intrinsically disordered proteins from unbiased molecular dynamics simulations

Abstract Molecular dynamics (MD) simulation is widely used to complement ensemble-averaged experiments of intrinsically disordered proteins (IDPs). However, MD often suffers from limitations of inaccuracy. Here, we show that enhancing the sampling using Hamiltonian replica-exchange MD (HREMD) led to unbiased and accurate ensembles, reproducing small-angle scattering and NMR chemical shift experiments, for three IDPs of varying sequence properties using two recently optimized force fields, indicating the general applicability of HREMD for IDPs. We further demonstrate that, unlike HREMD, standard MD can reproduce experimental NMR chemical shifts, but not small-angle scattering data, suggesting chemical shifts are insufficient for testing the validity of IDP ensembles. Surprisingly, we reveal that despite differences in their sequence, the inter-chain statistics of all three IDPs are similar for short contour lengths (< 10 residues). The results suggest that the major hurdle of generating an accurate unbiased ensemble for IDPs has now been largely overcome.

59 BASIC BIOLOGICAL SCIENCES↗