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Results for “Structure elucidation”

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 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Structural plasticity enables evolution and innovation of RuBisCO assemblies

Oligomerization is a core structural feature that defines the form and function of many proteins. Most proteins form molecular complexes; however, there remains a dearth of diversity-driven structural studies investigating the evolutionary trajectory of these assemblies. Ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO) is one such enzyme that adopts multiple assemblies, although the origins and distribution of its different oligomeric states remain cryptic. Here, we retrace the evolution of ancestral and extant form II RuBisCOs, revealing a complex and diverse history of oligomerization. We structurally characterize a newly discovered tetrameric RuBisCO, elucidating how solvent-exposed surfaces can readily adopt new interactions to interconvert or give rise to new oligomeric states. We further use these principles to engineer and demonstrate how changes in oligomerization can be mediated by relatively few mutations. Our findings yield insight into how structural plasticity may give rise to new oligomeric states.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries

Cathode materials are critical to the energy density, power density and safety of sodium-ion batteries (SIBs). Herein, we performed a comprehensive study to elucidate and exemplify the interplay mechanism between phase structures, interfacial microstrain and electrochemical properties of layered-structured Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 cathode materials for high voltage SIBs. The electrochemical test results showed that Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 with an intergrowth P2/O3/O1 structure demonstrates better electrochemical performance and better thermal stability than Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 with P2/O3 binary-phase integration and Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 where only the P phase is dominant. This result is caused by the distinct interfacial microstrain development during the synthesis and cycling of the P2/O3/O1 phase. In operando high energy X-ray diffraction further revealed that the intergrowth P2/O1/O3 cathode can inhibit the irreversible P2–O2 phase transformation and simultaneously improve the structure stability of the O3 and O1 phases during cycling. Here, we believe that interfacial microstrain can serve as an indispensable bridge to guide future design and synthesis of high performance SIB cathode materials and other high energy battery materials.

25 ENERGY STORAGE↗
NASA NTRSDate not supplied

The Influence of Yttria Content on the Thermal Stability of Yttria-Stabilized Zirconia Aerogels

Aerogels demonstrate extraordinarily low thermal conductivity and low density, presenting a promising form of lightweight insulation for aerospace applications. The primary challenge is stabilization of the highly porous structure at temperatures to 1200 °C. Upon collapse of the pore structure, the favorable thermal properties and low density are diminished. Yttria-stabilized zirconia (YSZ) aerogels are synthesized to investigate the effect of composition on morphology, phase behavior, and thermal stability (specific surface area, pore size distribution). This work demonstrates the improvement in thermal stability of zirconia aerogels with increased yttria content. To develop insight on the influence of structure on thermal stability, the effects of water content and solids loading are studied and in elucidation of the mechanism by which yttria stabilizes the pore structure. With an improved understanding of aerogel structure and performance, metal oxide aerogels can be developed to withstand the extreme environments of space exploration.

Nathaniel Olson↗
DOE OSTI2025

Structural insights into isoform-specific RAS-PI3Kα interactions and the role of RAS in PI3Kα activation

Abstract Mutations in RAS and PI3Kα are major drivers of human cancer. Their interaction plays a crucial role in activating PI3Kα and amplifying the PI3K-AKT-mTOR pathway. Disrupting RAS-PI3Kα interaction enhances survival in lung and skin cancer models and reduces tumor growth and angiogenesis, although the structural details of this interaction remain unclear. Here, we present structures of KRAS, RRAS2, and MRAS bound to the catalytic subunit (p110α) of PI3Kα, elucidating the interaction interfaces and local conformational changes upon complex formation. Structural and mutational analyses highlighted key residues in RAS and PI3Kα impacting binding affinity and revealed isoform-specific differences at the interaction interface in RAS and PI3K isoforms, providing a rationale for their differential affinities. Notably, in the RAS-p110α complex structures, RAS interaction with p110α is limited to the RAS-binding domain and does not involve the kinase domain. This study underscores the pivotal role of the RAS-PI3Kα interaction in PI3Kα activation and provides a blueprint for designing PI3Kα isoform-specific inhibitors to disrupt this interaction.

Science & Technology - Other Topics↗
DOE OSTI2018

Effect of atomic order/disorder on vacancy clustering in concentrated NiFe alloys

Using molecular dynamics simulations, we elucidate in this paper the effect of atomic structure on vacancy clustering in ordered (L1 0 ) and random NiFe. Based on our simulations, we predict the vacancy evolution to be in complete contrast between the two systems. While large vacancy clusters, i.e., stacking fault tetrahedra (SFT) are formed in the random structure, no clustering is observed in the ordered-L1 0 structure. Similar simulations are performed on L1 0 -CuAu and L1 0 -TiAl to understand whether SFT formation is generic in L1 0 structures, or is specific to NiFe. Both materials show SFT formation, thereby highlighting specific defect energetics in L1 0 NiFe that lead to the lack of vacancy clustering. We elucidate that L1 0 -NiFe has unique thermodynamic and kinetic defect energetics, i.e., antisite energies, vacancy sublattice preference, and directional migration energy barriers that collectively lead to the lack of vacancy clustering. Finally, understanding such defect energetics could open avenues to prevent defect clustering in the vision towards development of radiation-tolerant concentrated alloys for nuclear reactor applications.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2017

Investigating Li 2 NiO 2 –Li 2 CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

Li 2 Ni 1–x Cu x O 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2 Ni 1–x Cu x O 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, and charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.

25 ENERGY STORAGE↗
DOE OSTI2016

An unusual crystal structure of ferric-enterobactin bound FepB suggests novel functions of FepB in microbial iron uptake

Iron acquisition by siderophores is critical for the survival of most bacteria. Enterobactin is a kind of catechol siderophore that exhibits the highest affinity to iron atoms secreted by E. coli and several other species of Enterobacteriaceae. The periplasmic binding protein (PBP) FepB can transport ferric-enterobactin (Fe-Ent) from the outer membrane to the membrane-associated ATP-binding cassette transport system in E. coli. To elucidate this process, we solved the crystal structure of FepB in complex with Fe-Ent at a resolution of 1.8 Å. Consistent with previously reported NMR results, our crystal structure shows that, similar to the other type III PBPs, the FepB structure was folded with separated globular N- and C-termini linked by a long α-helix. Additionally, the structure showed that the Fe-Ent bound to the cleft between the N- and C-terminal domains. Exceptionally, FepB differs from the other known siderophore binding PBPs in that it forms a trimer by capturing four Fe-Ents that can each contribute to FepB trimerization. Dynamic light-scattering experiments are consistent with the structural observations and indicate that FepB forms a trimer in a Fe-Ent-dependent manner.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Discovery of a Kelch-like ECH-associated protein 1-inhibitory tetrapeptide and its structural characterization

Keap1 constitutively binds to the transcription factor Nrf2 to promote its degradation, resulting in negative modulation of genes involved in cellular protection against oxidative stress. Keap1 is increasingly recognized as an attractive target for treating diseases involving oxidative stress, including cancer, atherosclerosis, diabetes, arthritis, and neurodegeneration. We used phage-display peptide screening to identify a tetrapeptide showing moderate binding affinity, which inhibits the interaction between Nrf2 and Keap1. The tetrapeptide does not include an ETGE motif, which is a commonly found consensus sequence in known peptidic inhibitors. In addition to affinity parameters, IC{sub 50}, K{sub D}, and thermodynamic parameters, the crystal structure of the complex was determined to elucidate the binding conformation. The binding interactions resemble those of known small-molecule inhibitors as opposed to those of substrates and peptidic inhibitors. Although the tetrapeptide's affinity is not very high, our results may help facilitate the designing of small-molecule inhibitors during lead generation in drug discovery. - Highlights: • Keap1 inhibitory tetrapeptide with moderate affinity was discovered. • Crystal structure of the complex showed the unique binding mode. • Structural information gives a valuable insight for design of therapeutic compounds.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Tailoring Charge Transport and Magnetism in Complex Half-Heusler/Full-Heusler Nanocomposites (Final Report)

This project exploits (1) the facile co-crystallization of the half-Heusler (HH) and full-Heusler (FH) structures, (2) the high coherency and stability of the HH/FH interfaces, and (3) the solid-state inter-conversion between HH and FH structures through local atomic diffusion, to investigate, for selected compositions of the HH and FH phases, the effect of size, dimensionality, dispersion and volume fraction of FH nanostructures on the electronic, phonon and magnetic behavior of the resulting HH/FH nanocomposites. Our goal is to identify and control key material and growth parameters governing phase formation, microstructural evolution, and to understand the mechanism by which these changes of the internal structure modify the material’s performance. To elucidate the mechanism by which the FH nanostructures regulate electronic charge transport and induce ferromagnetism within non-magnetic and magnetic semiconducting HH matrices, suitable series of HH/0D-FH and HH/2D-FH nanocomposites will be fabricated using synthesis conditions suggested by theoretical calculations of the formation energy and stability of various FH phases (varying M) in HH matrices with known chemical composition. The structure of the HH/FH interfaces (size, chemical composition, volume fraction and dispersion) will be investigated along with the evaluation of the electronic (carrier density, mobility, thermopower, electrical conductivity, effective mass), thermal and magnetic (susceptibility, magnetization etc.) properties of the resulting HH/FH nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Chd9 mediates highly loosened chromatin structure in growing mouse oocytes

Highlights: • The chromatin in growing oocytes is highly loosened to a level comparable to that in early preimplantation embryos. • Chromodomain helicase DNA binding protein 9 (Chd9) is highly expressed in growing oocytes. • CHD9 is involved in the loosened chromatin structure in growing oocytes. • The loosened chromatin structure, which is mediated by CHD9, is a prerequisite for the acquisition of totipotency after fertilization. During oogenesis, oocytes prepare for embryonic development following fertilization. The mechanisms underlying this process are still unknown. Recently, it has been suggested that a loosened chromatin structure is involved in pluripotency and totipotency in embryonic stem (ES) cells and early preimplantation embryos, respectively. Here, we explored chromatin looseness in oocytes by fluorescence recovery after photobleaching (FRAP) using enhanced green fluorescent protein-tagged histone H2B. The results indicated that the chromatin in growing oocytes was already highly loosened to a level comparable to that in early preimplantation embryos. To elucidate the mechanism underlying the loosened chromatin structure in oocytes, we focused on chromodomain helicase DNA binding protein 9 (Chd9), which is highly expressed in growing oocytes. The oocytes from Chd9 knockout mice (Chd9{sup −/−}) generated using the CRISPR/Cas9 system exhibited a less loosened chromatin structure than that of wild-type mice, suggesting that Chd9 is involved in the loosened chromatin structure in growing oocytes. These results suggest that a loosened chromatin structure, which is mediated by Chd9, is a prerequisite for the acquisition of totipotency after fertilization.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1985

Structural Development and Gravity

Major research projects designed to elucidate the mechanisms by which gravity loading and/or fluid distribution alter bone formation and/or resorption in rat bone are reported. Projects completed include: (1) analysis of bone parameters in rats from 6 weeks to 68 weeks of age; (2) restricted access area in which rats on the model were not allowed to touch any side of the cage; and (3) the effect of dietary calcium levels on bone formation and resorption rates in controls and head-down rats.

Holton, E. M.↗
NASA NTRSDate not supplied

Simulating the Martian Middle and Upper Atmosphere with the NASA Ames Mars GCM.

The NASA Ames Mars Global Climate Model (MGCM) continues to be utilized to examine the dynamical coupling between the lower atmosphere and middle/upper atmosphere. This coupling impacts the transport of water, dust, and chemistry which augments the thermal structure and circulation. The interactions and coupling within the atmosphere are important for understanding the present-day and past atmosphere and climate. MGCM simulations are compared with observations from recent Mars missions to provide model constraints, and in turn, the simulations can then provide context to the observations. This cycle is important to move us forward in our understanding of planetary atmospheres. We will present on one of the fundamental atmospheric features, the thermal structure, and how the physics in the MGCM can elucidate the observed diurnal and seasonal behavior. Additionally, we will focus on the distribution of chemical species which influences the thermal structure and provides additional information on the coupling between the lower and middle/upper atmosphere. Lastly, we will provide a summary of the model capabilities, as the MGCM continues to be improved upon to properly simulate Mars’ atmosphere from the ground to ~250 km.

Amanda Susanne Brecht↗
DOE OSTI2026

Discovery of a new phase transition and high-valent redox mechanism in Fe-substituted Na 2 Mn 3 O 7

Sodium-ion batteries are a promising lower-cost alternative to lithium-ion batteries, but further improvements in electrochemical performance are required. One strategy to increase capacity is to enable reversible high-valent cationic and anionic redox in layered cathode materials; however, this is typically accompanied by structural degradation. Here, in this study, we elucidate the mechanism by which Fe-doped Na 2 Mn 3 O 7 , featuring ordered transition metal-vacancies, achieves reversible high-valent redox. Using Mössbauer spectroscopy, soft X-ray absorption spectroscopy (XAS), and in-situ hard XAS, we demonstrate reversible high-valent cationic redox involving both Fe and Mn while in-situ Raman confirms the absence of local structural degradation associated with oxygen redox. Combining in-situ X-ray diffraction with theoretical calculations, we further identify a previously unreported global phase transition from the $\bar{P1}$ to the $P2_1/c$ space group during electrochemical cycling and develop a physical model describing this structural evolution. These results provide insights for structurally stable layered sodium transition metal oxide cathodes with reversible high-valent redox.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Identification of a low-energy metastable 1 T -type phase for monolayer VSe 2

Elucidating the polymorphism of transition metal dichalcogenide layers and the interplay between structure and properties is a key challenge for the application of these materials. We identify a low-energy metastable phase of monolayer VSe 2 and elucidate its magnetic and electronic properties. This structure is distinct from the previously identified charge density wave (CDW) phase. However, while having rather distinct properties it is very close in energy to the CDW phase and is likely to be realized in experiments. Importantly, local bonding instabilities, as characterized by reconstruction of the electronic structure over a wide energy range, are important for this distortion, which includes both V off-centering in the octahedral coordination cages and a partial disproportionation into two distinct types of V. The phase does not have a ferromagnetic ground state. Furthermore, the results show that the physics of 1T–VSe 2 are richer than previously known with an interplay of Fermi surface instabilities and local bonding effects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Assessing the interfacial corrosion mechanism of Inconel 617 in chloride molten salt corrosion using multi-modal advanced characterization techniques

The United States Department of Energy (DOE) has committed to expanding the domestic clean energy portfolio in response to the rising challenges of energy security in the wake of climate change. Accordingly, the construction of a series of Generation IV reactor technologies are being demonstrated, including sodium-cooled, small modular, and molten chloride fast reactors (MCFRs). To date, there are no fully qualified structural materials for constructing MCFRs. A number of commercial structural alloys have been considered for the construction of MCFRs, including alloys from the Inconel and Hastelloy series. Informed qualification of structural materials for the construction of MCFRs in the future can only be ensured by expanding the current fundamental knowledgebase of information pertaining to material performance under environmental stressors relevant to operation of the reactor, including corrosion susceptibility. The purpose of this investigation is to illustrate how a correlative multi-modal electron microscopy characterization approach, including the novel application of focused-ion beam 3D reconstruction capabilities, can elucidate the corrosion mechanism of a candidate structural material Inconel 617 for MCFR in NaCl-MgCl 2 eutectic salt at 700°C for 1,000 h. Evidence of intergranular corrosion, Ni and Fe dealloying, and Cr-O enrichment along the grain boundary, which most likely corresponds to Cr 2 O 3 , is a phenomenon that has been documented in other Ni-based superalloys exposed to chloride molten salt systems. Additional corrosion products, including the formation of insoluble MgAl 2 O 4 , within the porous network produced by the salt attack is a novel observation. In addition, Mo 3 Si 5 and τ 2 precipitates are detected in the alloy bulk and are dissolved by the salt. Furthermore, the lack of detection of design γ' precipitates in Inconel 617 after 1,000 h could indicate that the molten salt corrosion mechanism has indirectly induced a phase transformation of Al 2 TiNi (τ 2 ) and Ni 3 (Al,Ti) (γ’) phase. This investigation provides a comprehensive understanding of molten salt corrosion mechanisms in a complex material system such as a commercial structural alloy for applications in MCFRs.

36 MATERIALS SCIENCE↗
DOE OSTI2025

On the dynamics of the fluoroethylene carbonate generated solid electrolyte interphase on silicon anodes during calendar life aging

Here, the widespread use of silicon (Si)-rich anodes in lithium-ion batteries (LIBs) is impeded by an unstable solid electrolyte interphase (SEI) incurring insufficient cell life. Fluoroethylene carbonate (FEC) additive in the electrolyte significantly improves cycle life. However, the gains on calendar life remain unclear; the SEI structure still undergoes detrimental alterations at rest. Thus, elucidating the SEI dynamics during calendar aging is critical to mitigating time-dependent capacity degradation. ATR-FTIR, XPS, and ToF-SIMS are used herein to investigate the SEI structure before and after calendar aging. Si cycled without FEC exhibits no notable SEI chemistry changes Pre- and Post-aging, leaving poor passivation as the main failure pathway. Conversely, the FEC-SEI starts as short oligomeric species from FEC/EC electroreduction prior to aging; after calendar aging, polymerized carbonates become consistently more prominent. Unexpectedly, the deposition of self-polymerized FEC species results from time exposure to the delithiated Si specifically as opposed to the lithiated surface. This unexpected finding is supported by another recent Si calendar-aging research, which albeit not investigating FEC, finds global failure of the SEI upon delithiation resulting in ∼247 fold more reactive surface compared to the lithiated.

Batteries↗
DOE OSTI2021

Melting Point Depression and Phase Identification of Sugar Alcohols Encapsulated in ZIF Nanopores

Sugar alcohols (SAs) have attractive characteristics as phase-change materials, but their relatively high melting temperature limits their application in the real world. Nanoconfinement can be a useful parameter to reduce the melting temperature to pragmatic ranges. Using molecular dynamics simulations, we investigate the phases and behaviors of encapsulated SA in ZIF-8 and ZIF-11, which cannot be experimentally observed. Based on reliable partial charges for the zeolitic imidazolate framework (ZIF) structures calculated by a density functional theory, structural analysis shows that the SA’s attractive interaction with the ZIF structure frustrates the SA crystallization and also elucidates the second-order phase transition between amorphous phases. A methodology is suggested to determine the phase transition temperature of confined materials and used to quantify the melting temperature depression of the ZIF-confined SAs. We also explored the thermal conductivity of SA-in-ZIF composites. Phonon frequency analysis verifies that the presence of SA molecules enhances the heat transfer by adding heat pathways between the nanoporous structure of ZIFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗