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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 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Effect of the Electric Field Strength on the Energy Resolution of Cr/CdTe/Pt Detectors

The electrical and spectrometric characteristics of the Cr/cadmium telluride (CdTe)/Pt structure with a metal-semiconductor type rectifying contact, used in X/γ-ray detectors, are investigated. For the detectors fabrication, chlorine-doped CdTe crystals with a resistivity of (3-6) × 10 9 Ω cm at 293 K were used. 137Cs spectra and their modification by applied voltage change were obtained. The reverse bias voltage corresponding to the best energy resolution of the Cr/CdTe/Pt structure is experimentally determined. The concentration of impurities N in the crystal, which determines the thickness of the space-charge region, is estimated. Finally, an energy resolution deterioration of the Cr/CdTe/Pt structure with increasing voltage is explained due to the Gunn effect.

47 OTHER INSTRUMENTATION↗
DOE OSTI2015

Transmission electron microscopy studying of structural features of NiTi B2 phase formed under pulsed electron-beam impact

By transmission electron microscopy method the evolution of structural-phase states on a depth of close to equiatomic NiTi modified layer has been studied. Modification performed by pulse impact on its surface low-energy high-current electron beam (beam energy density 10 J/sm{sup 2}, 10 pulses, pulse duration 50mks). It is established that during the treatment in the layer thickness of 8–10 μm, the melting of primary B2 phase and contained therein as Ti2Ni phase particles occurs. The result is change in the concentration ratio of titanium and nickel in the direction of increasing titanium content, which was confirmed by X-ray analysis in the form of increased unit cell parameter B2 phase. Analysis of the electron diffraction pattern showed that the modified layer is characterized as a highly distorted structure on the basis of bcc lattice. Lattice distortions are maximal near the surface and extends to a depth of melt. In subjacent layer there is gradual decline lattice distortions is observed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Regioselective Arene C−H Alkylation Enabled by Organic Photoredox Catalysis

Abstract Expanding the toolbox of C−H functionalization reactions applicable to the late‐stage modification of complex molecules is of interest in medicinal chemistry, wherein the preparation of structural variants of known pharmacophores is a key strategy for drug development. One manifold for the functionalization of aromatic molecules utilizes diazo compounds and a transition‐metal catalyst to generate a metallocarbene species, which is capable of direct insertion into an aromatic C−H bond. However, these high‐energy intermediates can often require directing groups or a large excess of substrate to achieve efficient and selective reactivity. Herein, we report that arene cation radicals generated by organic photoredox catalysis engage in formal C−H functionalization reactions with diazoacetate derivatives, furnishing sp 2 –sp 3 coupled products with moderate‐to‐good regioselectivity. In contrast to previous methods utilizing metallocarbene intermediates, this transformation does not proceed via a carbene intermediate, nor does it require the presence of a transition‐metal catalyst.

Holmberg‐Douglas, Natalie↗
DOE OSTI2020

Regioselective Arene C−H Alkylation Enabled by Organic Photoredox Catalysis

Abstract Expanding the toolbox of C−H functionalization reactions applicable to the late‐stage modification of complex molecules is of interest in medicinal chemistry, wherein the preparation of structural variants of known pharmacophores is a key strategy for drug development. One manifold for the functionalization of aromatic molecules utilizes diazo compounds and a transition‐metal catalyst to generate a metallocarbene species, which is capable of direct insertion into an aromatic C−H bond. However, these high‐energy intermediates can often require directing groups or a large excess of substrate to achieve efficient and selective reactivity. Herein, we report that arene cation radicals generated by organic photoredox catalysis engage in formal C−H functionalization reactions with diazoacetate derivatives, furnishing sp 2 –sp 3 coupled products with moderate‐to‐good regioselectivity. In contrast to previous methods utilizing metallocarbene intermediates, this transformation does not proceed via a carbene intermediate, nor does it require the presence of a transition‐metal catalyst.

Holmberg‐Douglas, Natalie↗
DOE OSTI2018

Effect of the Phase Composition of Catalysts Derived from Y-type Modified Zeolite on the Yield of C8 Hydrocarbons in the Alkylation of Isobutane by Olefins

Deviations in the activity parameters of previously synthesized catalysts derived from Y-type modified zeolite from the parameters of the basic phase composition (number of aluminum atoms in the unit cell, SiO{sub 2}/Al{sub 2}O{sub 3} ratio, unit cell size) are described. The results of a study of the structural changes in the crystalline phase of the zeolite upon its post-synthesis modification are presented.

2-METHYLPROPANE↗
DOE OSTI2017

Laser Nitriding of the Newly Developed Ti-20Nb-13Zr at.% Biomaterial Alloy to Enhance Its Mechanical and Corrosion Properties in Simulated Body Fluid

Despite the widespread application of Ti alloy in the biomedical field, surface treatments are typically applied to improve its resistance to corrosion and wear. A newly developed biomedical Ti-20Nb-13Zr at.% alloy (TNZ) was laser-treated in nitrogen environment to improve its surface characteristics with corrosion protection performance. Surface modification of the alloy by laser was performed through a Nd:YAG laser. The structural and surface morphological alterations in the laser nitrided layer were investigated by XRD and a FE-SEM. The mechanical properties have been evaluated using nanoindentation for laser nitride and as-received samples. The corrosion protection behavior was estimated using electrochemical corrosion analysis in a physiological medium (SBF). The obtained results revealed the production of a dense and compact film of TiN fine grains (micro-/nanosize) with 9.1 µm below the surface. The mechanical assessment results indicated an improvement in the modulus of elasticity, hardness, and resistance of the formed TiN layer to plastic deformation. The electrochemical analysis exhibited that the surface protection performance of the laser nitrided TNZ substrates in the SBF could be considerably enhanced compared to that of the as-received alloy due to the presence of fine grains in the TiN layer resulting from laser nitriding. Furthermore, the untreated and treated Ti-20Nb-13Zr alloy exhibited higher corrosion resistance than the CpTi and Ti6Al4V commercial alloys. The improvements in the surface hardness and corrosion properties of Ti alloy in a simulated body obtained using laser nitriding make this approach a suitable candidate for enhancing the properties of biomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Engineered bacterial microcompartments: apps for programming metabolism

Bacterial Microcompartments (BMCs) are used by diverse bacteria to compartmentalize enzymatic reactions, functioning analogously to the organelles of eukaryotes. The bounding membrane and encapsulated components are composed entirely of protein, which makes them ideal targets for modification by genetic engineering. In contrast to viruses, in which generally only one protein forms the capsid, the shells of BMCs consist of a variety of shell proteins, each a potential unit of selection. Despite their differences in permeability, the shell proteins are surprisingly interchangeable. Recent developments have shown that they are also highly amenable to engineered modifications which poise them for a variety of biotechnological applications. Additionally, given their modular structure, with a module defined as a semi-autonomous functional unit, BMCs can be considered apps for programming metabolism that can be de-bugged by adaptive evolution.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

NaSICON-type materials for lithium-ion battery applications: Progress and challenges

Lithium-ion batteries (LIBs) are widely used in electric vehicles, energy storage, smart grids, and portable devices due to their high average output voltage and energy density. NaSICON-type materials have been identified as potential candidates for electrode and solid electrolyte materials for LIBs due to their 3D framework, which contains Li + ions, excellent ionic conductivity, and thermal stability. NaSICON-type materials have a 3D framework and a fast Li + diffusion pathway, making them suitable for use in LIBs. However, their application as solid electrolytes is limited due to poorer ionic conductivity and interfacial stability compared to commercialized liquid electrolytes. Furthermore, their use as electrode materials is restricted by their low electronic conductivity. Here, this review provides an overview of NaSICON-type materials, including their common structure, Li + diffusion mechanism, and preparation strategies. The article also discusses the application and modification strategies of NaSICON-type materials for LIBs, classifying them as anode materials, cathode materials, and solid electrolyte materials. Additionally, the potential use of NaSICON-type materials as modification materials for cathode materials for LIBs is briefly mentioned. Building on previous work on NaSICON-type materials, we propose potential areas for further development and wider applications of these materials in LIBs.

25 ENERGY STORAGE↗
DOE OSTI2019

Differentiating Photoexcited Carrier and Phonon Dynamics in the Δ, L , and Γ Valleys of Si(100) with Transient Extreme Ultraviolet Spectroscopy

Transient extreme ultraviolet (XUV) spectroscopy probes core level transitions to unoccupied valence and conduction band states. Uncertainty remains as to what degree the core–hole created by the XUV transition modifies the measurement of photoexcited electron and hole energies. Here, the Si L 2,3 edge is measured after photoexcitation of electrons to the Δ, L, and Γ valleys of Si(100). The measured changes in the XUV transition probability do not energetically agree with the increasing electron photoexcitation energy. The data experimentally confirm that, for the Si L 2,3 edge, the time-dependent electron and hole energies are partially obscured by the core–hole perturbation. A model based on many-body approximations and the Bethe–Salpeter equation is successfully used to predict the core-hole modification of the final transition density of states in terms of both electronic and structural dynamics. The resulting fit time constants match the excited-state electron thermalization time and the intervalley electron–phonon, intravalley electron–phonon, and phonon–phonon scattering times previously measured in silicon. In conclusion, the outlined approach is a more comprehensive framework for interpreting transient XUV absorption spectra in photoexcited semiconductors.

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

Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal–Organic Frameworks

Comparison of defect-controlled leaching-kinetics modulation of metal–organic frameworks (MOFs) and porous functionalized silica-based materials was performed on the example of a radionuclide and radionuclide surrogate for the first time, revealing an unprecedented readsorption phenomenon. On a series of zirconium-based MOFs as model systems, we demonstrated the ability to capture and retain >99% of the transuranic 241 Am radionuclide after 1 week of storage. Here, we report the possibility of tailoring radionuclide release kinetics in MOFs through framework defects as a function of postsynthetically installed organic ligands including cation-chelating crown ether-based linkers. Based on comprehensive analysis using spectroscopy (EXAFS, UV–vis, FTIR, and NMR), X-ray crystallography (single crystal and powder), and theoretical calculations (nine kinetics models and structure simulations), we demonstrated the synergy of radionuclide integration methods, topological restrictions, postsynthetic scaffold modification, and defect engineering. This combination is inaccessible in any other material and highlights the advantages of using well-defined frameworks for gaining fundamental knowledge necessary for the advancement of actinide-based material development, providing a pathway for addressing upcoming challenges in the nuclear waste administration sector.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Ni-catalysed dicarbofunctionalization for the synthesis of sequence-encoded cyclooctene monomers

The properties of polymeric materials can be modulated by factors such as sequence control or functional group modifications. However, the synthesis of new macromolecular scaffolds is limited by the accessibility of structurally diverse monomers. This work describes a one-step, nickel-catalysed synthesis of 5,6-diaryl cyclooctene monomers from the feedstock chemical 1,5-cyclooctadiene. The reaction proceeds in a modular, regio- and diastereoselective fashion, granting access to both homo- and hetero-diaryl cyclooctene monomers that smoothly undergo ring-opening metathesis polymerization (ROMP). The resulting 1,2-diaryl-substituted polymers possess sequences with head-to-head styrene dyads that have not been previously explored, giving rise to unique and tunable properties. Density functional theory calculations highlight mechanistic aspects of the nickel-catalysed diarylation reaction and the ruthenium-catalysed ROMP process, revealing a previously unappreciated role of the boronic ester in promoting migratory insertion, which was leveraged to provide enantioinduction.

Catalytic mechanisms↗
DOE OSTI2016

Effect of Fe{sub 3}O{sub 4} nanoparticles on positive streamer propagation in transformer oil

Fe{sub 3}O{sub 4} nanoparticles with an average diameter of 10 nm were prepared and used to modify streamer characteristic of transformer oil. It was found that positive streamer propagation velocity in transformer oil-based Fe{sub 3}O{sub 4} nanofluid is greatly reduced by 51% in comparison with that in pure oil. The evolution of streamer shape is also dramatically affected by the presence of nanoparticles, changing from a tree-like shape with sharp branches in pure oil to a bush-like structure with thicker and denser branches in nanofluid. The TSC results reveal that the modification of Fe{sub 3}O{sub 4} nanoparticle can greatly increase the density of shallow trap and change space charge distribution in nanofluid by converting fast electrons into slow electrons via trapping and de-trapping process in shallow traps. These negative space charges induced by nanoparticles greatly alleviate the electric field distortion in front of the positive streamer tip and significantly hinder the propagation of positive streamer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Growth of electronically distinct manganite thin films by modulating cation stoichiometry

Nd 1-x Sr x MnO 3 (NSMO) is a well-known manganite due to close connection between structure, transport, magnetism, and chemistry. Thus, it would be an ideal system to study modification of physical properties by external stimuli including control of stoichiometry in growth. In this work, we show that abrupt change of electronic and magnetic properties can be achieved by subtle change of oxygen partial pressure in pulsed laser deposition. Interestingly, the pressure indeed modulates cation stoichiometry. We clearly observed that the films grown at 150 mTorr and higher showed clear insulator to metal transition and stronger magnetism, commonly found in less hole doping, while the films grown at 130 mTorr and lower showed insulating behavior and weak magnetism. From soft x-ray spectroscopic methods, we clearly observed the compositional difference in those thin films. This result is further supported by scattering of lighter elements in high oxygen partial pressure but not by anion deficiency in growth.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Anomalous lattice expansion of bcc Ta in helium-loaded diamond anvil cells

Anomalous lattice expansion of bcc Ta is observed in helium-loaded diamond anvil cell (DAC) experiments near 6 GPa and above 400 K, while co-loaded W, Mo, and Au exhibit normal thermal expansion. The Ta volume expansion increases with temperature, reaching ~14% near 650 K before plateauing, and is largely retained after recovery to ambient conditions. Time-resolved measurements at 500 K reveal progressive expansion over several hours, consistent with gradual, thermally activated He incorporation. The largely retained expansion during subsequent cooling and holding at 400 K indicates that the incorporated He is predominantly kinetically trapped. The data reveal two distinct regimes: below ~550 K, modest and spatially uniform expansion consistent with interstitial He trapping at isolated, randomly distributed vacancies; above ~550 K, He-vacancy cluster growth producing dramatically larger expansion, peak broadening, and a core–shell microstructure revealed by micron-resolution X-ray diffraction mapping. These results demonstrate that He is not always a passive pressure medium in DAC experiments and reveal a previously unrecognized regime of He-mediated lattice modification in Ta, complementing conventional ion-implantation studies relevant to nuclear and fusion structural materials.

Diamond anvil cell↗
DOE OSTI2018

Mechanism of tRNA-mediated +1 ribosomal frameshifting

Accurate translation of the genetic code is critical to ensure expression of proteins with correct amino acid sequences. Certain tRNAs can cause a shift out of frame (i.e., frameshifting) due to imbalances in tRNA concentrations, lack of tRNA modifications or insertions or deletions in tRNAs (called frameshift suppressors). Here, we determined the structural basis for how frameshift-suppressor tRNA SufA6 (a derivative of tRNA Pro ) reprograms the mRNA frame to translate a 4-nt codon when bound to the bacterial ribosome. After decoding at the aminoacyl (A) site, the crystal structure of the anticodon stem-loop of tRNA SufA6 bound in the peptidyl (P) site reveals ASL conformational changes that allow for recoding into the +1 mRNA frame. Furthermore, a crystal structure of full-length tRNA SufA6 programmed in the P site shows extensive conformational rearrangements of the 30S head and body domains similar to what is observed in a translocation intermediate state containing elongation factor G (EF-G). The 30S movement positions tRNA SufA6 toward the 30S exit (E) site disrupting key 16S rRNA–mRNA interactions that typically define the mRNA frame. In summary, this tRNA-induced 30S domain change in the absence of EF-G causes the ribosome to lose its grip on the mRNA and uncouples the canonical forward movement of the tRNAs during elongation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Symmetry breaking of fluorophore binding to a G-quadruplex generates an RNA aptamer with picomolar K D

Fluorogenic RNA aptamer tags with high affinity enable RNA purification and imaging. The G-quadruplex (G4) based Mango (M) series of aptamers were selected to bind a thiazole orange based (TO1-Biotin) ligand. Using a chemical biology and reselection approach, we have produced a MII.2 aptamer–ligand complex with a remarkable set of properties: Its unprecedented K D of 45 pM, formaldehyde resistance (8% v/v), temperature stability and ligand photo-recycling properties are all unusual to find simultaneously within a small RNA tag. Crystal structures demonstrate how MII.2, which differs from MII by a single A23U mutation, and modification of the TO1-Biotin ligand to TO1-6A-Biotin achieves these results. MII binds TO1-Biotin heterogeneously via a G4 surface that is surrounded by a stadium of five adenosines. Breaking this pseudo-rotational symmetry results in a highly cooperative and homogeneous ligand binding pocket: A22 of the G4 stadium stacks on the G4 binding surface while the TO1-6A-Biotin ligand completely fills the remaining three quadrants of the G4 ligand binding face. Similar optimization attempts with MIII.1, which already binds TO1-Biotin in a homogeneous manner, did not produce such marked improvements. We use the novel features of the MII.2 complex to demonstrate a powerful optically-based RNA purification system.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Pressure-induced modifications of the magnetic order in the spin-chain compound C a 3 C o 2 O 6

The structural and magnetic properties of the Ca 3 Co 2 O 6 spin-chain compound have been studied by means of neutron and x-ray powder diffraction at pressures up to 6.8 and 32 GPa, respectively. A suppression of the initial spin-density wave state (T N = 25 K) and stabilization of the collinear commensurate antiferromagnetic (AFM) state at high pressures (T NC = 26 K at P = 2.1 GPa) were observed. The pressure behavior of the competing intra- and interchain magnetic interactions was analyzed on the basis of obtained structural data and their role in the formation of the magnetic phase diagram is discussed. Here, the pressure behavior of the Néel temperature of the commensurate AFM phase was evaluated within the mean field theory approach and a good agreement with the experimental value dT NC /dP = 0.65 K/GPa was obtained.

1-dimensional spin chains↗