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At least 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

The formation and characterization of large twin related domains

The enhanced properties of grain boundary engineered metals are a result of their unique microstructures, which contain large clusters of twinned grains, called twin related domains. These large twin related domains in grain boundary engineered Ni were found to form through recrystallization. Orientation mapping showed that sparse nucleation and multiple twinning resulted in twin related domains containing hundreds of grains connected together in complex morphologies. A correlation was found between the size of the twin related domains and the overall twin boundary fraction. The same correlation was also observed in Cu and a Ni superalloy, showing that this is a general observation for grain boundary engineered microstructures. This finding can be understood through the topology of the twin related domains and an accompanying scaling relation is provided. The crystal orientations contained within each twin related domain were observed to depend on both the spatial correlation of twinning variants and the degree of branching in the twin boundary network. The results suggest a natural way of quantifying grain boundary engineered microstructures and provide a step toward making a closer connection between processing, microstructure, and performance.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Intercalated rare-earth metals under graphene on SiC

Intercalation of rare earth metals (RE = Eu, Dy, and Gd) is achieved by depositing the RE metal on graphene that is grown on silicon-carbide (SiC) and by subsequent annealing at high temperatures to promote intercalation. STM images of the films reveal that the graphene layer is defect free and that each of the intercalated metals has a distinct nucleation pattern. Intercalated Eu forms nano-clusters that are situated on the vertices of a Moirè pattern, while Dy and Gd form randomly distributed nano-clusters. X-ray magnetic circular dichroism (XMCD) measurements of intercalated films reveal the magnetic properties of these REs nano-clusters. Furthermore, field dependence and temperature dependence of the magnetic moments extracted from the XMCD show paramagnetic-like behaviors with moments that are generally smaller than those predicted by the Brillouin function. XMCD measurements of RE-oxides compared with those of the intercalated REs under graphene after exposure to air for months indicate that the graphene membranes protect these intercalants against oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Control of single-ligand chemistry on thiolated Au 25 nanoclusters

Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but control of surface ligand number at a given cluster size is rare. Here we demonstrate that reversible addition and elimination of a single surface thiolate ligand (-SR) on gold nanoclusters can be realized, opening the door to precision ligand engineering on atomically precise nanoclusters. We find that oxidative etching of [Au 25 SR 18 ] – nanoclusters adds an excess thiolate ligand and generates a new species, [Au 25 SR 19 ] 0 . The addition reaction can be reversed by CO reduction of [Au 25 SR 19 ] 0 , leading back to [Au 25 SR 18 ] – and eliminating precisely one surface ligand. Intriguingly, we show that the ligand shell of Au 25 nanoclusters becomes more fragile and rigid after ligand addition. This reversible addition/elimination reaction of a single surface ligand on gold nanoclusters shows potential to precisely control the number of surface ligands and to explore new ligand space at each nuclearity.

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

Reversing sintering effect of Ni particles on γ-Mo 2 N via strong metal support interaction

Reversing the thermal induced sintering phenomenon and forming high temperature stable fine dispersed metallic centers with unique structural and electronic properties is one of the ever-lasting targets of heterogeneous catalysis. Here we report that the dispersion of metallic Ni particles into under-coordinated two-dimensional Ni clusters over γ-Mo 2 N is a thermodynamically favorable process based on the AIMD simulation. A Ni-4nm/γ-Mo 2 N model catalyst is synthesized and used to further study the reverse sintering effect by the combination of multiple in-situ characterization methods, including in-situ quick XANES and EXAFS, ambient pressure XPS and environmental SE/STEM etc. The under-coordinated two-dimensional layered Ni clusters on molybdenum nitride support generated from the Ni-4nm/γ-Mo 2 N has been demonstrated to be a thermally stable catalyst in 50 h stability test in CO 2 hydrogenation, and exhibits a remarkable catalytic selectivity reverse compared with traditional Ni particles-based catalyst, leading to a chemo-specific CO 2 hydrogenation to CO.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

When using the TiO 2 (110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd 7 -3D/TiO 2 (110) at low coverage to Pd 7 -2D/TiO 2 (110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO 2 (110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O 2 dissociation and CO oxidation via bifunctional synergy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Exohedral M–C{sub 60} and M{sub 2}–C{sub 60} (M = Pt, Pd) systems as tunable-gap building blocks for nanoarchitecture and nanocatalysis

Transition metal–fullerenes complexes with metal atoms bound on the external surface of C{sub 60} are promising building blocks for next-generation fuel cells and catalysts. Yet, at variance with endohedral M@C{sub 60}, they have received a limited attention. By resorting to first principles simulations, we elucidate structural and electronic properties for the Pd–C{sub 60}, Pt–C{sub 60}, PtPd–C{sub 60}, Pd{sub 2}–C{sub 60}, and Pt{sub 2}–C{sub 60} complexes. The most stable structures feature the metal atom located above a high electron density site, namely, the π bond between two adjacent hexagons (π-66 bond). When two metal atoms are added, the most stable configuration is those in which metal atoms still stand on π-66 bonds but tends to clusterize. The electronic structure, rationalized in terms of localized Wannier functions, provides a clear picture of the underlying interactions responsible for the stability or instability of the complexes, showing a strict relationship between structure and electronic gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Cluster decomposition of full configuration interaction wave functions: A tool for chemical interpretation of systems with strong correlation

Approximate full configuration interaction (FCI) calculations have recently become tractable for systems of unforeseen size, thanks to stochastic and adaptive approximations to the exponentially scaling FCI problem. The result of an FCI calculation is a weighted set of electronic configurations, which can also be expressed in terms of excitations from a reference configuration. The excitation amplitudes contain information on the complexity of the electronic wave function, but this information is contaminated by contributions from disconnected excitations, i.e., those excitations that are just products of independent lower-level excitations. The unwanted contributions can be removed via a cluster decomposition procedure, making it possible to examine the importance of connected excitations in complicated multireference molecules which are outside the reach of conventional algorithms. We present an implementation of the cluster decomposition analysis and apply it to both true FCI wave functions, as well as wave functions generated from the adaptive sampling CI algorithm. Furthermore, the cluster decomposition is useful for interpreting calculations in chemical studies, as a diagnostic for the convergence of various excitation manifolds, as well as as a guidepost for polynomially scaling electronic structure models. Applications are presented for (i) the double dissociation of water, (ii) the carbon dimer, (iii) the π space of polyacenes, and (iv) the chromium dimer. While the cluster amplitudes exhibit rapid decay with an increasing rank for the first three systems, even connected octuple excitations still appear important in Cr 2 , suggesting that spin-restricted single-reference coupled-cluster approaches may not be tractable for some problems in transition metal chemistry.

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

Modulating metal-centered dimerization of a lanthanide chaperone protein for separation of light lanthanides

Elucidating details of biology’s selective uptake and trafficking of rare earth elements, particularly the lanthanides, has the potential to inspire sustainable biomolecular separations of these essential metals for myriad modern technologies. Here, we biochemically and structurally characterize Methylobacterium (Methylorubrum) extorquens LanD, a periplasmic protein from a bacterial gene cluster for lanthanide uptake. This protein provides only four ligands at its surface-exposed lanthanide-binding site, allowing for metal-centered protein dimerization that favors the largest lanthanide, La III . However, the monomer prefers Nd III and Sm III , which are disfavored lanthanides for cellular utilization. Structure-guided mutagenesis of a metal-ligand and an outer-sphere residue weakens metal binding to the LanD monomer and enhances dimerization for Pr III and Nd III by 100-fold. Selective dimerization enriches high-value Pr III and Nd III relative to low-value La III and Ce III in an all-aqueous process, achieving higher separation factors than lanmodulins and comparable or better separation factors than common industrial extractants. Finally, we show that LanD interacts with lanmodulin (LanM), a previously characterized periplasmic protein that shares LanD’s preference for Nd III and Sm III . Our results suggest that LanD’s unusual metal-binding site transfers less-desirable lanthanides to LanM to siphon them away from the pathway for cytosolic import. The properties of LanD show how relatively weak chelators can achieve high selectivity, and they form the basis for the design of protein dimers for separation of adjacent lanthanide pairs and other metal ions.

lanthanide biochemistry↗
DOE OSTI2021

Structural analysis of the catalytic domain of Artemis endonuclease/SNM1C reveals distinct structural features

The endonuclease Artemis is responsible for opening DNA hairpins during V(D)J recombination and for processing a subset of pathological DNA double-strand breaks. Artemis is an attractive target for the development of therapeutics to manage various B cell and T cell tumors, because failure to open DNA hairpins and accumulation of chromosomal breaks may reduce the proliferation and viability of pre-T and pre-B cell derivatives. However, structure-based drug discovery of specific Artemis inhibitors has been hampered by a lack of crystal structures. Here, we report the structure of the catalytic domain of recombinant human Artemis. The catalytic domain displayed a polypeptide fold similar overall to those of other members in the DNA cross-link repair gene SNM1 family and in mRNA 3'-end-processing endonuclease CPSF-73, containing metallo-β-lactamase and β-CASP domains and a cluster of conserved histidine and aspartate residues capable of binding two metal atoms in the catalytic site. As in SNM1A, only one zinc ion was located in the Artemis active site. However, Artemis displayed several unique features. Unlike in other members of this enzyme class, a second zinc ion was present in the β-CASP domain that leads to structural reorientation of the putative DNA-binding surface and extends the substrate-binding pocket to a new pocket, pocket III. Moreover, the substrate-binding surface exhibited a dominant and extensive positive charge distribution compared with that in the structures of SNM1A and SNM1B, presumably because of the structurally distinct DNA substrate of Artemis. The structural features identified here may provide opportunities for designing selective Artemis inhibitors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

HUBBLE SPACE TELESCOPE FUV SPECTRA OF THE POST-COMMON-ENVELOPE HYADES BINARY V471 Tauri

We have carried out an analysis of the Hubble Space Telescope (HST)/STIS archival spectra of the magnetic white dwarf (WD) in the Hyades eclipsing-spectroscopic, post-common-envelope binary V471 Tauri, time resolved on the orbit and on the X-ray rotational phase of the magnetic WD. An HST/STIS spectrum obtained during primary eclipse reveals a host of transition region/chromospheric emission features including N V (1238, 1242), Si IV (1393, 1402), C IV (1548, 1550), and He II (1640). The spectroscopic characteristics and emission line fluxes of the transition region/chromosphere of the very active, rapidly rotating, K2V component of V471 Tauri are compared with the emission characteristics of fast rotating K dwarfs in young open clusters. We have detected a number of absorption features associated with metals accreted onto the photosphere of the magnetic WD from which we derive radial velocities. All of the absorption features are modulated on the 555 s rotation period of the WD with maximum line strength at rotational phase 0.0 when the primary magnetic accretion region is facing the observer. The photospheric absorption features show no clear evidence of Zeeman splitting and no evidence of a correlation between their variations in strength and orbital phase. We report clear evidence of a secondary accretion pole. We derive C and Si abundances from the Si IV and C III features. All other absorption lines are either interstellar or associated with a region above the WD and/or with coronal mass ejection events illuminated as they pass in front of the WD.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

Comparative genomics of freshwater Fe-oxidizing bacteria: implications for physiology, ecology, and systematics

The two microaerophilic, Fe-oxidizing bacteria (FeOB) Sideroxydans ES-1 and Gallionella ES-2 have single circular chromosomes of 3.00 and 3.16 Mb that encode 3049 and 3006 genes, respectively. Multi-locus sequence analysis (MLSA) confirmed the relationship of these two organisms to one another, and indicated they may form a novel order, the Gallionellalaes, within the Betaproteobacteria. Both are adapted for chemolithoautotropy, including pathways for CO2-fixation, and electron transport pathways adapted for growth at low O2-levels, an important adaptation for growing on Fe(II). Both genomes contain Mto-genes implicated in iron-oxidation, as well as other genes that could be involved in Fe-oxidation. Nearly 10% of their genomes are devoted to environmental sensing, signal transduction, and chemotaxis, consistent with their requirement for growing in narrow redox gradients of Fe(II) and O2. There are important differences as well. Sideroxydans ES-1 is more metabolically flexible, and can utilize reduced S-compounds, including thiosulfate, for lithotrophic growth. It has a suite of genes for nitrogen fixation. Gallionella ES-2 contains additional gene clusters for exopolysaccharide production, and has more capacity to resist heavy metals. Both strains contain genes for hemerythrins and globins, but ES-1 has an especially high numbers of these genes that may be involved in oxygen homeostasis, or storage. The two strains share homology with the marine FeOB Mariprofundus ferrooxydans PV-1 in CO2 fixation genes, and respiratory genes. In addition, ES-1 shares a suite of 20 potentially redox active genes with PV-1, as well as a large prophage. Combined these genetic, morphological, and physiological differences indicate that these are two novel species, Sideroxydans lithotrophicus ES-1T (ATCC 700298T; JCM 14762; DSMZ 22444; NCMA B100), and Gallionella capsiferriformans ES-2T (ATCC 700299T; JCM 14763; DSMZ 22445; NCMA B101).

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1993

Diffuse X-ray emission from the NGC 2300 group of galaxies - Implications for dark matter and galaxy evolution in small groups

The discovery of diffuse X-ray emission from the NGC 2300 group of galaxies using the ROSAT Position Sensitive Proportional Counter is reported. The gas distributions is roughly symmetric and extends to a radius of at least 0.2/h(50) Mpc. A Raymond-Smith hot plasma model provides an excellent fit the X-ray spectrum with a best-fit value temperature of 0.9 + -/15 or - 0.14 keV and abundance 0.06 + 0/.12 or - 0.05 solar. The assumption of gravitational confinement leads to a total mass of the group of 3.0 + 0.4 or - 0.5 x 10 exp 13 solar. Baryons can reasonably account for 4 percent of this mass, and errors could push this number not higher than 10-15 percent. This is one of the strongest pieces of evidence that dark matter dominates small groups such as this one. The intragroup medium in this system has the lowest metal abundance yet found in diffuse gas in a group or cluster.

Mulchaey, John S.↗
DOE OSTI2023

Optical tags comprising rare earth metal-organic frameworks

Optical tags provide a way to identify assets quickly and unambiguously, an application relevant to anti-counterfeiting and protection of valuable resources or information. The present invention is directed to a tag fluorophore that encodes multilayer complexity in a family of heterometallic rare-earth metal-organic frameworks (RE-MOFs) based on highly connected polynuclear clusters and carboxylic acid-based linkers. Both overt (visible) and covert (near infrared, NIR) properties with concomitant multi-emissive spectra and tunable luminescence lifetimes impart both intricacy and security. Tag authentication can be validated with a variety of orthogonal detection methodologies. The relationships between structure, composition, and optical properties of the family of RE-MOFs can be used to create a large library of rationally designed, highly complex, difficult to counterfeit optical tags.

Sava Gallis, Dorina F.↗
DOE OSTI2016

Line-of-sight velocity and metallicity measurements of the palomar 5 tidal stream

We present Subaru/Faint Object Camera and Spectrograph and Keck/Deep Imaging Multi-Object Spectrometer medium-resolution spectroscopy of a tidally disrupting Milky Way (MW) globular cluster Palomar 5 (Pal 5) and its tidal stream. The observed fields are located to cover an angular extent of ∼17° along the stream, providing an opportunity to investigate a trend in line-of-sight velocities (V {sub los}) along the stream, which is essential to constrain its orbit and underlying gravitational potential of the MW’s dark matter halo. A spectral fitting technique is applied to the observed spectra to obtain stellar parameters and metallicities ([Fe/H]) of the target stars. The 19 stars most likely belonging to the central Pal 5 cluster have a mean V {sub los} of −58.1 ± 0.7 km s{sup −1} and metallicity [Fe/H] = −1.35 ± 0.06 dex, both of which are in good agreement with those derived in previous high-resolution spectroscopic studies. Assuming that the stream stars have the same [Fe/H] as the progenitor cluster, the derived [Fe/H] and V{sub los} values are used to estimate the possible V {sub los} range of the member stars at each location along the stream. Because of the heavy contamination of the field MW stars, the estimated V {sub los} range depends on prior assumptions about the stream’s V{sub los}, which highlights the importance of more definitely identifying the member stars using proper motion and chemical abundances to obtain unbiased information of V {sub los} in the outer part of the Pal 5 stream. The models for the gravitational potential of the MW’s dark matter halo that are compatible with the estimated V {sub los} range are discussed.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

On Decoration of a Zigzag Edge of Epitaxial Graphene

Two approaches are proposed to the problem of the coupling of adsorbed particles with atoms of a zigzag edge of graphene formed on a metal substrate. The first approach is based on the Kalkstein and Soven scheme, which makes it possible to determine the electronic structure of a semi-infinite graphene sheet. The second approach is based on a cluster model of a zigzag edge. Analytical expressions are obtained for the local densities of the system’s states and the occupation numbers of a carbon adatom and an adparticle. The case of an isolated adparticle is considered in detail, and a method of taking into account the dipole–dipole interaction of particles aligned along the edge is proposed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Effect of Electron–Phonon Interaction on the Conductivity and Work Function of Epitaxial Graphene

In the context of the cluster model of epitaxial graphene, the condition for a stepwise change in the charge of carbon atoms under the action of graphene–substrate electron–phonon interaction and an external electric field is derived. Such charge transfer brings about corresponding steps of the static conductivity and work function of epitaxial graphene. Numerical estimates for the case of weak coupling of quasi-free graphene with metal and semiconductor substrates are given.

36 MATERIALS SCIENCE↗
NASA NTRS1988

The ultraviolet spectra of M31 globular clusters

Ultraviolet spectra of 11 of the brightest globular clusters in M31 show that some exhibit residual flux below 3000 A, greater than that expected from the bright, evolved stars in the cluster. There seems to be no apparent correlation of the strength of this ultraviolet flux with parameters such as metallicity, U-B color, visual magnitude, X-ray emission, or location within the parent galaxy. However, comparison of the ultraviolet colors of the M31 globular clusters with those in the Galaxy and in the Large Magellanic Cloud suggests that the M31 clusters may contain a high percentage of blue horizontal-branch stars or that some clusters could be as young as about 2 x 10 to the 9th yr.

Cowley, A. P.↗