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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Synthesis, structural characterization, and electronic structure of the novel Zintl phase Ba 2 ZnP 2

The novel Zintl phase dibarium zinc diphosphide (Ba 2 ZnP 2 ) was synthesized for the first time. This was accom­plished using the Pb flux technique, which allowed for the growth of crystals of adequate size for structural determination via single-crystal X-ray diffraction methods. The Ba 2 ZnP 2 com­pound was determined to crystallize in a body-centered ortho­rhom­bic space group, Ibam (No. 72). Formally, this crystallographic arrangement belongs to the K 2 SiP 2 structure type. Therefore, the structure can be best described as infinite [ZnP 2 ] 4– polyanionic chains with divalent Ba 2+ cations located between the chains. All valence electrons are partitioned, which conforms to the Zintl–Klemm concept and suggests that Ba 2 ZnP 2 is a valence-precise com­position. In conclusion, the electronic band structure of this new com­pound, com­puted with the aid of the TB–LMTO–ASA code, shows that Ba 2 ZnP 2 is an intrinsic semiconductor with a band gap of ca 0.6 eV.

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

Crystal Structure of BamB from Pseudomonas aeruginosa and Functional Evaluation of Its Conserved Structural Features

The assembly of β-barrel Outer Membrane Proteins (OMPs) in the outer membrane is essential for Gram-negative bacteria. The process requires the β-Barrel Assembly Machine (BAM), a multiprotein complex that, in E. coli, is composed of the OMP BamA and four lipoproteins BamB-E. Whereas BamA and BamD are essential, deletion of BamB, C or E produce membrane permeability defects. Here we present the high-resolution structure of BamB from Pseudomonas aeruginosa. This protein can complement the deletion of bamB in E. coli indicating that they are functionally equivalent. Conserved structural features include an eight-bladed β-propeller fold stabilized by tryptophan docking motifs with a central pore about 8 Å in diameter at the narrowest point. This pore distinguishes BamB from related b-propellers, such as quinoprotein dehydrogenases. However, a double mutation designed to block this pore was fully functional indicating that the opening is not essential. Two loops protruding from the bottom of the propeller are conserved and mediate binding to BamA. Conversely, an additional loop only present in E. coli BamB is not required for function. A cluster of highly conserved residues in a groove between blades 6 and 7 is crucial for proper BamB folding or biogenesis. It has been proposed that BamB may bind nascent OMPs by β-augmentation to its propeller outer strands, or recognize the aromatic residue signature at the C-terminus of OMPs. However, Isothermal Titration Calorimetry experiments and structural analysis do not support these proposals. The structural and mutagenesis analysis suggests that the main function of BamB is to bind and modulate BamA, rather than directly interact with nascent OMPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Structural characteristics of lipocalin allergens: Crystal structure of the immunogenic dog allergen Can f 6

Lipocalins represent the most important protein family of the mammalian respiratory allergens. Four of the seven named dog allergens are lipocalins: Can f 1, Can f 2, Can f 4, and Can f 6. We present the structure of Can f 6 along with data on the biophysical and biological activity of this protein in comparison with other animal lipocalins. The Can f 6 structure displays the classic lipocalin calyx-shaped ligand binding cavity within a central β-barrel similar to other lipocalins. Despite low sequence identity between the different dog lipocalin proteins, there is a high degree of structural similarity. On the other hand, Can f 6 has a similar primary sequence to cat, horse, mouse lipocalins as well as a structure that may underlie their cross reactivity. Interestingly, the entrance to the ligand binding pocket is capped by a His instead of the usually seen Tyr that may help select its natural ligand binding partner. Our highly pure recombinant Can f 6 is able to bind to human IgE (hIgE) demonstrating biological antigenicity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

The Structure of Glycine Dihydrate: Implications for the Crystallization of Glycine from Solution and Its Structure in Outer Space

Glycine, the simplest amino acid, is also the most polymorphous. Herein, we report the structure determination of an unknown phase of glycine which was firstly reported by Pyne and Suryanarayanan in 2001. To date, the new phase has only been prepared at 208 K as nanocrystals within ice. Through computational crystal structure prediction and powder X-ray diffraction methods, we identified this elusive phase as glycine dihydrate (GDH), representing a first report on a hydrated glycine structure. The structure of GDH has important implications for the state of glycine in aqueous solution, and the mechanisms of glycine crystallization. GDH may also be the form of glycine that comes to Earth from extraterrestrial sources.

amino acid↗
DOE OSTI2012

Structural, kinetic, and thermodynamic studies of specificity designed HIV-1 protease

HIV-1 protease recognizes and cleaves more than 12 different substrates leading to viral maturation. While these substrates share no conserved motif, they are specifically selected for and cleaved by protease during viral life cycle. Drug resistant mutations evolve within the protease that compromise inhibitor binding but allow the continued recognition of all these substrates. While the substrate envelope defines a general shape for substrate recognition, successfully predicting the determinants of substrate binding specificity would provide additional insights into the mechanism of altered molecular recognition in resistant proteases. We designed a variant of HIV protease with altered specificity using positive computational design methods and validated the design using X-ray crystallography and enzyme biochemistry. The engineered variant, Pr3 (A28S/D30F/G48R), was designed to preferentially bind to one out of three of HIV protease's natural substrates; RT-RH over p2-NC and CA-p2. In kinetic assays, RT-RH binding specificity for Pr3 increased threefold compared to the wild-type (WT), which was further confirmed by isothermal titration calorimetry. Crystal structures of WT protease and the designed variant in complex with RT-RH, CA-p2, and p2-NC were determined. Structural analysis of the designed complexes revealed that one of the engineered substitutions (G48R) potentially stabilized heterogeneous flap conformations, thereby facilitating alternate modes of substrate binding. Our results demonstrate that while substrate specificity could be engineered in HIV protease, the structural pliability of protease restricted the propagation of interactions as predicted. These results offer new insights into the plasticity and structural determinants of substrate binding specificity of the HIV-1 protease.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Interstitial Atoms and the Frustrated and Allowed Structural Transitions Principle: Tunability in the Electronic Structure of AuCu 3 ‐type Frameworks in Dy 4 T 1− x Ga 12 (T = Ag, Ir)

In this Article, we explore how the chemical pressure (CP) features of an intermetallic phase may provide opportunities to couple perturbations in electron count with the stabilization of the underlying geometrical structure. AuCu 3 ‐type LnGa 3 (Ln = lanthanide or group 3 metal) phases contain octahedral cavities of negative CP held open by overly compressed Ln–Ga interactions, leading to a series of transition metal‐stuffed derivatives. We present new additions to this family with the synthesis and crystal structures of Dy 4 T 1−x Ga 12 with (T, x) = (Ag, 0.29) and (Ir, 0.15), adopting Y 4 PdGa 12 ‐type superstructures of the AuCu 3 ‐type. density functional Ttheory (DFT)‐CP calculations, when adjusted to avoid dipolar CP features, affirm that T atom incorporation provides a mechanism for the relief of packing tensions, while electronic density of states distributions illustrate that the T atoms serve largely as electron or hole donors to the band structure, as needed for them to attain d 10 configurations. The maximum obtainable value for x may be limited by a mismatch between the Fermi energy and pseudogap, in line with the balance of factors envisioned by the frustrated and allowed structural transitions principle. Furthermore, trends in resistivity measurements on T = Ir, Pd, and Ag compounds are interpretable in terms of the varying degrees of disorder arising from x < 1.0.

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

Rationalizing the photophysical properties of BODIPY laser dyes via aromaticity and electron-donor-based structural perturbations

The absorption and fluorescence properties of six boron dipyrromethene (BODIPY) laser dyes with simple non-aromatic substituents are rationalized by relating them to observable structural perturbations within the molecules of the dyes. An empirical relationship involving the structure and the optical properties is derived using a combination of single-crystal X-ray diffraction data, quantum chemical calculations and electronic constants: i.e. the tendency of the pyrrole bond lengths towards aromaticity and the UV-vis absorption and fluorescence wavelengths correlating with the electron-donor properties of the substituents. The effect of molecular conformation on the solid-state optical properties of the dyes is also discussed. The findings in this study also demonstrate the usefulness and limitations of using crystal structure data to develop structure-property relationships in this class of optical materials, contributing to the growing effort to design optoelectronic materials with tunable properties via molecular engineering.

absorption↗
DOE OSTI2012

Synthesis, crystal structures and properties of lanthanide-organic frameworks based benzene carboxylates with two/three-dimensional structure

A series of lanthanide coordination polymers, {l_brace}[Dy{sub 3}(1,3-BDC){sub 4}(NO{sub 3})(phen){sub 3}]{center_dot}2H{sub 2}O{r_brace}{sub n} (1), {l_brace}[Dy{sub 2}(1,3-BDC){sub 3}(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace}{sub n} (2), {l_brace}[Ln{sub 4}(1,3-BDC){sub 6}(DMF)(H{sub 2}O){sub 4}]{center_dot}DMF{center_dot}2H{sub 2}O{r_brace}{sub n} (Ln=Tb (3), Ho (4), Er (5), 1,3-H{sub 2}BDC=1,3-benzenedicarboxylate, phen=1,10-phenanthroline, DMF=N,N-dimethylformamide), have been synthesized and characterized. In coordination polymer 1, each Dy{sup 3+} ion is connected to its neighboring Dy{sup 3+} ion through bridging carboxyl oxygen atoms of the 1,3-BDC{sup 2-} ligands to form a new three-dimensional open-framework structure which the Schlaefli symbol of {l_brace}6{sup 4}{center_dot}8{sup 2}{r_brace}{sub 2}{l_brace}6{sup 6}{r_brace}. In coordination polymer 2, center metal dysprosium ions are interlaced and connected through bridging carboxyl oxygen atoms to form an infinite helix chain. Two helix chains are linked through the 1,3-BDC{sup 2-} ligand to give rise to the two-dimensional layered structure. Coordination polymers 3-5 are isomorphous, which displays a (3,4)-connected net with the point symbol of {l_brace}4{sup 2}{center_dot}6{sup 3}{center_dot}8{r_brace}{l_brace}4{sup 2}{center_dot}6{r_brace}. The solid-state photoluminescence properties and lifetimes of the Dy (1 and 2) and Tb (3) coordination polymers have been measured at room temperature. Highlights: Black-Right-Pointing-Pointer Five lanthanide coordination polymers based on 1,3-H{sub 2}BDC were obtained. Black-Right-Pointing-Pointer The polymers were structurally characterized by single-crystal X-ray diffraction. Black-Right-Pointing-Pointer Coordination polymers 1-5 display different topological structures. Black-Right-Pointing-Pointer They show characteristic emissions of lanthanide ions in the solid state.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Investigation of magnetic properties and electronic structure of layered-structure borides AlT{sub 2}B{sub 2} (T=Fe, Mn, Cr) and AlFe{sub 2–x}Mn{sub x}B{sub 2}

The ternary phases AlT{sub 2}B{sub 2} (T=Fe, Mn, Cr) and quaternary phases AlFe{sub 2–x}Mn{sub x}B{sub 2} have been synthesized by arc-melting and characterized by powder X-ray diffraction, magnetic measurements, Mössbauer spectroscopy, and electronic band structure calculations. All the compounds adopt the AlFe{sub 2}B{sub 2}-type structure, in which infinite zigzag chains of B atoms are connected by Fe atoms into [Fe{sub 2}B{sub 2}] slabs that alternate with layers of Al atoms along the b axis. The magnetic measurements reveal that AlFe{sub 2}B{sub 2} is a ferromagnet with T{sub C}=282 K while AlMn{sub 2}B{sub 2} and AlCr{sub 2}B{sub 2} do not show magnetic ordering in the studied temperature range of 1.8–400 K. A systematic investigation of solid solutions AlFe{sub 2−x}Mn{sub x}B{sub 2} showed a non-linear change in the structural and magnetic behavior. The ferromagnetic ordering temperature is gradually decreased as the Mn content (x) increases. The Mössbauer spectra reveal the presence of non-magnetic (NM) and ferromagnetic (FM) spectral components in all Mn-containing samples, with the amount of NM fraction increasing as the Mn content increases. While for the AlFe{sub 2−x}Mn{sub x}B{sub 2} samples with x=0.0 and 0.4 the hyperfine splitting of the FM spectral component collapses at temperatures close to the Curie temperatures determined from the magnetic measurements, for the x=1.2 and 1.6 samples the FM fraction exhibits a sizable unquenched hyperfine splitting at room temperature, a finding that is inconsistent with the observed magnetic properties. Along with the increase in the amount of the NM fraction, this observation suggests formation of Fe-rich and Mn-rich regions in the structure of the solid solutions. Quantum-chemical calculations and crystal orbital Hamilton population analysis provide a clear explanation of the distinction in properties for this series of compounds and also reveal the importance of electronic factors in modifying the magnetic properties of these materials. - Graphical abstract: We follow a gradual evolution of magnetic properties in a series of ternary borides AlT{sub 2}B{sub 2}, from non-magnetic AlCr{sub 2}B{sub 2} and AlMn{sub 2}B{sub 2} to ferromagnetic AlFe{sub 2}B{sub 2}. - Highlights: • AlT{sub 2}B{sub 2} (T=Fe, Mn, Cr) and AlFe{sub 2−x}Mn{sub x}B{sub 2} were prepared by arc‐melting. • Bulk ferromagnetism of AlFe{sub 2}B{sub 2} is gradually suppressed by the introduction of Mn. • AlMn{sub 2}B{sub 2} and AlCr{sub 2}B{sub 2} do not exhibit magnetic ordering. • Nonmagnetic (Mn‐rich) and ferromagnetic (Fe‐rich) clustering in AlFe{sub 2–x}Mn{sub x}B{sub 2}. • Ferromagnetism is suppressed due to weakening of antibonding T–T interactions.

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

Structural, magnetic and electronic structure properties of Co doped ZnO nanoparticles

Highlights: • XRD and HR-TEM results show the single phase nature of Co doped ZnO nanoparticles. • XMCD and dc magnetization results indicate the RT-FM in Co doped ZnO nanoparticles. • Co L{sub 3,2} NEXAFS spectra infer that Co ions are in 2+ valence state. • O K edge NEXAFS spectra show that O vacancy increases with Co doping in ZnO. - Abstract: We reported structural, magnetic and electronic structure studies of Co doped ZnO nanoparticles. Doping of Co ions in ZnO host matrix has been studied and confirmed using various methods; such as X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersed X-ray (EDX), high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, magnetic hysteresis loop measurements and X-ray magnetic circular dichroism (XMCD). From the XRD and HR-TEM results, it is observed that Co doped ZnO nanoparticles have single phase nature with wurtzite structure and exclude the possibility of secondary phase formation. FE-SEM and TEM micrographs show that pure and Co doped nanoparticles are nearly spherical in shape. O K edge NEXAFS spectra indicate that O vacancies increase with Co doping. The Co L{sub 3,2} edge NEXAFS spectra revealed that Co ions are in 2+ valence state. DC magnetization hysteresis loops and XMCD results clearly showed the intrinsic origin of temperature ferromagnetism in Co doped ZnO nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗