Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Structural”

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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

A Ni(II) Bis(diphosphine)-Hydride Complex Containing Proton Relays - Structural Characterization and Electrocatalytic Studies

The syntheses of the new 1,5-diphenyl-3,7-di(isopropyl)-1,5-diaza-3,7-diphosphacyclooctane ligand, PiPr2NPh2, is reported. The two equivalents of the ligand react with [Ni(CH3CN)6](BF4)2 to form the bis-diphosphine Ni(II)-complex [Ni(PiPr2NPh2)2](BF4)2, which acts as a proton reduction electrocatalyst. In addition to [Ni(PiPr2NPh2)2]2+, we report the syntheses and structural characterization of the Ni(0)-complex Ni(PiPr2NPh2)2, and the Ni(II)-hydride complex [HNi(PiPr2NPh2)2]BF4. The [HNi(PiPr2NPh2)2]BF4 complex represents the first Ni(II)-hydride in the [Ni(PR2NR'2)2]2+ family of compounds to be isolated and structurally characterized. In addition to the experimental data, the mechanism of electrocatalysis facilitated by [Ni(PiPr2NPh2)2]2+ is analyzed using linear free energy relationships recently established for the [Ni(PR2NR'2)2]2+ family. We thank Dr. Aaron Appel, Dr. Simone Raugei and Dr. Eric Wiedner for helpful discussions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Mass spectrometry was provided at W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s office of Biological and Environmental Research located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

diphosphine↗
DOE OSTI2016

The structure of a doripenem‐bound OXA‐51 class D β‐lactamase variant with enhanced carbapenemase activity

Abstract OXA‐51 is a class D β‐lactamase that is thought to be the native carbapenemase of Acinetobacter baumannii . Many variants of OXA‐51 containing active site substitutions have been identified from A. baumannii isolates, and some of these substitutions increase hydrolytic activity toward carbapenem antibiotics. We have determined the high‐resolution structures of apo OXA‐51 and OXA‐51 with one such substitution (I129L) with the carbapenem doripenem trapped in the active site as an acyl‐intermediate. The structure shows that acyl‐doripenem adopts an orientation very similar to carbapenem ligands observed in the active site of OXA‐24/40 (doripenem) and OXA‐23 (meropenem). In the OXA‐51 variant/doripenem complex, the indole ring of W222 is oriented away from the doripenem binding site, thereby eliminating a clash that is predicted to occur in wildtype OXA‐51. Similarly, in the OXA‐51 variant complex, L129 adopts a different rotamer compared to I129 in wildtype OXA‐51. This alternative position moves its side chain away from the hydroxyethyl moiety of doripenem and relieves another potential clash between the enzyme and carbapenem substrates. Molecular dynamics simulations of OXA‐51 and OXA‐51 I129L demonstrate that compared to isoleucine, a leucine at this position greatly favors a rotamer that accommodates the ligand. These results provide a molecular justification for how this substitution generates enhanced binding affinity for carbapenems, and therefore helps explain the prevalence of this substitution in clinical OXA‐51 variants.

June, Cynthia M.↗
DOE OSTI2018

4-Hydroxy-tetrahydrodipicolinate reductase from Neisseria gonorrhoeae – structure and interactions with coenzymes and substrate analog

Highlights: • N. gonorrhoeae is an obligate human pathogen which is a leading cause of communicable diseases. • 4-Hydroxy-tetrahydrodipicolinate reductase from N. gonorrhoeae (NgDapB) is a new drug target, and its structure was determined. • ITC we have demonstrated and characterized binding of NADH, NADPH and an inhibitor (2,6-PDC) to NgDapB. • In the case of NgDapB, the ITC results suggest random sequential mechanism for substrate binding. • A large scale analysis of DapBs' sequences revealed that DapBs can be segregated into three distinct groups. Neisseria gonorrhoeae, an obligate human pathogen, is a leading cause of communicable diseases globally. Due to rapid development of drug resistance, the rate of successfully curing gonococcal infections is rapidly decreasing. Hence, research is being directed toward finding alternative drugs or drug targets to help eradicate these infections. 4-Hydroxy-tetrahydrodipicolinate reductase (DapB), an important enzyme in the meso-diaminopimelate pathway, is a promising target for the development of new antibiotics. This manuscript describes the first structure of DapB from N. gonorrhoeae determined at 1.85 Å. This enzyme uses NAD(P)H as cofactor. Details of the interactions of the enzyme with its cofactors and a substrate analog/inhibitor are discussed. A large scale bioinformatics analysis of DapBs' sequences is also described.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2013

Controlling structure distortions in 3-layer ferroelectric Aurivillius oxides

Combined Rietveld refinements of x-ray and neutron powder diffraction data were used to understand the subtle structure distortions in 3-layer Aurivillius oxides that yield off-centering displacements in ferroelectric and multiferroic compositions. Ferroelectric phases including Bi{sub 2}A{sub 2}Ti{sub 3}O{sub 12} (A=La, Pr, Nd, La/Pr, La/Nd, Pr/Nd), Bi{sub 2}A{sub 2}TiNb{sub 2}O{sub 12} (A=Ca/Sr, Sr, and Sr/Ba) and Bi{sub 2}A{sub 2}TiTa{sub 2}O{sub 12} (A=Ca/Sr, and Sr/Ba) were studied to separate the effects of cation size and charge on the structure distortions and properties. A new approach to describing the local coordination around the Ti, Nb, and/or Ta ions is presented, where the oxygen octahedra are characterized as containing kinks in three dimensions. The kink angles follow trends with the A-site ionic radius and the ferroelectric polarization. The driving force for extensive cation site mixing between the Bi and A-site cations has been clearly established, with site mixing required to maintain interlayer bonding. - Graphical abstract: Distortion of the oxygen octahedra from planar geometries can be controlled via choice of the perovskite A-site cation, and the kink angle correlates with cation off-centering and ferroelectric polarization. Highlights: Black-Right-Pointing-Pointer A-site cations define the tilt and distortion of the octahedral. Black-Right-Pointing-Pointer Distortions of oxygen octahedra, ignoring the central cation, link to ferroelectric polarization. Black-Right-Pointing-Pointer Bi ion occupancy in the perovskite causes distortion of the oxygen sublattice. Black-Right-Pointing-Pointer We predict multiferroic behavior from off-centering caused by the Bi ion lone pair.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Three Dimensional Mapping of Nicle Oxidation States Using Full Field Xray Absorption Near Edge Structure Nanotomography

The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Non-Gaussian structure of B-mode polarization after delensing

The B-mode polarization of the cosmic microwave background on large scales has been considered as a probe of gravitational waves from the cosmic inflation. Ongoing and future experiments will, however, suffer from contamination due to the B-modes of non-primordial origins, one of which is the lensing induced B-mode polarization. Subtraction of the lensing B-modes, usually referred to as delensing, will be required for further improvement of detection sensitivity of the gravitational waves. In such experiments, knowledge of statistical properties of the B-modes after delensing is indispensable to likelihood analysis particularly because the lensing B-modes are known to be non-Gaussian. In this paper, we study non-Gaussian structure of the delensed B-modes on large scales, comparing it with that of the lensing B-modes. In particular, we investigate the power spectrum correlation matrix and the probability distribution function (PDF) of the power spectrum amplitude. Assuming an experiment in which the quadratic delensing is an almost optimal method, we find that delensing reduces correlations of the lensing B-mode power spectra between different multipoles, and that the PDF of the power spectrum amplitude is well described as a normal distribution function with a variance larger than that in the case of a Gaussian field. These features are well captured by an analytic model based on the 4th order Edgeworth expansion. As a consequence of the non-Gaussianity, the constraint on the tensor-to-scalar ratio after delensing is degraded within approximately a few percent, which depends on the multipole range included in the analysis.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

Event structure and double helicity asymmetry in jet production from polarized p+p collisions at (sq rt) s = 200 GeV

We report on the event structure and double helicity asymmetry (A{sub LL}) of jet production in longitudinally polarized p+p collisions at {radical}s = 200 GeV. Photons and charged particles were measured by the PHENIX experiment at midrapidity |{eta}| < 0.35 with the requirement of a high-momentum (> 2 GeV/c) photon in the event. Event structure, such as multiplicity, p{sub T} density and thrust in the PHENIX acceptance, were measured and compared with the results from the pythia event generator and the geant detector simulation. The shape of jets and the underlying event were well reproduced at this collision energy. For the measurement of jet ALL, photons and charged particles were clustered with a seed-cone algorithm to obtain the cluster p{sub T} sum (p{sub T}{sup reco}). The effect of detector response and the underlying events on p{sub T}{sup reco} was evaluated with the simulation. The production rate of reconstructed jets is satisfactorily reproduced with the next-to-leading-order and perturbative quantum chromodynamics jet production cross section. For 4 < p{sub T}{sup reco} < 12 GeV/c with an average beam polarization of <P> = 49% we measured A{sub LL} = -0.0014 {+-} 0.0037{sup stat} at the lowest p{sub T}{sup reco} bin (4-5 GeV/c) and -0.0181 {+-} 0.0282{sup stat} at the highest p{sub T}{sup reco} bin (10-12 GeV/c) with a beam polarization scale error of 9.4% and a p{sub T} scale error of 10%. Jets in the measured p{sub T}{sup reco} range arise primarily from hard-scattered gluons with momentum fraction 0.02 < x < 0.3 according to pythia. The measured A{sub LL} is compared with predictions that assume various {Delta}G(x) distributions based on the Gluck-Reya-Stratmann-Vogelsang parameterization. The present result imposes the limit -1.1 < {integral}{sub 0.02}{sup 0.3}dx{Delta}G(x,{mu}{sup 2} = 1 GeV{sup 2}) < 0.4 at 95% confidence level or {integral}{sub 0.02}{sup 0.3}dx{Delta}G(x,{mu}2 = 1 GeV{sup 2}) < 0.5 at 99% confidence level.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗