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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 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2010

Evidence of antimagnetic rotation in odd-A {sup 105}Cd

The lifetimes of the levels above spin 23/2{sup -} in the negative-parity yrast band of {sup 105}Cd have been measured using the Doppler shift attenuation method. The obtained B(E2) values are small and show a decrease with an increase in spin. This establishes, for the first time, antimagnetic rotation (AMR) in an odd-A nucleus. An excellent agreement between the theoretical (semiclassical model) and experimental results along with a large I{sup (2)}/B(E2) ratio for the states strongly suggests that the structure of the levels beyond spin 23/2{sup -} has the character of a twin-shears type AMR band resulting from the coupling of a pair of g{sub 9/2} proton holes with aligned h{sub 11/2} and (g{sub 7/2}){sup 2} neutron particles, along with a small contribution from the core rotation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2010

QCD corrections to nonstandard WZ+jet production with leptonic decays at the LHC

We discuss the impact of anomalous WW{gamma} and WWZ couplings on WZ+jet production at next-to-leading order QCD, including full leptonic decays of the electroweak gauge bosons. While the inclusive hadronic cross sections do not exhibit any particular sensitivity to anomalous couplings once the residual QCD scale uncertainties are taken into account, the transverse momentum distributions show substantial deviations from the standard model, provided that the anomalous vertices are probed at large enough momentum transfers.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

W{sup {+-}H{+-}} production and CP asymmetry at the LHC

The dominant contributions to W{sup {+-}H{+-}} production at the LHC are the tree-level bb annihilation and the gg fusion. We perform for the case of the complex minimal supersymmetric standard model (MSSM) a complete calculation of the next-to-leading order (NLO) electroweak corrections to the bb annihilation channel and a consistent combination with other contributions including the standard and supersymmetric-QCD (SUSY-QCD) corrections and the gg fusion, with resummation of the leading radiative corrections to the bottom-Higgs couplings and the neutral Higgs boson propagators. We observe a large CP-violating asymmetry, arising mainly from the gg channel.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Higgs phenomenology in warped extra dimensions with a fourth generation

We study a warped extra-dimension scenario where the standard model fields lie in the bulk, with the addition of a fourth family of fermions. We concentrate on the flavor structure of the Higgs couplings with fermions in the flavor anarchy ansatz. Even without a fourth family, these couplings will be generically misaligned with respect to the standard model fermion mass matrices. The presence of the fourth family typically enhances the misalignment effects and we show that one should expect them to be highly nonsymmetrical in the (34) intergenerational mixing. The radiative corrections from the new fermions and their flavor-violating couplings to the Higgs affect negligibly known experimental precision measurements such as the oblique parameters and Z{yields}bb or Z{yields}{mu}{sup +}{mu}{sup -}. On the other hand, {Delta}F=1, 2 processes, mediated by tree-level Higgs exchange, as well as radiative corrections to b{yields}s{gamma} and {mu}{yields}e{gamma} put some generic pressure on the allowed size of the flavor-violating couplings. But more importantly, these couplings will alter the Higgs decay patterns as well as those of the new fermions, and produce very interesting new signals associated to Higgs phenomenology in high energy colliders. These signals might become very important indirect signals for these type of models as they would be present even when the KK mass scale is high and no heavy KK particle is discovered.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2010

Bounding W-W{sup '} Mixing with Spin Asymmetries at RHIC

The W boson can obtain a small right-handed coupling to quarks and leptons through mixing with a hypothetical W{sup '} boson that appears in many extensions of the standard model. Measuring or even bounding this coupling to the light quarks is very challenging. Only one model independent bound on the absolute value of the complex mixing parameter has been obtained to date. Here we discuss a method sensitive to both the real and CP-violating imaginary parts of the coupling, independent of assumptions on the new physics, and demonstrate quantitatively the feasibility of its measurement at RHIC.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Search for High Mass Resonances Decaying to Muon Pairs in {radical}(s)=1.96 TeV pp Collisions

We present a search for a new narrow, spin-1, high mass resonance decaying to {mu}{sup +}{mu}{sup -}+X, using a matrix-element-based likelihood and a simultaneous measurement of the resonance mass and production rate. In data with 4.6 fb{sup -1} of integrated luminosity collected by the CDF detector in pp collisions at {radical}(s)=1960 GeV, the most likely signal cross section is consistent with zero at 16% confidence level. We therefore do not observe evidence for a high mass resonance and place limits on models predicting spin-1 resonances, including M>1071 GeV/c{sup 2} at 95% confidence level for a Z{sup '} boson with the same couplings to fermions as the Z boson.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Conserved conformational dynamics determine enzyme activity

Homologous enzymes often exhibit different catalytic rates despite a fully conserved active site. The canonical view is that an enzyme sequence defines its structure and function and, more recently, that intrinsic protein dynamics at different time scales enable and/or promote catalytic activity. Here, we show that, using the protein tyrosine phosphatase PTP1B, residues surrounding the PTP1B active site promote dynamically coordinated chemistry necessary for PTP1B function. However, residues distant to the active site also undergo distinct intermediate time scale dynamics and these dynamics are correlated with its catalytic activity and thus allow for different catalytic rates in this enzyme family. We identify these previously undetected motions using coevolutionary coupling analysis and nuclear magnetic resonance spectroscopy. Our findings strongly indicate that conserved dynamics drives the enzymatic activity of the PTP family. Characterization of these conserved dynamics allows for the identification of novel regulatory elements (therapeutic binding pockets) that can be leveraged for the control of enzymes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Further Evidence of Modified Spin-down in Sun-like Stars: Pileups in the Temperature–Period Distribution

We combine stellar surface rotation periods determined from NASA's Kepler mission with spectroscopic temperatures to demonstrate the existence of pileups at the long-period and short-period edges of the temperature–period distribution for main-sequence stars with temperatures exceeding ~5500 K. The long-period pileup is well described by a curve of constant Rossby number, with a critical value of Ro crit ≲ Ro ⊙ . The long-period pileup was predicted by van Saders et al. as a consequence of weakened magnetic braking, in which wind-driven angular momentum losses cease once stars reach a critical Rossby number. Stars in the long-period pileup are found to have a wide range of ages (~2–6 Gyr), meaning that, along the pileup, rotation period is strongly predictive of a star's surface temperature but weakly predictive of its age. The short-period pileup, which is also well described by a curve of constant Rossby number, is not a prediction of the weakened magnetic braking hypothesis but may instead be related to a phase of slowed surface spin-down due to core-envelope coupling. The same mechanism was proposed by Curtis et al. to explain the overlapping rotation sequences of low-mass members of differently aged open clusters. The relative dearth of stars with intermediate rotation periods between the short- and long-period pileups is also well described by a curve of constant Rossby number, which aligns with the period gap initially discovered by McQuillan et al. in M-type stars. These observations provide further support for the hypothesis that the period gap is due to stellar astrophysics, rather than a nonuniform star formation history in the Kepler field.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

Oxidase uncoupling in heme monooxygenases: Human cytochrome P450 CYP3A4 in Nanodiscs

Highlights: ► Substantial reducing equivalents are lost in human P450 CYP3A4 via an oxidase channel. ► Substrate binding has a pronounced effect on uncoupling in cytochrome P450. ► Anionic phospholipids improve the overall coupling in CYP3A4 Nanodiscs. -- Abstract: The normal reaction mechanism of cytochrome P450 operates by utilizing two reducing equivalents to reduce atmospheric dioxygen, producing one molecule of water and an oxygenated product in an overall stoichiometry of 2 electrons:1 dioxygen:1 product. However, three alternate unproductive pathways exist where the intermediate iron–oxygen states in the catalytic cycle can yield reduced oxygen products without substrate metabolism. The first involves release of superoxide from the oxygenated intermediate while the second occurs after input of the second reducing equivalent. Superoxide rapidly dismutates and hence both processes produce hydrogen peroxide that can be cytotoxic to the organism. In both cases, the formation of hydrogen peroxide involves the same overall stoichiometry as oxygenases catalysis. The key step in the catalytic cycle of cytochrome P450 involves scission of the oxygen–oxygen bond of atmospheric dioxygen to produce a higher valent iron-oxo state termed “Compound I”. This intermediate initiates a radical reaction in the oxygenase pathway but also can uptake two additional reducing equivalents from reduced pyridine nucleotide (NADPH) and the flavoprotein reductase to produce a second molecule of water. This non-productive decay of Compound I thus yields an overall oxygen to NADPH ratio of 1:2 and does not produce hydrocarbon oxidation. This water uncoupling reaction provides one of a limited means to study the reactivity of the critical Compound I intermediate in P450 catalysis. We measured simultaneously the rates of NADPH and oxygen consumption as a function of substrate concentration during the steady-state hydroxylation of testosterone catalyzed by human P450 CYP3A4 reconstituted in Nanodiscs. We discovered that the “oxidase” uncoupling pathway is also operating in the substrate free form of the enzyme with rate of this pathway substantially increasing with the first substrate binding event. Surprisingly, a large fraction of the reducing equivalents used by the P450 system is wasted in this oxidase pathway. In addition, the overall coupling with testosterone and bromocryptine as substrates is significantly higher in the presence of anionic lipids, which is attributed to the changes in the redox potential of CYP3A4 and reductase.

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

Strongly Coupled Magnetic and Electronic Transitions in Multivalent Strontium Cobaltites

Here, the topotactic phase transition in SrCoO x (x = 2.5–3.0) makes it possible to reversibly transit between the two distinct phases, i.e. the brownmillerite SrCoO 2.5 that is a room-temperature antiferromagnetic insulator (AFM-I) and the perovskite SrCoO 3 that is a ferromagnetic metal (FM-M), owing to their multiple valence states. For the intermediate x values, the two distinct phases are expected to strongly compete with each other. With oxidation of SrCoO 2.5 , however, it has been conjectured that the magnetic transition is decoupled to the electronic phase transition, i.e., the AFM-to-FM transition occurs before the insulator-to-metal transition (IMT), which is still controversial. Here, we bridge the gap between the two-phase transitions by density-functional theory calculations combined with optical spectroscopy. We confirm that the IMT actually occurs concomitantly with the FM transition near the oxygen content x = 2.75. Strong charge-spin coupling drives the concurrent IMT and AFM-to-FM transition, which fosters the near room-T magnetic transition characteristic. Ultimately, our study demonstrates that SrCoO x is an intriguingly rare candidate for inducing coupled magnetic and electronic transition via fast and reversible redox reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Plasmonic Conducting Metal Oxide-Based Optical Fiber Sensors for Chemical and Intermediate Temperature-Sensing Applications

The demand for real-time sensors in harsh environments at elevated temperature is significant and increasing. In this manuscript, the chemical and temperature sensing using the optical response through the practical fiber platform is demonstrated, and principle component analysis is coupled with targeted experimental film characterization to understand the fundamental sensing layer properties, which dominate measured gas sensing responses in complex gas mixtures. More specifically, tin-doped indium oxide-decorated sensors fabricated with the sol–gel method show stable and stepwise transmission responses varying over a wide range of H2 concentration (5–100%) at 250–350 °C as well as responses to CH4 and CO to a lesser extent. Measured responses are attributed to modifications to the surface plasmon resonance absorption in the near-infrared range and are dominated by the highest concentrations of the most-reducing analyte based upon systematic mixed gas stream experiments. Principal component analysis is utilized for this type of sensor to improve the quantitative and qualitative understanding of responses, clearly identifying that the dominant principle component (PC #1) accounts for ~78% of total data variance. Correlations between PC #1 and the experimentally derived free carrier concentration confirm that this material property plays the strongest role on the ITO gas sensing mechanism, while correlations between the free carrier mobility and the second most important principle component (PC #2) suggest that this quantity may play a significant but secondary role. As such, the results presented here clarify the relationship between generalized principle components and fundamental sensing materials properties thereby suggesting the pathway toward improved multicomponent gas speciation through sensor layer engineering. Furthermore, the work presented represents a significant step toward the ultimate objective of optical waveguide sensors integrated with multivariate data analytics for multiparameter monitoring with a single sensor element.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗
DOE OSTI2021

Ligand modulation of the conformational dynamics of the A 2A adenosine receptor revealed by single-molecule fluorescence

G protein-coupled receptors (GPCRs) are the largest class of transmembrane proteins, making them an important target for therapeutics. Activation of these receptors is modulated by orthosteric ligands, which stabilize one or several states within a complex conformational ensemble. The intra- and inter-state dynamics, however, is not well documented. Here, we used single-molecule fluorescence to measure ligand-modulated conformational dynamics of the adenosine A 2A receptor (A 2A R) on nanosecond to millisecond timescales. Experiments were performed on detergent-purified A 2R in either the ligand-free (apo) state, or when bound to an inverse, partial or full agonist ligand. Single-molecule Förster resonance energy transfer (smFRET) was performed on detergent-solubilized A 2A R to resolve active and inactive states via the separation between transmembrane (TM) helices 4 and 6. The ligand-dependent changes of the smFRET distributions are consistent with conformational selection and with inter-state exchange lifetimes ≥ 3 ms. Local conformational dynamics around residue 229 6.31 on TM6 was measured using fluorescence correlation spectroscopy (FCS), which captures dynamic quenching due to photoinduced electron transfer (PET) between a covalently-attached dye and proximal aromatic residues. Global analysis of PET-FCS data revealed fast (150–350 ns), intermediate (50–60 μs) and slow (200–300 μs) conformational dynamics in A 2A R, with lifetimes and amplitudes modulated by ligands and a G-protein mimetic (mini-G s ). Most notably, the agonist binding and the coupling to mini-G s accelerates and increases the relative contribution of the sub-microsecond phase. Molecular dynamics simulations identified three tyrosine residues (Y112, Y288 7.53 , and Y290 7.55 ) as being responsible for the dynamic quenching observed by PET-FCS and revealed associated helical motions around residue 229 6.31 on TM6. As a result, this study provides a quantitative description of conformational dynamics in A 2A R and supports the idea that ligands bias not only GPCR conformations but also the dynamics within and between distinct conformational states of the receptor.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

From random stacking faults to polytypes: A 12-layer NiSn 4 polytype

NiSn 4 grows in diffusion couples (Ni plates with electrodeposited Sn) in a temperature range from room temperature up to 353 K. Previously, the crystal structure of NiSn 4 grown at ambient temperature was identified to be an intermediate stacking variant between the orthorhombic PtSn 4 -type and the tetragonal β-IrSn 4 -type structure, with a slight tendency towards the tetragonal type. Now it is reported that NiSn 4 forming at 333 K and above, exhibits a 12-layer polytype (space group P4 2 /nbc, a = b = 6.250 Å, c = 69.00 Å) due to ordered incorporation of stacking faults into the structure. Here, this NiSn 4 structure was derived by comparison of its diffraction patterns with those of the exhaustively generated NiSn 4 polytypes. First-principles calculations on a series of selected NiSn 4 polytypes demonstrate that the experimentally observed polytype is energetically favoured as compared to others.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electrocatalytic Reductive Amination of Aldehydes and Ketones with Aqueous Nitrite

The electrocatalytic utilization of oxidized nitrogen waste for C–N coupling chemistry is an exciting research area with great potential to be adopted as a sustainable method for generation of organonitrogen molecules. The most widely used C–N coupling reaction is reductive amination. In this work, we develop an alternative electrochemical reductive amination reaction that can proceed in neutral aqueous electrolyte with nitrite as the nitrogenous reactant and via an oxime intermediate. We develop a selection criterion for nitrite reduction electrocatalysts suited for oxime electrosynthesis and, in doing so, find Pd to be a highly efficient catalyst for this reaction, reaching an oxime Faradaic efficiency of 82% at −0.21 V vs the reversible hydrogen electrode. The aliphatic or aromatic structure of the carbonyl reactant impacts the efficacy of the catalyst, with aromatic substrates leading to suppressed oxime formation and detrimental reduction of the carbonyl to the alcohol. We developed a Pb/PbO electrocatalyst that selectively performs oxime reduction in the neutral aqueous electrolyte. With acetone as a model substrate, we demonstrate an efficient one-pot, two-step electrochemical reaction for the conversion of acetone to isopropyl amine with 85% yield and 50% global Faradaic efficiency.

catalysts↗
DOE OSTI2026

Mechanism of Tyrosine-Driven Deprotonation in Photosystem II Revealed by Multiscale Simulations

Photosystem II (PSII) drives light-induced water oxidation via stepwise redox transitions of its oxygen-evolving complex (OEC), a Mn 4 Ca cluster advancing through five intermediate S-states (S 0 –S 4 ). The S 2 → S 3 transition involves a redox event in which a Mn ion donates an electron to the redox-active tyrosine YZ, coupled to deprotonation of an OEC-bound water ligand─yet the underlying coupling mechanism remains unresolved. Time-resolved serial femtosecond crystallography (TR-SFX) has revealed transient electron density shifts near the redox-active tyrosine Y Z , interpreted as sequential oxidation and reduction, with reduction initiating ∼1 μs after excitation and substantially progressed by 30 μs. However, this interpretation conflicts with kinetics from photothermal beam deflection (PBD), time-resolved X-ray absorption spectroscopy (TR-XAS), and electron paramagnetic resonance (EPR), which place electron transfer at 190–400 μs and proton transfer around 30 μs. Here, we reconcile these discrepancies using quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations. We show that oxidation of P680 and Y Z breaks the symmetry of the nearby hydrogen bonds involving water molecule W4, displacing Y Z and replicating the TR-SFX features of Y Z and Q165 observed at 1 μs. This local perturbation propagates through a hydrogen-bond network, transmitting the electrostatic signal from Y Z to the E65-E312 dyad and triggering redox-coupled deprotonation via the Cl1 channel. By 30 μs, the hydrogen-bond symmetry is restored through deprotonation of W2 (or alternatively W1), reproducing the disappearance of TR-SFX density differences around Y Z and Q165 without requiring Y Z reduction. Our proposed mechanism also gives molecular insights into the O6* density, assigning it to water reorganization rather than a discrete Ca-bound hydroxide species. Here, our results reveal a detailed atomistic mechanism linking Y Z oxidation to long-range proton release and suggest a functional role for the nearby Cl – ion in proton transfer. More broadly, this study underscores the importance of hydrogen-bond dynamics in mediating redox-driven proton transport and demonstrates how integrative simulations can resolve mechanistic ambiguities.

Deprotonation↗
DOE OSTI2024

Reaction dynamics of S( 3 P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S( 3 P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H 2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C 3 H 4 S (loss of ethene or H 2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Lang, Jinxin↗