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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

On convexity of H-infinity Riccati solutions and its applications

The celebrated two-Riccati-equation solution to a standard H-infinity control problem can be used to characterize all possible stabilizing optimal or suboptimal H-infinity controllers if the optimal H-infinity norm or gamma, an upper bound of a suboptimal H-infinity norm, is given. In this note, some properties of these H-infinity Riccati solutions are revealed. Among them, the most prominent one is that the spectral radius of the product of these two Riccati solutions is a continuous, nonincreasing, convex function of gamma on the domain of interest. Based on these properties, a quadratically convergent algorithm is developed to compute the optimal H-infinity norm.

Li, X. P.↗
NASA NTRS1994

Classical H II regions in the Magellanic Clouds. 2: Stellar content

In this second in a series of papers on the nature of classical H II regions in the Magellanic Clouds I investigate the properties of the underlying stellar content of the nebulae. Particular emphasis is placed on identifying and classifying the ionizing source(s) for each H II region. With the exception of the LMC H II regions DEM 20 and DEM 8c, I find that all of the objects in this sample are ionized by more than one O or B star. Even the faintest H II regions reflect the formation of a handful of massive, albeit early B type, stars. Typically, one star accounts for 60% - 70% of the ionizing photons and 2 - 5 less massive stars provide the remaining 30% - 40%. From the statistics of the hottest stars in these H II regions, and from considering all the blue stars contained within each region, the distribution of massive stars with spectral type is consistent with results found in similar galactic H II regions.

Wilcots, Eric M.↗
NASA NTRS1995

A high spectral resolution VLA search for H I absorption towards A496, A1795, and A2584

In this paper, we present the results of a Very Large Array (VLA) search for H I absorption with high spectral resolution (1.6 km/s) towards A496, A1795, A2584, and A2597. These observations are well matched to the properties of cold, optically thick H I clouds, where the line width is given by the width of an individual cloud rather than the dispersion in an ensemble of clouds. We do not detect any H I absorption with narrow linewidths in these clusters. Our limits mainly apply to clouds which are larger than a few tenths parsec-i.e., if the clouds are much smaller than the background radio source and have a low covering factor in velocity space, they could still escape detection. The estimated limits on column density (for clouds in this regime of parameter space) are 2-3 orders of magnitude less than the 10(exp 21)/sq cm required to explain the x-ray absorption seen in some cooling flow clusters. The combination of our high spectral resolution H I absorption searches with the existing lower spectral resolution H I absorption searches and the searches for H I emission makes it unlikely that atomic hydrogen is the dominant component of the cold x-ray absorbing gas in the inter-cloud medium (ICM).

O'Dea, Christopher P.↗
NASA NTRS1995

A surprise at the bottom of the main sequence: Rapid rotation and NO H-alpha emission

We report Kech Observatory high-resolution echelle spectra from 640-850 nm for eight stars near the faint end of the main sequence. These spectra are the highest resolution spectra of such late-type stars, and clearly resolve the TiO, VO, and atomic lines. The sample includes the field brown-dwarf candidate, BRI 0021-0214 (M9.5+). Very unexpectedly, it shows the most rapid rotation in the entire samples, v sin i approximately 40 km/s, which is 20x faster than typical field nonemission M stars. Equally surprising is that BRI 0021 exhibits no emission or absorptionat H-alpha. We argue that this absence is not simply due to its cool photosphere, but that stellar activity declines in a fundamental way at the end of the main sequence. As it is the first very late M dwarf observed at high spectral resolution, BRI 0021 may be signaling a qualitative change in the angular momentum loss rate among the lowest mass stars. Conventionally, its rapid rotation would have marked BRI 0021 as very young, consistent with the selection effect which arises if the latest-type dwarfs are really brown dwarfs on cooling curves. In any case, it is unprecedented to find no sign of stellar activity in such a rapidly rotating convective star. We also discuss the possible conflict between this observation and the extremely strong H-alpha seen in another very cool star, PC 0025+0447. Extrapolation of M-L relations for BRI 0021 yields M approximately 0.065 solar mass, and the other sample objects have expected masses near the H-burning limit. These include two Pleiades brown-dwarf candidates, four field M6 dwarfs and one late-type T Tauri star. The two Pleiades M6 dwarfs have v sin i of 26 and 37 km/s, H-alpha in emission, and radial velocities consistent with Pleiades M6 dwarfs have v sin i of 26 and 37 km/s, H-alpha in emission, and radial velocities consistent with Pleiades membership. Similarly, the late-type T Tauri star has v sin i approximately 30 km/s and H alpha emission indicate of its youth. Two of the four late-type field dMe star also exhibit rotation above 5 km/s, consistent with expectations. BRI 0021 has no measurable absoprtion due to lithium, indicating that it is likely to be more massive than 0.065 solar mass.

Basri, Gibor↗
NASA NTRS1998

Galaxy Cluster Shapes and Systematic Errors in H_0 as Determined by the Sunyaev-Zel'dovich Effect

Imaging of the Sunyaev-Zeldovich (SZ) effect in galaxy clusters combined with cluster plasma x-ray diagnostics promises to measure the cosmic distance scale to high accuracy. However, projecting the inverse-Compton scattering and x-ray emission along the cluster line-of-sight will introduce systematic error's in the Hubble constant, H_0, because the true shape of the cluster is not known. In this paper we present a study of the systematic errors in the value of H_0, as determined by the x-ray and SZ properties of theoretical samples of triaxial isothermal "beta-model" clusters, caused by projection effects and observer orientation relative to the model clusters' principal axes. We calculate three estimates for H_0 for each cluster, based on their large and small apparent angular core radii, and their arithmetic mean. We average the estimates for H_0 for a sample of 25 clusters and find that the estimates have limited systematic error: the 99.7% confidence intervals for the mean estimated H_0 analyzing the clusters using either their large or mean angular core r;dius are within 14% of the "true" (assumed) value of H_0 (and enclose it), for a triaxial beta model cluster sample possessing a distribution of apparent x-ray cluster ellipticities consistent with that of observed x-ray clusters.

Sulkanen, Martin E.↗
NASA NTRS2000

Scattering/Transmission of Energetic H(sup +), He(sup +), and O(sup +) Through a Thin Composite Si/Lexan/C Foil

The need for a thin foil to serve both as an extreme ultraviolet (EUV) radiation attenuator and as a secondary electron generator for time-of-flight (TOF) instruments and energetic neutral atom (ENA) imagers has led us to test the scattering and transmission characteristics of a layered foil of nominal aerial thicknesses of 5 microns/sq cm Si, 4 microns/sq.cm Lexan ((C16)H(14)O3), and 1 micron/sq.cm C. We report the scattering and transmission results of subjecting this foil to H(sup +), He(sup +), and O(sup +) beams of energy less than 120 keV. The scattering of these particles, defined by the half-angular-width at half-maximum (HWHM), decreases with increasing energy and is found to be 10 deg for 10 keV H(sup +), 22 keV for He(sup +), and 100 keV for O(sup +). The 50% transmission threshold for these particles was found to be 3.9 keV for H(sup +), 8.6 keV for He(sup +), and 49.5 keV for O(sup +). Additionally, ion transmission shows evidence of resonance scattering from a rectangular potential independent of incident ion mass. Particularly evident is a local transmission minimum at 70 keV possessing a Gaussian-width of 20 keV. For incident energies below 50 keV, computer simulations of H+-foil interactions using SRIM96 agree well with the H(sup +) data, while yielding less scattering and higher transmission than indicated by the O(sup +) data.

Adrian, M. L.↗
NASA NTRS1992

Regulation of an H-ras-related transcript by parathyroid hormone in rat osteosarcoma cells

The rat osteosarcoma cell line UMR 106-01 is a commonly used model system for the study of osteoblast function. However, it also expresses a phenotype characteristic of transformed cells. To test whether the latter could be accounted for by aberrant oncogene expression, we probed Northern blots of UMR and other osteoblastic cells with a panel of oncogene probes. These blots, when probed with a cDNA specific for v-H-ras, revealed a 7.0-kilobase (kb) H-ras-related transcript (designated HRRT) in UMR 106-01 cells that was not expressed in other osteoblastic cells. Osteoblast-enriched calvarial cells expressed the typical 1.1-kb H-ras mRNA, which was absent in UMR cells. Additionally, Western blots of lysates of UMR cells documented the presence of three proteins immunologically related to H-rasp21. To determine whether HRRT represented a recombinant retrovirus product, Northern blots were probed with a cDNA specific for the highly conserved gag-pol region of Moloney murine leukemia virus. These blots showed parallel cross-reactivity with an apparently identical transcript of 7.0 kb. The 7.0-kb transcripts detected by both v-H-ras and gag-pol probes declined to the same extent after treatment with concentrations of PTH known to inhibit proliferation of these cells. PTH regulated the abundance of HRRT in a time- and dose-dependent manner, with greatest repression of the transcript after 8 h of treatment with 10(-8) M PTH. The decrease in HRRT could not be completely accounted for by changes in transcriptional activity, as determined by nuclear run-on assays.(ABSTRACT TRUNCATED AT 250 WORDS).

Non-NASA Center↗
NASA NTRS1991

Enhanced vagal baroreflex response during 24 h after acute exercise

We evaluated carotid-cardiac baroreflex responses in eight normotensive men (25-41 yr) on two different test days, each separated by at least 1 wk. On one day, baroreflex response was tested before and at 3, 6, 12, 18, and 24 h after graded supine cycle exercise to volitional exhaustion. On another day, this 24-h protocol was repeated with no exercise (control). Beat-to-beat R-R intervals were measured during external application of graded pressures to the carotid sinuses from 40 to -65 mmHg; changes of R-R intervals were plotted against carotid pressure (systolic pressure minus neck chamber pressure). The maximum slope of the response relationship increased (P less than 0.05) from preexercise to 12 h (3.7 +/- 0.4 to 7.1 +/- 0.7 ms/mmHg) and remained significantly elevated through 24 h. The range of the R-R response was also increased from 217 +/- 24 to 274 +/- 32 ms (P less than 0.05). No significant differences were observed during the control 24-h period. An acute bout of graded exercise designed to elicit exhaustion increases the sensitivity and range of the carotid-cardiac baroreflex response for 24 h and enhances its capacity to buffer against hypotension by increasing heart rate. These results may represent an underlying mechanism that contributes to blood pressure stability after intense exercise.

Vagus Nerve/physiology↗
NASA NTRS2015

Predicting the Redshift 2 H-Alpha Luminosity Function Using [OIII] Emission Line Galaxies

Upcoming space-based surveys such as Euclid and WFIRST-AFTA plan to measure Baryonic Acoustic Oscillations (BAOs) in order to study dark energy. These surveys will use IR slitless grism spectroscopy to measure redshifts of a large number of galaxies over a significant redshift range. In this paper, we use the WFC3 Infrared Spectroscopic Parallel Survey (WISP) to estimate the expected number of H-alpha emitters observable by these future surveys. WISP is an ongoing Hubble Space Telescope slitless spectroscopic survey, covering the 0.8 - 1.65 micrometers wavelength range and allowing the detection of H-alpha emitters up to z approximately equal to 1.5 and [OIII] emitters to z approximately equal to 2.3. We derive the H-alpha-[OIII] bivariate line luminosity function for WISP galaxies at z approximately equal to 1 using a maximum likelihood estimator that properly accounts for uncertainties in line luminosity measurement, and demonstrate how it can be used to derive the H-alpha luminosity function from exclusively fitting [OIII] data. Using the z approximately equal to 2 [OIII] line luminosity function, and assuming that the relation between H-alpha and [OIII] luminosity does not change significantly over the redshift range, we predict the H-alpha number counts at z approximately equal to 2 - the upper end of the redshift range of interest for the future surveys. For the redshift range 0.7 less than z less than 2, we expect approximately 3000 galaxies per sq deg for a flux limit of 3 x 10(exp −16) ergs per sec per sq cm (the proposed depth of Euclid galaxy redshift survey) and approximately 20,000 galaxies per sq deg for a flux limit of approximately 10(exp −16) ergs per sec per sq cm (the baseline depth of WFIRST galaxy redshift survey).

Redshift↗
DOE OSTI2022

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Abstract C−H amination and amidation by catalytic nitrene transfer are well‐established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C−H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd−N) with a diradical nitrogen ligand that is singly bonded to Pd II . Despite the subvalent nitrene character, selective C−H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N 3 SiMe 3 . Based on these results, a photocatalytic protocol for aldehyde C−H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C−H nitrogen atom transfer offers facile access to primary amides after deprotection.

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

DFT Mechanism Studies: Biomimetic 1,4-NADH Chemoselective, Co-factor Regeneration with [Cp*Rh(bpy)H] + , in Tandem with the Biocatalysis Pathways of a Core Model of the (HLADH)-Zn(II) Mediated Enzyme, in the Enantioselective Reduction of Achiral Ketones to Chiral S-Alcohols

In this study, Quantum Chemical (QC) calculations, utilizing Density Functional Theory (DFT), were performed to investigate the mechanistic aspects of the chemoselective catalyzed reaction of [Cp*Rh(bpy)H] + with the biomimetic NAD + analogues, N-benzylnicotinamide triflate, 1, and β-nicotinamide ribose-5'-methyl phosphate, 2, in the conversion to their 1,4-NADH analogues, 1,4-dihydro-N-benzylnicotinamide, 4, and β-1,4-dihydronicotinamide-5'-ribose methyl phosphate, 5. This reaction was in tandem with the 1,4-NADH dependent HLADH-Zn(II)- catalyzed reduction of achiral ketones to chiral S-alcohols. The [Cp*Rh(bpy)H] + complex, and not its equilibrium tautomer, [η 4 -Cp*HRh(bpy)] + , was found to control the hydride transfer during the biomimetic NAD + /1,4-NADH conversion, through the non-covalent interactions of the biomimetic co-factors with [Cp*Rh(bpy)H] + . The thermodynamics and kinetics for the chiral reduction of the Zn(II) bound ketones, 2-pentanone and 4-phenyl-2-butanone, with co-factor, 4, catalyzed by Zn(SCH 3 ) 2 (Imidazole), a core model of the Zn(II)-based catalytic center of HLADH, was also investigated by the evaluation of two possible reaction pathways: (1) formation of a ZnH from the C4-H hydride transfer of co-factor, 4, followed by reaction of the postulated ZnH with the bound 2-pentanone or 4-phenyl-2-butanone substrate, and (2), the direct C4-H transfer to the bound achiral ketone substrates, to provide the dominant chiral alcohols, S-2-pentanol or S-4-phenyl-2-butanol. The latter pathway was found most viable, and DFT calculations also revealed an essential η 2 -coordination of the 5,6 double bond of co-factor, 4, to the HLADH-Zn(II) metal ion center, upon imidazole decomplexation, providing an asymmetric differentiation of S-η 2 -5,6-1,4-NADH-Zn(II) binding. A proposed new paradigm for the Zn(II)'s non-innocent role in the HLADH-Zn(II) biocatalysis reduction mechanism, for enantioselective hydride transfer to a Zn(II) bound ketone, providing S-alcohols.

1,4 NADH co-factors↗
DOE OSTI2024

Measurement of 3 Λ H production in Pb–Pb collisions at √ s NN = 5.02 TeV

The first measurement of 3 Λ H and $^{3}_{\overline{Λ}}$$\overline{H}$ differential production with respect to transverse momentum and centrality in Pb–Pb collisions at √ s NN = 5.02 TeV is presented. The 3 Λ H has been reconstructed via its two-charged-body decay channel, i.e., 3 Λ H → 3 He → π - . A Blast-Wave model fit of the p T -differential spectra of all nuclear species measured by the ALICE collaboration suggests that the kinetic freeze-out surface is consistent with that of other nuclei. The ratio between the integrated yields of 3 Λ H and 3 He is compared to predictions from the statistical hadronisation model and the coalescence model, with the latter being favoured by the presented measurements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Microscopic Investigation of H 2 Reduced CuO x /Cu(111) and ZnO/CuO x /Cu(111) Inverse Catalysts: STM, AP-XPS, and DFT Studies

Understanding the reduction mechanism of ZnO/CuO x interfaces by hydrogen is of great importance for advancing the performance of industrial catalysts for CO 2 hydrogenation to methanol. Here, the reduction of pristine and ZnO-modified CuO x /Cu(111) by H 2 was investigated using ambient pressure scanning tunnelling microscopy (AP-STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT). The morphological changes and reaction rates seen for the reduction of CuO x /Cu(111) and ZnO/CuO x /Cu(111) are very different. On CuO x /Cu(111), perfect "44" and "29" structures displayed a very low reactivity towards H 2 at room temperature. A long induction period associated with an autocatalytic process was observed to enable the reduction by the removal of chemisorbed non-lattice oxygen initially and lattice oxygen sequentially at the CuO x -Cu interface, which led to formation of oxygen deficient "5-7" hex and honeycomb structures. In the final stages of the reduction process, regions of residual oxygen species and metallic Cu were seen. The addition of ZnO particles to CuO x /Cu(111) opened new reaction channels. On the ZnO sites, the dissociation of H 2 was fast and H adatoms easily migrated to adjacent regions of copper oxide. This hydrogen spillover substantially enhanced the rate of oxygen removal, resulting in the rapid reduction of the copper oxide located in the periphery of the zinc oxide islands with no signs for the reduction of ZnO. The deposited ZnO completely modified the dynamics for H 2 dissociation and hydrogen migration, providing an excellent source for CO 2 hydrogenation processes on the inverse oxide/metal system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2010

Massive Star Formation of the SGR a East H (sub II) Regions Near the Galactic Center

A group of four compact H II regions associated with the well-known 50 km/s molecular cloud is the closest site of on-going star formation to the dynamical center of the Galaxy, at a projected distance of approximately 6 pc. We present a study of ionized gas based on the [Ne II] (12.8 micron) line, as well as multi-frequency radio continuum, Hubble Space Telescope Pa alpha, and Spitzer Infrared Array Camera observations of the most compact member of the H II group, Sgr A East H II D. The radio continuum image at 6 cm shows that this source breaks up into two equally bright ionized features, D1 and D2. The spectral energy distribution of the D source is consistent with it being due to a 25 =/- 3 solar mass star with a luminosity of 8 +/- 3 x 10(exp 4) Solar luminosity . The inferred mass, effective temperature of the UV source, and the ionization rate are compatible with a young O9-B0 star. The ionized features D1 and D2 are considered to be ionized by UV radiation collimated by an accretion disk. We consider that the central massive star photoevaporates its circumstellar disk on a timescale of 3x (exp 4) years giving a mass flux approximately 3 x 10(exp -5) Solar Mass / year and producing the ionized material in D1 and D2 expanding in an inhomogeneous medium. The ionized gas kinematics, as traced by the [Ne II] emission, is difficult to interpret, but it could be explained by the interaction of a bipolar jet with surrounding gas along with what appears to be a conical wall of lower velocity gas. The other H II regions, Sgr A East A-C, have morphologies and kinematics that more closely resemble cometary flows seen in other compact H II regions, where gas moves along a paraboloidal surface formed by the interaction of a stellar wind with a molecular cloud.

Yusef-Zadeh, F.↗
DOE OSTI2022

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Abstract C−H amination and amidation by catalytic nitrene transfer are well‐established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C−H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd−N) with a diradical nitrogen ligand that is singly bonded to Pd II . Despite the subvalent nitrene character, selective C−H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N 3 SiMe 3 . Based on these results, a photocatalytic protocol for aldehyde C−H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C−H nitrogen atom transfer offers facile access to primary amides after deprotection.

Schmidt‐Räntsch, Till↗
DOE OSTI2022

Unusual Changes of C−H Bond Lengths in Chiral Zinc Complexes Induced by Noncovalent Interactions

In order to better understand the effect of non-covalent weak interactions on molecules, we have explored a variety of weak interactions, such as improper H-bonding (HB), tetrel bonds (TBs) and halogen bonds, in fluorinated chiral zinc complexes. High resolution neutron diffraction studies revealed a methylene carbon-hydrogen bond elongation and shortening due to TB and improper HB interactions, respectively. To show the accumulative effects of multiple weak interactions on the C-H bond, three types of tetrel bonds have been carefully examined. We have also shown how C-H bond elongation can be easily offset by forming an improper HB with the H atom from this C-H bond. Non-covalent interaction and electrostatic potential analysis investigations have been used to affirm the nature of the interactions based on density functional theory (DFT) and other related calculations.

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

Chapter One - Selectivity in the activation of C–H bonds by rhodium and iridium complexes

Trispyrazolylborate complexes of rhodium and iridium have been extensively investigated over the past 3 decades with special attention to their ability to activate C–H bonds. The rhodium complexes of tris-(3,5-dimethylpyrazolyl)borate have been the subject of numerous thermodynamic investigations that provide information about rhodium-metal carbon bond strengths. This insight arises as a result of the reversibility of C–H activation with rhodium. In the case of iridium, C–H bond activation reactions are also widespread, and some of these also show reversibility. Access to some key trispyrazolylborate iridium(I) and iridium(III) starting materials has given way to a multitude of studies of reactions with small molecules in which C–H bonds are made and broken reversibly. The stability of Fischer carbenes plays a role in the observed products. Here, the reactivity of trispyrazolylborate complexes of rhodium and iridium compounds over the past decade (since 2010) are summarized here. Related reactions of X–H bonds with these trispyrazolylborate compounds are also included for completeness (X = O, N, S, B, Si).

02 PETROLEUM↗