Signatures of oxygen on Cu(3)Au(100): From isolated impurity to oxide regimes

We analyze the scanning tunneling microscopy (STM) signatures for the O/Cu(3)Au(100) surface from the low-coverage (isolated impurity) to high-coverage (oxide) regimes. First-principles calculations show that oxygen signatures switch from dark to bright spots as the oxygen coverage increases. This behavior is nicely traced back to a change in the oxygen orbital character of the Fermi-level electronic states. Our results allow for the chemical identification by STM of oxygen and copper atoms in the fully ordered O/Cu(3)Au(100)-c(2x2) surface.

The metal content of bulge field stars from FLAMES-GIRAFFE spectra - I. Stellar parameters and iron abundances

Aims. We determine the iron distribution function (IDF) for bulge field stars, in three different fields along the Galactic minor axis and at latitudes b = -4 degrees, b = -6 degrees, and b = -12 degrees. A fourth field including NGC 6553 is also included in the discussion. Methods. About 800 bulge field K giants were observed with the GIRAFFE spectrograph of FLAMES@VLT at spectral resolution R similar to 20 000. Several of them were observed again with UVES at R similar to 45 000 to insure the accuracy of the measurements. The LTE abundance analysis yielded stellar parameters and iron abundances that allowed us to construct an IDF for the bulge that, for the first time, is based on high-resolution spectroscopy for each individual star. Results. The IDF derived here is centered on solar metallicity, and extends from [Fe/H] similar to -1.5 to [Fe/H] similar to + 0.5. The distribution is asymmetric, with a sharper cutoff on the high-metallicity side, and it is narrower than previously measured. A variation in the mean metallicity along the bulge minor axis is clearly between b = -4 degrees and b = -6 degrees ([Fe/H] decreasing similar to by 0.6 dex per kpc). The field at b = -12 degrees. is consistent with the presence of a gradient, but its quantification is complicated by the higher disk/bulge fraction in this field. Conclusions. Our findings support a scenario in which both infall and outflow were important during the bulge formation, and then suggest the presence of a radial gradient, which poses some challenges to the scenario in which the bulge would result solely from the vertical heating of the bar.

Alpha element abundances and gradients in the Milky Way bulge from FLAMES-GIRAFFE spectra of 650 K giants

Aims. We present the analysis of the [alpha/Fe] abundance ratios for a large number of stars at several locations in the Milky Way bulge with the aim of constraining its formation scenario. Methods. We obtained FLAMES-GIRAFFE spectra (R = 22 500) at the ESO Very Large Telescope for 650 bulge red giant branch (RGB) stars and performed spectral synthesis to measure Mg, Ca, Ti, and Si abundances. This sample is composed of 474 giant stars observed in 3 fields along the minor axis of the Galactic bulge and at latitudes b = -4 degrees, b = -6 degrees, b = -12 degrees. Another 176 stars belong to a field containing the globular cluster NGC 6553, located at b = -3 degrees and 5 degrees away from the other three fields along the major axis. Stellar parameters and metallicities for these stars were presented in Zoccali et al. (2008, A&A, 486, 177). We have also re-derived stellar parameters and abundances for the sample of thick and thin disk red giants analyzed in Alves-Brito et al. (2010, A&A, 513, A35). Therefore using a homogeneous abundance database for the bulge, thick and thin disk, we have performed a differential analysis minimizing systematic errors, to compare the formation scenarios of these Galactic components. Results. Our results confirm, with large number statistics, the chemical similarity between the Galactic bulge and thick disk, which are both enhanced in alpha elements when compared to the thin disk. In the same context, we analyze [alpha/Fe] vs. [Fe/H] trends across different bulge regions. The most metal rich stars, showing low [alpha/Fe] ratios at b = -4 degrees disappear at higher Galactic latitudes in agreement with the observed metallicity gradient in the bulge. Metal-poor stars ([Fe/H] < -0.2) show a remarkable homogeneity at different bulge locations. Conclusions. We have obtained further constrains for the formation scenario of the Galactic bulge. A metal-poor component chemically indistinguishable from the thick disk hints for a fast and early formation for both the bulge and the thick disk. Such a component shows no variation, neither in abundances nor kinematics, among different bulge regions. A metal-rich component showing low [alpha/Fe] similar to those of the thin disk disappears at larger latitudes. This allows us to trace a component formed through fast early mergers (classical bulge) and a disk/bar component formed on a more extended timescale.

First stars XIV. Sulfur abundances in extremely metal-poor stars

Context. Precise S abundances are important in the study of the early chemical evolution of the Galaxy. In particular the site of the formation remains uncertain because, at low metallicity, the trend of this alpha-element versus [Fe/H] remains unclear. Moreover, although sulfur is not bound significantly in dust grains in the ISM, it seems to behave differently in DLAs and old metal-poor stars. Aims. We attempt a precise measurement of the S abundance in a sample of extremely metal-poor stars observed with the ESO VLT equipped with UVES, taking into account NLTE and 3D effects. Methods. The NLTE profiles of the lines of multiplet 1 of S I were computed with a version of the program MULTI, including opacity sources from ATLAS9 and based on a new model atom for S. These profiles were fitted to the observed spectra. Results. We find that sulfur in EMP stars behaves like the other alpha-elements, with [S/Fe] remaining approximately constant below [Fe/H] = -3. However, [S/Mg] seems to decrease slightly with increasing [Mg/H]. The overall abundance patterns of O, Na, Mg, Al, S, and K are most closely matched by the SN model yields by Heger & Woosley. The [S/Zn] ratio in EMP stars is solar, as also found in DLAs. We derive an upper limit to the sulfur abundance [S/Fe] < +0.5 for the ultra metal-poor star CS 22949-037. This, along with a previously reported measurement of zinc, argues against the conjecture that the light-element abundance pattern of this star (and by analogy, the hyper iron-poor stars HE 0107-5240 and HE 1327-2326) would be due to dust depletion.

Chemical evolution models for spiral disks: the Milky Way, M31, and M33

Context. The distribution of chemical abundances and their variation with time are important tools for understanding the chemical evolution of galaxies. In particular, the study of chemical evolution models can improve our understanding of the basic assumptions made when modelling our Galaxy and other spirals. Aims. We test a standard chemical evolution model for spiral disks in the Local Universe and study the influence of a threshold gas density and different efficiencies in the star formation rate (SFR) law on radial gradients of abundance, gas, and SFR. The model is then applied to specific galaxies. Methods. We adopt a one-infall chemical evolution model where the Galactic disk forms inside-out by means of infall of gas, and we test different thresholds and efficiencies in the SFR. The model is scaled to the disk properties of three Local Group galaxies (the Milky Way, M31 and M33) by varying its dependence on the star formation efficiency and the timescale for the infall of gas onto the disk. Results. Using this simple model, we are able to reproduce most of the observed constraints available in the literature for the studied galaxies. The radial oxygen abundance gradients and their time evolution are studied in detail. The present day abundance gradients are more sensitive to the threshold than to other parameters, while their temporal evolutions are more dependent on the chosen SFR efficiency. A variable efficiency along the galaxy radius can reproduce the present day gas distribution in the disk of spirals with prominent arms. The steepness in the distribution of stellar surface density differs from massive to lower mass disks, owing to the different star formation histories. Conclusions. The most massive disks seem to have evolved faster (i.e., with more efficient star formation) than the less massive ones, thus suggesting a downsizing in star formation for spirals. The threshold and the efficiency of star formation play a very important role in the chemical evolution of spiral disks. For instance, an efficiency varying with radius can be used to regulate the star formation. The oxygen abundance gradient can steepen or flatten in time depending on the choice of this parameter.

A FIRST CONSTRAINT ON THE THICK DISK SCALE LENGTH: DIFFERENTIAL RADIAL ABUNDANCES IN K GIANTS AT GALACTOCENTRIC RADII 4, 8, AND 12 kpc

Based on high-resolution spectra obtained with the MIKE spectrograph on the Magellan telescopes, we present detailed elemental abundances for 20 red giant stars in the outer Galactic disk, located at Galactocentric distances between 9 and 13 kpc. The outer disk sample is complemented with samples of red giants from the inner Galactic disk and the solar neighborhood, analyzed using identical methods. For Galactocentric distances beyond 10 kpc, we only find chemical patterns associated with the local thin disk, even for stars far above the Galactic plane. Our results show that the relative densities of the thick and thin disks are dramatically different from the solar neighborhood, and we therefore suggest that the radial scale length of the thick disk is much shorter than that of the thin disk. We make a first estimate of the thick disk scale length of L(thick) = 2.0 kpc, assuming L(thin) = 3.8 kpc for the thin disk. We suggest that radial migration may explain the lack of radial age, metallicity, and abundance gradients in the thick disk, possibly also explaining the link between the thick disk and the metal-poor bulge.

VLT-FLAMES analysis of 8 giants in the bulge metal-poor globular cluster NGC 6522: oldest cluster in the Galaxy? Analysis of 8 giants in NGC 6522

Context. NGC 6522 has been the first metal-poor globular cluster identified in the bulge by Baade. Despite its importance, very few high-resolution abundance analyses of stars in this cluster are available. The bulge metal-poor clusters may be important tracers of the early chemical enrichment of the Galaxy. Aims. The main purpose of this study is to determine metallicity and elemental ratios in individual stars of NGC 6522. Methods. High-resolution spectra of 8 giants of the bulge's globular cluster NGC 6522 were obtained at the 8m VLT UT2-Kueyen telescope with the FLAMES+GIRAFFE spectrograph. Multiband V, I, J, K(s) photometry was used to derive effective temperatures as reference values. Spectroscopic parameters were derived from Fe I and Fe II lines, and adopted for the derivation of abundance ratios. Results. The present analysis provides a metallicity [Fe/H] = -1.0 +/- 0.2. The alpha-elements oxygen, magnesium and silicon show [O/Fe] = +0.4 +/- 0.3, [Mg/Fe] = [Si/Fe] = +0.25 +/- 0.15, whereas calcium and titanium show shallower ratios of [Ca/Fe] = [Ti/Fe] = +0.15 +/- 0.15. The neutron-capture r-process element europium appears to be overabundant by [Eu/Fe] = +0.4 +/- 0.4. The neutron-capture s-elements lanthanum and barium are enhanced by [La/Fe] = +0.35 +/- 0.2 and [Ba/Fe] = +0.5 +/- 0.5. The large internal errors, indicating the large star-to-star variation in the barium and europium abundances, are also discussed. Conclusions. The moderate metallicity combined to a blue horizontal branch (BHB), are characteristics similar to those of HP 1 and NGC 6558, pointing to a population of very old globular clusters in the Galactic bulge. Also, the abundance ratios in NGC 6522 resemble those in HP 1 and NGC 6558. The ultimate conclusion is that the bulge is old, and went through an early prompt chemical enrichment.

Beryllium abundances along the evolutionary sequence of the open cluster IC 4651-A new test for hydrodynamical stellar models

Context. Previous analyses of lithium abundances in main sequence and red giant stars have revealed the action of mixing mechanisms other than convection in stellar interiors. Beryllium abundances in stars with Li abundance determinations can offer valuable complementary information on the nature of these mechanisms. Aims. Our aim is to derive Be abundances along the whole evolutionary sequence of an open cluster. We focus on the well-studied open cluster IC 4651. These Be abundances are used with previously determined Li abundances, in the same sample stars, to investigate the mixing mechanisms in a range of stellar masses and evolutionary stages. Methods. Atmospheric parameters were adopted from a previous abundance analysis by the same authors. New Be abundances have been determined from high-resolution, high signal-to-noise UVES spectra using spectrum synthesis and model atmospheres. The careful synthetic modeling of the Be lines region is used to calculate reliable abundances in rapidly rotating stars. The observed behavior of Be and Li is compared to theoretical predictions from stellar models including rotation-induced mixing, internal gravity waves, atomic diffusion, and thermohaline mixing. Results. Beryllium is detected in all the main sequence and turn-off sample stars, both slow- and fast-rotating stars, including the Li-dip stars, but is not detected in the red giants. Confirming previous results, we find that the Li dip is also a Be dip, although the depletion of Be is more modest than for Li in the corresponding effective temperature range. For post-main-sequence stars, the Be dilution starts earlier within the Hertzsprung gap than expected from classical predictions, as does the Li dilution. A clear dispersion in the Be abundances is also observed. Theoretical stellar models including the hydrodynamical transport processes mentioned above are able to reproduce all the observed features well. These results show a good theoretical understanding of the Li and Be behavior along the color-magnitude diagram of this intermediate-age cluster for stars more massive than 1.2 M(circle dot).

Mn, Cu, and Zn abundances in barium stars and their correlations with neutron capture elements

Barium stars are optimal sites for studying the correlations between the neutron-capture elements and other species that may be depleted or enhanced, because they act as neutron seeds or poisons during the operation of the s-process. These data are necessary to help constrain the modeling of the neutron-capture paths and explain the s-process abundance curve of the solar system. Chemical abundances for a large number of barium stars with different degrees of s-process excesses, masses, metallicities, and evolutionary states are a crucial step towards this goal. We present abundances of Mn, Cu, Zn, and various light and heavy elements for a sample of barium and normal giant stars, and present correlations between abundances contributed to different degrees by the weak-s, mains, and r-processes of neutron capture, between Fe-peak elements and heavy elements. Data from the literature are also considered in order to better study the abundance pattern of peculiar stars. The stellar spectra were observed with FEROS/ESO. The stellar atmospheric parameters of the eight barium giant stars and six normal giants that we analyzed lie in the range 4300 < T(eff)/K < 5300, -0.7 < [Fe/H] <= 0.12 and 1.5 <= log g < 2.9. Carbon and nitrogen abundances were derived by spectral synthesis of the molecular bands of C(2), CH, and CN. For all other elements we used the atomic lines to perform the spectral synthesis. A very large scatter was found mainly for the Mn abundances when data from the literature were considered. We found that [Zn/Fe] correlates well with the heavy element excesses, its abundance clearly increasing as the heavy element excesses increase, a trend not shown by the [Cu/Fe] and [Mn/Fe] ratios. Also, the ratios involving Mn, Cu, and Zn and heavy elements usually show an increasing trend toward higher metallicities. Our results suggest that a larger fraction of the Zn synthesis than of Cu is owed to massive stars, and that the contribution of the main-s process to the synthesis of both elements is small. We also conclude that Mn is mostly synthesized by SN Ia, and that a non-negligible fraction of the synthesis of Mn, Cu, and Zn is owed to the weak s-process.

Hyperbaric Oxygen Prevents Early Death Caused by Experimental Cerebral Malaria

Background: Cerebral malaria (CM) is a syndrome characterized by neurological signs, seizures and coma. Despite the fact that CM presents similarities with cerebral stroke, few studies have focused on new supportive therapies for the disease. Hyperbaric oxygen (HBO) therapy has been successfully used in patients with numerous brain disorders such as stroke, migraine and atherosclerosis. Methodology/Principal Findings: C57BL/6 mice infected with Plasmodium berghei ANKA (PbA) were exposed to daily doses of HBO (100% O(2), 3.0 ATA, 1-2 h per day) in conditions well-tolerated by humans and animals, before or after parasite establishment. Cumulative survival analyses demonstrated that HBO therapy protected 50% of PbA-infected mice and delayed CM-specific neurological signs when administrated after patent parasitemia. Pressurized oxygen therapy reduced peripheral parasitemia, expression of TNF-alpha, IFN-gamma and IL-10 mRNA levels and percentage of gamma delta and alpha beta CD4(+) and CD8(+) T lymphocytes sequestered in mice brains, thus resulting in a reduction of blood-brain barrier (BBB)dysfunction and hypothermia. Conclusions/Significance: The data presented here is the first indication that HBO treatment could be used as supportive therapy, perhaps in association with neuroprotective drugs, to prevent CM clinical outcomes, including death.

The role of oxygen vacancy in the photoluminescence property at room temperature of the CaTiO(3)

In this paper, electron paramagnetic resonance, photoluminescence (PL) emission, and quantum mechanical calculations were used to observe and understand the structural order-disorder of CaTiO(3), paying special attention to the role of oxygen vacancy. The PL phenomenon at room temperature of CaTiO(3) is directly influenced by the presence of oxygen vacancies that yield structural order-disorder. These oxygen vacancies bonded at Ti and/or Ca induce new electronic states inside the band gap. Ordered and disordered CaTiO(3) was obtained by the polymeric precursor method. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3190524]

Direct evidence of singlet molecular oxygen generation from peroxynitrate, a decomposition product of peroxynitrite

The decomposition of peroxynitrite to nitrite and dioxygen at neutral pH follows complex kinetics, compared to its isomerization to nitrate at low pH. Decomposition may involve radicals or proceed by way of the classical peracid decomposition mechanism. Peroxynitrite (ONOOH/ONOO(-)) decomposition has been proposed to involve formation of peroxynitrate (O(2)NOOH/O(2)NOO(-)) at neutral pH (D. Gupta, B. Harish, R. Kissner and W. H. Koppenol, Dalton Trans., 2009, DOI: 10.1039/b905535e, see accompanying paper in this issue). Peroxynitrate is unstable and decomposes to nitrite and dioxygen. This study aimed to investigate whether O(2)NOO(-) formed upon ONOOH/ONOO(-) decomposition generates singlet molecular oxygen [O(2) ((1)Delta(g))]. As unequivocally revealed by the measurement of monomol light emission in the near infrared region at 1270 nm and by chemical trapping experiments, the decomposition of ONOO(-) or O(2)NOOH at neutral to alkaline pH generates O(2) ((1)Delta(g)) at a yield of ca. 1% and 2-10%, respectively. Characteristic light emission, corresponding to O(2) ((1)Delta(g)) monomolecular decay was observed for ONOO(-) and for O(2)NOOH prepared by reaction of H(2)O(2) with NO(2)BF(4) and of H(2)O(2) with NO(2)(-) in HClO(4). The generation of O(2) ((1)Delta(g)) from ONOO(-) increased in a concentration-dependent manner in the range of 0.1-2.5 mM and was dependent on pH, giving a sigmoid pro. le with an apparent pK(a) around pD 8.1 (pH 7.7). Taken together, our results clearly identify the generation of O(2) ((1)Delta(g)) from peroxynitrate [O(2)NOO(-) -> NO(2)(-) + O(2) ((1)Delta(g))] generated from peroxynitrite and also from the reactions of H(2)O(2) with either NO(2)BF(4) or NO(2)(-) in acidic media.

Singlet molecular oxygen trapping by the fluorescent probe diethyl-3,3 '-(9,10-anthracenediyl)bisacrylate synthesized by the Heck reaction

Singlet molecular oxygen O(2)((1)Delta(g)) is a potent oxidant that can react with different biomolecules, including DNA, lipids and proteins. Many polycyclic aromatic hydrocarbons have been studied as O(2)((1)Delta(g)) chemical traps. Nevertheless, a suitable modification in the polycyclic aromatic ring must be made to increase the yield of O(2)((1)Delta(g)) chemical trapping. With this goal, an anthracene derivative, diethyl-3,3 '-(9,10-anthracenediyl)bisacrylate (DADB), was obtained from the reaction of 9,10-dibromoanthracene and ethyl acrylate through the Heck coupling reaction. The coupling of ethyl acrylate with the anthracene ring produced a new lipophilic, esterified, fluorescent probe reactive toward O(2)((1)Delta(g)). This compound reacts with O(2)((1)Delta(g)) at a rate of k(r) = 1.69 x 10(6) M(-1) s(-1) forming a stable endoperoxide (DADBO(2)), which was characterized by UV-Vis, fluorescence, HPLC/MS and (1)H and (13)C NMR techniques. The photophysical, photochemical and thermostability features of DADB were also evaluated. Furthermore, this compound has the potential for great application in biological systems because it is easily synthetized in large amount and generates specific endoperoxide (DADBO(2)), which can be easily detected by HPLC tandem mass spectrometry (HPLC/MS/MS).

Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen

Physical and electrochemical properties of nanostructured Ni-doped manganese oxides (MnO(x)) catalysts supported on different carbon powder substrates were investigated so as to characterize any carbon substrate effect toward the oxygen reduction reaction (ORR) kinetics in alkaline medium. These NiMnO(x)/C materials were characterized using physicochemical analyses. Small insertion of Ni atoms in the MnO(x) lattice was observed, which consists of a true doping of the manganese oxide phase. The corresponding NiMnO(x) phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm (from x-ray diffraction analyses). Layered manganite (MnOOH) phase has been detected for the Monarch 1000-supported NiMnO(x) material, while different species of MnO(x) phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnO(x) catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnO(x)/C catalysts, with the occurrence of minority HO(2)(-) disproportionation reaction. The HO(2)(-) disproportionation reaction progressively increases with the Ni content in NiMnO(x) materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3528439] All rights reserved.

Complex Oscillatory Response of a PEM Fuel Cell Fed with H(2)/CO and Oxygen

Oscillatory kinetics is commonly observed in the electrocatalytic oxidation of most species that can be used in fuel cell devices. Examples include formic acid, methanol, ethanol, ethylene glycol, and hydrogen/carbon monoxide mixtures, and most papers refer to half-cell experiments. We report in this paper the experimental investigation of the oscillatory dynamics in a proton exchange membrane (PEM) fuel cell at 30 degrees C. The system consists of a Pt/C cathode fed with oxygen and a PtRu (1:1)/C anode fed with H(2) mixed with 100 ppm of CO, and was studied at different cell currents and anode flow rates. Many different states including periodic and nonperiodic series were observed as a function of the cell current and the H(2)/CO flow rate. In general, aperiodic/chaotic states were favored at high currents and low flow rates. The dynamics was further characterized in terms of the relationship between the oscillation amplitude and the subsequent time required for the anode to get poisoned by carbon monoxide. Results are discussed in terms of the mechanistic aspects of the carbon monoxide adsorption and oxidation. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3463725] All rights reserved.