445 research outputs found

    A hydrodynamic study of the circumstellar envelope of alpha Scorpii

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    Context: Both the absolute mass-loss rates and the mechanisms that drive the mass loss of late-type supergiants are still not well known. Binaries such as alpha Sco provide the most detailed empirical information about the winds of these stars. Aims: The goal was to improve the binary technique for the determination of the mass-loss rate of alpha Sco A by including a realistic density distribution and velocity field from hydrodynamic and plasma simulations. Methods: We performed 3D hydrodynamic simulations of the circumstellar envelope of alpha Sco in combination with plasma simulations accounting for the heating, ionization, and excitation of the wind by the radiation of alpha Sco B. These simulations served as the basis for an examination of circumstellar absorption lines in the spectrum of alpha Sco B as well as of emission lines from the Antares nebula. Results: The present model of the extended envelope of alpha Sco reproduces some of the structures that were observed in the circumstellar absorption lines in the spectrum of alpha Sco B. Our theoretical density and velocity distributions of the outflow deviate considerably from a spherically expanding model, which was used in previous studies. This results in a higher mass-loss rate of (2 +/- 0.5) x 10^-6 M_sun/yr. The hot H II region around the secondary star induces an additional acceleration of the wind at large distances from the primary, which is seen in absorption lines of Ti II and Cr II at -30 km/s.Comment: 12 pages, 14 figures, accepted for publication in A&

    Mechanistic Investigations of the Asymmetric Hydrogenation of Enamides with Neutral Bis(phosphine) Cobalt Precatalysts

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    The mechanism of the asymmetric hydrogenation of prochiral enamides by well-defined, neutral bis(phosphine) cobalt(0) and cobalt(II) precatalysts has been explored using(R,R)-iPrDuPhos ((R,R)-iPrDuPhos = (+)-1,2-bis[(2R,5R)-2,5-diisopropylphospholano]benzene) as a representative chiral bis(phosphine) ligand. A series of (R,R)-(iPrDuPhos)Co(enamide) (enamide = methyl-2-acetamidoacrylate (MAA), methyl(Z)-α-acetamidocinnamate (MAC), and methyl(Z)-acetamido(4-fluorophenyl)acrylate (4FMAC)) complexes (1-MAA, 1-MAC, and 1-4FMAC), as well as a dinuclear cobalt tetrahydride, [(R,R)-(iPrDuPhos)Co]2(μ2-H)3(H) (2), were independently synthesized, characterized, and evaluated in both stoichiometric and catalytic hydrogenation reactions. Characterization of (R,R)-(iPrDuPhos)Co(enamide) complexes by X-ray diffraction established the formation of the pro-(R) diastereomers in contrast to the (S)-alkane products obtained from the catalytic reaction. In situ monitoring of the cobalt-catalyzed hydrogenation reactions by UV–visible and freeze-quench electron paramagnetic resonance spectroscopies revealed (R,R)-(iPrDuPhos)Co(enamide) complexes as the catalyst resting state for all the three enamides studied. Variable time normalization analysis kinetic studies of the cobalt-catalyzed hydrogenation reactions in methanol established a rate law that is first order in (R,R)-(iPrDuPhos)Co(enamide) and H2 but independent of the enamide concentration. Deuterium-labeling studies, including measurement of an H2/D2 kinetic isotope effect and catalytic hydrogenations with HD, established an irreversible H2 addition step to the bound enamide. Density functional theory calculations support that this step is both rate and selectivity determining. Calculations, as well as HD-labeling studies, provide evidence for two-electron redox cycling involving cobalt(0) and cobalt(II) intermediates during the catalytic cycle. Taken together, these experiments support an unsaturated pathway for the [(R,R)-(iPrDuPhos)Co]-catalyzed hydrogenation of prochiral enamides

    Radial Velocity Studies of Close Binary Stars. IX

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    Radial-velocity measurements and sine-curve fits to the orbital velocity variations are presented for the eighth set of ten close binary systems: AB And, V402 Aur, V445 Cep, V2082 Cyg, BX Dra, V918 Her, V502 Oph, V1363 Ori, KP Peg, V335 Peg. Half of the systems (V445 Cep, V2082 Cyg, V918 Her, V1363 Ori, V335 Peg) were discovered photometrically by the Hipparcos mission and all systems are double-lined (SB2) contact binaries. The broadening function method permitted improvement of the orbital elements for AB And and V502 Oph. The other systems have been observed for radial velocity variations for the first time; in this group are five bright (V<7.5) binaries: V445 Cep, V2082 Cyg, V918 Her, KP Peg and V335 Peg. Several of the studied systems are prime candidates for combined light and radial-velocity synthesis solutions.Comment: 17+ pages, 2 tables, 4 figure

    Speckle observations with PISCO in Merate - V. Astrometric measurements of visual binaries in 2006

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    International audienceWe present relative astrometric measurements of visual binaries made during the first semester of 2006, with the Pupil Interferometry Speckle camera and COronagraph at the 102-cm Zeiss telescope of the Brera Astronomical Observatory, in Merate. Our sample contains orbital couples as well as binaries whose motion is still uncertain. We obtained 217 new measurements of 194 objects, with angular separations in the range 0.1-4.2arcsec, and an average accuracy of 0.01arcsec. The mean error on the position angles is 0.5°. About half of those angles could be determined without the usual 180° ambiguity by the application of triple-correlation techniques. We also present a revised orbit for ADS 277 for which the previously published orbit resulted in a large residual from our measurements

    Extraction of cocoa proanthocyanidins and their fractionation by sequential centrifugal partition chromatography and gel permeation chromatography

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    Erworben im Rahmen der Schweizer Nationallizenzen (http://www.nationallizenzen.ch)Cocoa beans contain secondary metabolites ranging from simple alkaloids to complex polyphenols with most of them believed to possess significant health benefits. The increasing interest in these health effects has prompted the need to develop techniques for their extraction, fractionation, separation, and analysis. This work provides an update on analytical procedures with a focus on establishing a gentle extraction technique. Cocoa beans were finely ground to an average particle size of <100 μm, defatted at 20°C using n-hexane, and extracted three times with 50 % aqueous acetone at 50°C. Determination of the total phenolic content was done using the Folin-Ciocalteu assay, the concentration of individual polyphenols was analyzed by electrospray ionization high performance liquid chromatography-mass spectrometry (ESI-HPLC/MS). Fractions of bioactive compounds were separated by combining sequential centrifugal partition chromatography (SCPC) and gel permeation column chromatography using Sephadex LH-20. For SCPC, a two-phase solvent system consisting of ethyl acetate/n-butanol/water (4:1:5, v/v/v) was successfully applied for the separation of theobromine, caffeine, and representatives of the two main phenolic compound classes flavan-3-ols and flavonols. Gel permeation chromatography on Sephadex LH-20 using a stepwise elution sequence with aqueous acetone has been shown for effectively separating individual flavan-3-ols. Separation was obtained for (-)-epicatechin, proanthocyanidin dimer B2, trimer C1, and tetramer cinnamtannin A2. The purity of alkaloids and phenolic compounds was determined by HPLC analysis and their chemical identity was confirmed by mass spectrometry
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