Subarcsecond Submillimeter Imaging of the Ultracompact HII Region G5.89-0.39

We present the first subarcsecond submillimeter images of the enigmatic ultracompact HII region (UCHII) G5.89-0.39. Observed with the SMA, the 875 micron continuum emission exhibits a shell-like morphology similar to longer wavelengths. By using images with comparable angular resolution at five frequencies obtained from the VLA archive and CARMA, we have removed the free-free component from the 875 micron image. We find five sources of dust emission: two compact warm objects (SMA1 and SMA2) along the periphery of the shell, and three additional regions further out. There is no dust emission inside the shell, supporting the picture of a dust-free cavity surrounded by high density gas. At subarcsecond resolution, most of the molecular gas tracers encircle the UCHII region and appear to constrain its expansion. We also find G5.89-0.39 to be almost completely lacking in organic molecular line emission. The dust cores SMA1 and SMA2 exhibit compact spatial peaks in optically-thin gas tracers (e.g. 34SO2), while SMA1 also coincides with 11.9 micron emission. In CO(3-2), we find a high-velocity north/south bipolar outflow centered on SMA1, aligned with infrared H2 knots, and responsible for much of the maser activity. We conclude that SMA1 is an embedded intermediate mass protostar with an estimated luminosity of 3000 Lsun and a circumstellar mass of ~1 Msun. Finally, we have discovered an NH3 (3,3) maser 12 arcsec northwest of the UCHII region, coincident with a 44 GHz CH3OH maser, and possibly associated with the Br gamma outflow source identified by Puga et al. (2006).Comment: 41 pages, 11 figures, published in The Astrophysical Journal (2008) Volume 680, Issue 2, pp. 1271-1288. An error in the registration of the marker positions in Figure 11 has been corrected in this versio

Revealing the mid-infrared emission structure of IRAS 16594-4656 and IRAS 07027-7934

TIMMI2 diffraction-limited mid-infrared images of a multipolar proto-planetary nebula IRAS 16594-4656 and a young [WC] elliptical planetary nebula IRAS 07027-7934 are presented. Their dust shells are for the first time resolved (only marginally in the case of IRAS 07027-7934) by applying the Lucy-Richardson deconvolution algorithm to the data, taken under exceptionally good seeing conditions (<0.5"). IRAS 16594-4656 exhibits a two-peaked morphology at 8.6, 11.5 and 11.7 microns which is mainly attributed to emission from PAHs. Our observations suggest that the central star is surrounded by a toroidal structure observed edge-on with a radius of 0.4" (~640 AU at an assumed distance of 1.6 kpc) with its polar axis at P.A.~80 degrees, coincident with the orientation defined by only one of the bipolar outflows identified in the HST optical images. We suggest that the material expelled from the central source is currently being collimated in this direction and that the multiple outflow formation has not been coeval. IRAS 07027-7934 shows a bright, marginally extended emission (FWHM=0.3") in the mid-infrared with a slightly elongated shape along the N-S direction, consistent with the morphology detected by HST in the near-infrared. The mid-infrared emission is interpreted as the result of the combined contribution of small, highly ionized PAHs and relatively hot dust continuum. We propose that IRAS 07027-7934 may have recently experienced a thermal pulse (likely at the end of the AGB) which has produced a radical change in the chemistry of its central star.Comment: 35 pages, 8 figures (figures 1, 2, 4 and 6 are in low resolution) accepted for publication in Ap

Combined lignin defunctionalisation and synthesis gas formation by acceptorless dehydrogenative decarbonylation

The valorization of lignin, consisting of various phenylpropanoids building blocks, is hampered by its highly functionalized nature. The absence of the γ-carbinol group in an unnatural C2 β-O-4 motif compared to the native lignin C3 β-O-4 motif provides great opportunities for developing new valorization routes. Thus efficient defunctionalisation approaches that transform the C3 β-O-4 motif into a simplified C2 β-O-4 motif are of interest. Based on a study with a series of model compounds, we established a feasible application of an iridium-catalysed acceptorless dehydrogenative decarbonylation method to efficiently remove the γ-carbinol group in a single step. This defunctionalisation generates valuable synthesis gas, which can be collected as a reaction product. By this direct catalytic transformation, a yield of ∼70% could be achieved for a C3 β-O-4 model compound that was protected from undergoing retro-aldol cleavage by alkoxylation of the benzylic secondary alcohol in the α position. A phenylcoumaran model compound containing a γ-carbinol group as well as a benzylic primary alcohol also proved to be reactive under dehydrogenative decarbonylation conditions, which can further contribute to the reduction of the structural complexity of lignin. Notably, the liberation of synthesis gas was confirmed and the signals for the defunctionalized C2 β-O-4 motif were observed when this dehydrogenative decarbonylation approach was applied on organosolv lignins. This selective defunctionalized lignin in conjunction with the formation of synthesis gas has the potential to enhance the development of profitable and sustainable biorefineries.</p

Spitzer Space Telescope spectral observations of AGB stars in the Fornax dwarf spheroidal galaxy

We have observed five carbon-rich AGB stars in the Fornax dwarf spheroidal (dSph) galaxy, using the Infrared Spectrometer on board the Spitzer Space Telescope. The stars were selected from a near-infrared survey of Fornax and include the three reddest stars, with presumably the highest mass-loss rates, in that galaxy. Such carbon stars probably belong to the intermediate-age population (2-8 Gyr old and metallicity of [Fe/H] -1) of Fornax. The primary aim of this paper is to investigate mass-loss rate, as a function of luminosity and metallicity, by comparing AGB stars in several galaxies with different metallicities. The spectra of three stars are fitted with a radiative transfer model. We find that mass-loss rates of these three stars are 4-7x10^-6 Msun yr-1. The other two stars have mass-loss rates below 1.3x10^-6 Msun yr-1. We find no evidence that these rates depend on metallicity, although we do suggest that the gas-to-dust ratio could be higher than at solar metallicity, in the range 240 to 800. The C2H2 bands are stronger at lower metallicity because of the higher C/O ratio. In contrast, the SiC fraction is reduced at low metallicity, due to low silicon abundance. The total mass-loss rate from all known carbon-rich AGB stars into the interstellar medium of this galaxy is of the order of 2x10^-5 Msun yr-1. This is much lower than that of the dwarf irregular galaxy WLM, which has a similar visual luminosity and metallicity. The difference is attributed to the younger stellar population of WLM. The suppressed gas-return rate to the ISM accentuates the difference between the relatively gas-rich dwarf irregular and the gas-poor dwarf spheroidal galaxies. Our study will be useful to constrain gas and dust recycling processes in low metallicity galaxies.Comment: MNRAS accepte

A Spitzer IRS Spectral Atlas of Luminous 8 micron Sources in the Large Magellanic Cloud

We present an atlas of Spitzer Space Telescope Infrared Spectrograph (IRS) spectra of highly luminous, compact mid-infrared sources in the Large Magellanic Cloud. Sources were selected on the basis of infrared colors and 8 micron (MSX) fluxes indicative of highly evolved, intermediate- to high-mass stars with current or recent mass loss at large rates. We determine the chemistry of the circumstellar envelope from the mid-IR continuum and spectral features and classify the spectral types of the stars. In the sample of 60 sources, we find 21 Red Supergiants (RSGs), 16 C-rich Asymptotic Giant Branch (AGB) stars, 11 HII regions, 4 likely O-rich AGB stars, 4 Galactic O-rich AGB stars, 2 OH/IR stars, and 2 B[e] supergiants with peculiar IR spectra. We find that the overwhelming majority of the sample AGB stars (with typical IR luminosities ~1.0E4 L_sun) have C-rich envelopes, while the O-rich objects are predominantly luminous RSGs with L_IR ~ 1.0E5 L_sun. We determine mean bolometric corrections to the stellar K-band flux densities and find that for carbon stars, the bolometric corrections depend on the infrared color, whereas for RSGs, the bolometric correction is independent of IR color. Our results reveal that objects previously classified as PNe on the basis of IR colors are in fact compact HII regions with very red IRS spectra that include strong atomic recombination lines and PAH emission features. We demonstrate that the IRS spectral classes in our sample separate clearly in infrared color-color diagrams that use combinations of 2MASS data and synthetic IRAC/MIPS fluxes derived from the IRS spectra. On this basis, we suggest diagnostics to identify and classify, with high confidence levels, IR-luminous evolved stars and HII regions in nearby galaxies using Spitzer and near-infrared photometry.Comment: 46 pages, 9 figures; accepted for publication in AJ; abstract abridge

Double logarithms, ln2(1/x)ln^2(1/x), and the NLO DGLAP evolution for the non-singlet component of the nucleon spin structure function, g1g_1

Theoretical predictions show that at low values of Bjorken $x$ the spin structure function, $g_1$ is influenced by large logarithmic corrections, $ln^2(1/x)$, which may be predominant in this region. These corrections are also partially contained in the NLO part of the standard DGLAP evolution. Here we calculate the non-singlet component of the nucleon structure function, $g_1^{NS}=g_1^p-g_1^n$, and its first moment, using a unified evolution equation. This equation incorporates the terms describing the NLO DGLAP evolution and the terms contributing to the $ln^2(1/x)$ resummation. In order to avoid double counting in the overlapping regions of the phase-space, a unique way of including the NLO terms into the unified evolution equation is proposed. The scheme-independent results obtained from this unified evolution are compared to the NLO fit to experimental data, GRSV'2000. Analysis of the first moments of $g_1^{NS}$ shows that the unified evolution including the $ln^2(1/x)$ resummation goes beyond the NLO DGLAP analysis. Corrections generated by double logarithms at low $x$ influence the $Q^2$-dependence of the first moments strongly.Comment: 13 pages, latex, 2 figures; Appendix adde

Chemical Abundances of Planetary Nebulae in the Sagittarius Dwarf Elliptical Galaxy

Spectrophotometry and imaging of the two planetary nebulae He2-436 and Wray16-423, recently discovered to be in the Sagittarius dwarf elliptical galaxy, are presented. Wray16-423 is a high excitation planetary nebula (PN) with a hot central star. In contrast He2-436 is a high density PN with a cooler central star and evidence of local dust, the extinction exceeding that for Wray16-423 by E(B-V)=0.28. The extinction to Wray16-423, (E(B-V)=0.14), is consistent with the extinction to the Sagittarius (Sgr) Dwarf. Both PN show Wolf-Rayet features in their spectra, although the lines are weak in Wray16-423. Images in [O III] and H-alpha+[N II], although affected by poor seeing, yield a diameter of 1.2'' for Wray16-423 after deconvolution; He~2-436 was unresolved. He2-436 has a luminosity about twice that of Wray16-423 and its size and high density suggest a younger PN. In order to reconcile the differing luminosity and nebular properties of the two PN with similar age progenitor stars, it is suggested that they are on He burning tracks The abundance pattern is very similar in both nebulae and shows an oxygen depletion of -0.4 dex with respect to the mean O abundance of Galactic PN and [O/H] = -0.6. The Sgr PN progenitor stars are representative of the higher metallicity tail of the Sgr population. The pattern of abundance depletion is similar to that in the only other PN in a dwarf galaxy companion of the Milky Way, that in Fornax, for which new spectra are presented. However the abundances are larger than for Galactic halo PN suggesting a later formation age. The O abundance of the Sgr galaxy deduced from its PN, shows similarities with that of dwarf ellipticals around M31, suggesting that this galaxy was a dwarf elliptical before its interaction with the Milky Way.Comment: 24 pages, Latex (aas2pp4.sty) including 5 postscript figures. To appear in Ap

Sequential Catalytic Modification of the Lignin alpha-Ethoxylated beta-O-4 Motif To Facilitate C-O Bond Cleavage by Ruthenium-Xantphos Catalyzed Hydrogen Transfer

Lignin is an abundant natural biopolymer that has the potential to act as a renewable feedstock for valuable aromatic compounds via selective catalytic depolymerization. In recent years, elegant, mild, catalytic hydrogen neutral C-O bond cleavage methodologies have been developed on model compounds yielding acetophenone derivatives. However, none of these have been reported to be effective once applied to lignin. One of the reasons for this is the highly functionalized nature of the native lignin beta-O-4 motif; which is often not taken into account in the beta-O-4 model compounds used for methodology development. In this work, we demonstrate the development of a stepwise modification protocol on lignin beta-O-4 model compounds to overall yield a partially defunctionalized beta-O-4 motif. This was achieved by making use of an a-ethoxylated beta-O-4 motif that is readily available from ethanosolv extraction of lignocellulosic biomass. This specific motif allowed us to apply selective copper catalyzed aerobic oxidation and subsequent rhodium catalyzed decarbonylation of the primary hydroxyl group in the y position. The obtained partially defunctionalized beta-O-4 lignin motif allowed effective homogeneous ruthenium catalyzed hydrogen neutral C-O bond cleavage (>99% of 3,4-dimethoxyacetophenone and >99% of guaiacol). The stepwise modification strategy was extended to walnut ethanosolv lignin, demonstrating that the specific structural motifs are accessible from such a readily available lignin. Overall, this work illustrates that the structure of lignin can be strategically modified to allow access to otherwise inaccessible specific aromatic compounds via selective depolymerization methodologies