Discovery of interstellar isocyanogen (CNCN): further evidence that dicyanopolyynes are abundant in space

It is thought that dicyanopolyynes could be potentially abundant interstellar molecules, although their lack of dipole moment makes it impossible to detect them through radioastronomical techniques. Recently, the simplest member of this chemical family, cyanogen (NCCN), was indirectly probed for the first time in interstellar space through the detection of its protonated form toward the dense clouds L483 and TMC-1. Here we present a second firm evidence of the presence of NCCN in interstellar space, namely the detection of the metastable and polar isomer isocyanogen (CNCN). This species has been identified in L483 and tentatively in TMC-1 by observing various rotational transitions in the 3 mm band with the IRAM 30m telescope. We derive beam-averaged column densities for CNCN of 1.6e12 cm-2 in L483 and 9e11 cm-2 in TMC-1, which imply fractional abundances relative to H2 in the range (5-9)e-11. While the presence of NCCN in interstellar clouds seems out of doubt owing to the detection of NCCNH+ and CNCN, putting tight constraints on its abundance is still hampered by the poor knowledge of the chemistry that links NCCN with NCCNH+ and especially with CNCN. We estimate that NCCN could be fairly abundant, in the range 1e-9 - 1e-7 relative to H2, as other abundant nitriles like HCN and HC3N.Comment: Accepted for publication in ApJ Letter

Detection of interstellar HCS and its metastable isomer HSC: new pieces in the puzzle of sulfur chemistry

We present the first identification in interstellar space of the thioformyl radical (HCS) and its metastable isomer HSC. These species were detected toward the molecular cloud L483 thanks to observations carried out with the IRAM 30m telescope in the 3 mm band. We derive beam-averaged column densities of 7e12 cm-2 for HCS and 1.8e11 cm-2 for HSC, which translate to fractional abundances relative to H2 of 2e-10 and 6e-12, respectively. Although the amount of sulfur locked by these radicals is low, their detection allows to put interesting constraints on the chemistry of sulfur in dark clouds. Interestingly, the H2CS/HCS abundance ratio is found to be quite low, around 1, in contrast with the oxygen analogue case, in which the H2CO/HCO abundance ratio is around 10 in dark clouds. Moreover, the radical HCS is found to be more abundant than its oxygen analogue, HCO. The metastable species HOC, the oxygen analogue of HSC, has not been yet observed in space. These observational constraints are confronted with the outcome of a recent model of the chemistry of sulfur in dark clouds. The model underestimates the fractional abundance of HCS by at least one order of magnitude, overestimates the H2CS/HCS abundance ratio, and does not provide an abundance prediction for the metastable isomer HSC. These observations should prompt a revision of the chemistry of sulfur in interstellar clouds.Comment: Accepted for publication in A&A Letter

Nascent bipolar outflows associated with the first hydrostatic core candidates Barnard 1b-N and 1b-S

In the theory of star formation, the first hydrostatic core (FHSC) phase is a critical step in which a condensed object emerges from a prestellar core. This step lasts about one thousand years, a very short time compared with the lifetime of prestellar cores, and therefore is hard to detect unambiguously. We present IRAM Plateau de Bure observations of the Barnard 1b dense molecular core, combining detections of H2CO and CH3OH spectral lines and dust continuum at 2.3" resolution (~ 500 AU). The two compact cores B1b-N and B1b-S are detected in the dust continuum at 2mm, with fluxes that agree with their spectral energy distribution. Molecular outflows associated with both cores are detected. They are inclined relative to the direction of the magnetic field, in agreement with predictions of collapse in turbulent and magnetized gas with a ratio of mass to magnetic flux somewhat higher than the critical value, \mu ~ 2 - 7. The outflow associated with B1b-S presents sharp spatial structures, with ejection velocities of up to ~ 7 kms from the mean velocity. Its dynamical age is estimated to be ~2000 yrs. The B1b-N outflow is smaller and slower, with a short dynamical age of ~1000 yrs. The B1b-N outflow mass, mass-loss rate, and mechanical luminosity agree well with theoretical predictions of FHSC. These observations confirm the early evolutionary stage of B1b-N and the slightly more evolved stage of B1b-S.Comment: 6 pages, 3 figure

Prescribing Albumin in a Central Hospital. New Standards versus Old Habits

O presente estudo teve como objectivo aferir a adequação da prescrição de albumina humana num hospital central à evidência científica nesta área actualmente disponível. O estudo foi retrospectivo e analisou os pedidos de albumina aos serviços farmacêuticos entre Setembro de 2007 e Agosto de 2008. Analisadas 761 requisições de 619 doentes com idade média de 58,1 +/- 14,7 anos, 510 (77%) dos quais do sexo masculino. Foram avaliados parâmetros analíticos globais (proteínas totais, albumina sérica, creatinina e INR) à data da requisição de albumina, grandes grupos nosológicos e os motivos de prescrição. Dos 556.831 frascos de albumina requisitados, foram efectivamente administrados 5.033 (0,9%). Os doentes com patologia hepática foram o grupo nosológico mais representado (60%). Verificou-se que 36% dos pedidos correspondiam aos critérios científicos com suporte de evidência, sendo a hipoalbuminémia o motivo mais frequente de pedido (53%). Concluímos que é necessário um maior cuidado no fundamento dos pedidos de albumina, de forma a adequá-los à evidência científica. Normas restritivas dos serviços farmacêuticos para o fornecimento de albumina encontram-se justificadas

A line confusion-limited millimeter survey of Orion KL. III. Sulfur oxide species

We present a study of the sulfur-bearing species detected in a line confusion-limited survey towards Orion KL performed with the IRAM 30m telescope in the range 80-281 GHz. The study is part of an analysis of the line survey divided into families of molecules. Our aim is to derive accurate physical conditions and molecular abundances in the different components of Orion KL from observed SO and SO2 lines. First we assumed LTE conditions obtain rotational temperatures. We then used a radiative transfer model, assuming either LVG or LTE excitation to derive column densities of these molecules in the different components of Orion KL. We have detected 68 lines of SO, 34SO, 33SO, and S18O and 653 lines of SO2, 34SO2, 33SO2, SO18O and SO2 v2=1. We provide column densities for all of them and also upper limits for the column densities of S17O, 36SO, 34S18O, SO17O and 34SO2 v2=1 and for several undetected sulfur-bearing species. In addition, we present 2'x2' maps around Orion IRc2 of SO2 transitions with energies from 19 to 131 K and also maps with four transitions of SO, 34SO and 34SO2. We observe an elongation of the gas along the NE-SW direction. An unexpected emission peak appears at 20.5 km/s in most lines of SO and SO2. A study of the spatial distribution of this emission feature shows that it is a new component ~5" in diameter, which lies ~4" west of IRc2. We suggest the emission from this feature is related to shocks associated to the BN object. The highest column densities for SO and SO2 are found in the high-velocity plateau (a region dominated by shocks) and in the hot core. These values are up to three orders of magnitude higher than the results for the ridge components. We also find high column densities for their isotopologues in both components. Therefore, we conclude that SO and SO2 are good tracers, not only of regions affected by shocks, but also of regions with warm dense gas.Comment: Paper (ref AA/2013/21285) accepted for publication by A&A. 52 Pages, 26 figures, 13 table

Investigation of HNCO isomers formation in ice mantles by UV and thermal processing: an experimental approach

Current gas phase models do not account for the abundances of HNCO isomers detected in various environments, suggesting a formation in icy grain mantles. We attempted to study a formation channel of HNCO and its possible isomers by vacuum-UV photoprocessing of interstellar ice analogues containing H$_2$O, NH$_3$, CO, HCN, CH$_3$OH, CH$_4$, and N$_2$ followed by warm-up, under astrophysically relevant conditions. Only the H$_2$O:NH$_3$:CO and H$_2$O:HCN ice mixtures led to the production of HNCO species. The possible isomerization of HNCO to its higher energy tautomers following irradiation or due to ice warm-up has been scrutinized. The photochemistry and thermal chemistry of H$_2$O:NH$_3$:CO and H$_2$O:HCN ices was simulated using the Interstellar Astrochemistry Chamber (ISAC), a state-of-the-art ultra-high-vacuum setup. The ice was monitored in situ by Fourier transform mid-infrared spectroscopy in transmittance. A quadrupole mass spectrometer (QMS) detected the desorption of the molecules in the gas phase. UV-photoprocessing of H$_2$O:NH$_3$:CO/H$_2$O:HCN ices lead to the formation of OCN$^-$ as main product in the solid state and a minor amount of HNCO. The second isomer HOCN has been tentatively identified. Despite its low efficiency, the formation of HNCO and the HOCN isomers by UV-photoprocessing of realistic simulated ice mantles, might explain the observed abundances of these species in PDRs, hot cores, and dark clouds

CH2D+, the Search for the Holy Grail

CH2D+, the singly deuterated counterpart of CH3+, offers an alternative way to mediate formation of deuterated species at temperatures of several tens of K, as compared to the release of deuterated species from grains. We report a longstanding observational search for this molecular ion, whose rotational spectroscopy is not yet completely secure. We summarize the main spectroscopic properties of this molecule and discuss the chemical network leading to the formation of CH2D+, with explicit account of the ortho/para forms of H2, H3+ and CH3+. Astrochemical models support the presence of this molecular ion in moderately warm environments at a marginal level.Comment: 25 pages, 6 Figures Accepted in Journal of Physical Chemistry A. "Oka Festschrift: Celebrating 45 years of Astrochemistry

Extended warm gas in Orion KL as probed by methyl cyanide

In order to study the temperature distribution of the extended gas within the Orion Kleinmann-Low nebula, we have mapped the emission by methyl cyanide (CH3CN) in its J=6_K-5_K, J=12_K-11_K, J=13_K-12_K, and J=14_K-13_K transitions at an average angular resolution of ~10 arcsec (22 arcsec for the 6_K-5_K lines), as part of a new 2D line survey of this region using the IRAM 30m telescope. These fully sampled maps show extended emission from warm gas to the northeast of IRc2 and the distinct kinematic signatures of the hot core and compact ridge source components. We have constructed population diagrams for the four sets of K-ladder emission lines at each position in the maps and have derived rotational excitation temperatures and total beam-averaged column densities from the fitted slopes. In addition, we have fitted LVG model spectra to the observations to determine best-fit physical parameters at each map position, yielding the distribution of kinetic temperatures across the region. The resulting temperature maps reveal a region of hot (T > 350 K) material surrounding the northeastern edge of the hot core, whereas the column density distribution is more uniform and peaks near the position of IRc2. We attribute this region of hot gas to shock heating caused by the impact of outflowing material from active star formation in the region, as indicated by the presence of broad CH3CN lines. This scenario is consistent with predictions from C-shock chemical models that suggest that gas-phase methyl cyanide survives in the post-shock gas and can be somewhat enhanced due to sputtering of grain mantles in the passing shock front.Comment: 24 pages, 20 figures, accepted for publication in A&

Insoluble soybean polysaccharides: Obtaining and evaluation of their O/W emulsifying properties

The aims of this work were to obtain different samples of insoluble soybean polysaccharides (ISPS) from defatted soy flour and to study their potential application as O/W emulsifier. In this regard, the insoluble residue (okara) resulting from an aqueous extraction (60 °C, pH 9.0), was submitted to an acidic extraction (pH 3.5, 120 °C) without or with a pretreatment (high pressure homogenization or sonication treatment). The insoluble residues of these extractions were dried (oven, 70 °C or vacuum post-treatment with 2-propanol, 40 °C) yielding different ISPS samples. Aqueous dispersions of ISPS samples (1?2% w/w, pH 3 and 7), were used to prepare coarse and fine O/W emulsions. Emulsion stability against creaming and coalescence processes, and the rheological behavior were analyzed. ISPS samples obtained by okara pretreatment and vacuum dried post-treatment with 2-propanol allow to produces emulsions with high values of flocculation degree, increasing the stability of the particle size, and allowing the formation of stronger gel-like emulsions. These pretreatments expose internal sites of the polysaccharide and protein structures, increasing their superficial hydrophobicity and, therefore, allow a strong absorption of the macromolecules at the oil-water interface and/or the formation of external layers, increasing the rigidity of the interfacial film and contributing to the formation of hydrated flocs, Also, these treatments could solubilize certain compounds in okara that would interfere negatively in the formation of the interfacial film. Particularly, sample obtained by high pressures homogenization of the okara presented the best emulsifying properties and it was not significantly affected by variations in the pH of the emulsion. The results of this research work demonstrate a high potential of application of the ISPS samples as O/W emulsifier, under acid and neutral conditions, increasing the added value of an important by-product of the soybean industry.Fil: Porfiri, María Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología. Laboratorio de Investigación en Funcionalidad y Tecnología de Alimentos; ArgentinaFil: Vaccaro, J.. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología. Laboratorio de Investigación en Funcionalidad y Tecnología de Alimentos; ArgentinaFil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Navarro, Diego Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Wagner, Jorge Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología. Laboratorio de Investigación en Funcionalidad y Tecnología de Alimentos; ArgentinaFil: Cabezas, Dario Marcelino. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología. Laboratorio de Investigación en Funcionalidad y Tecnología de Alimentos; Argentin