Hydrogen Isocyanide in Comet 73P/Schwassmann-Wachmann (Fragment B)

We present a sensitive 3-sigma upper limit of 1.1% for the HNC/HCN abundance ratio in comet 73P/Schwassmann-Wachmann (Fragment B), obtained on May 10-11, 2006 using Caltech Submillimeter Observatory (CSO). This limit is a factor of ~7 lower than the values measured previously in moderately active comets at 1 AU from the Sun. Comet 73P/Schwassmann-Wachmann was depleted in most volatile species, except of HCN. The low HNC/HCN ratio thus argues against HNC production from polymers produced from HCN. However, thermal degradation of macromolecules, or polymers, produced from ammonia and carbon compounds, such as acetylene, methane, or ethane appears a plausible explanation for the observed variations of the HNC/HCN ratio in moderately active comets, including the very low ratio in comet 73P/Schwassmann-Wachmann reported here. Similar polymers have been invoked previously to explain anomalous 14N/15N ratios measured in cometary CN.Comment: 6 pages, 5 figures, 2 table

Nitrogen isotopic ratios in Barnard 1: a consistent study of the N2H+, NH3, CN, HCN and HNC isotopologues

The 15N isotopologue abundance ratio measured today in different bodies of the solar system is thought to be connected to 15N-fractionation effects that would have occured in the protosolar nebula. The present study aims at putting constraints on the degree of 15N-fractionation that occurs during the prestellar phase, through observations of D, 13C and 15N-substituted isotopologues towards B1b. Both molecules from the nitrogen hydride family, i.e. N2H+ and NH3, and from the nitrile family, i.e. HCN, HNC and CN, are considered in the analysis. As a first step, we model the continuum emission in order to derive the physical structure of the cloud, i.e. gas temperature and H2 density. These parameters are subsequently used as an input in a non-local radiative transfer model to infer the radial abundances profiles of the various molecules. Our modeling shows that all the molecules are affected by depletion onto dust grains, in the region that encompasses the B1-bS and B1-bN cores. While high levels of deuterium fractionation are derived, we conclude that no fractionation occurs in the case of the nitrogen chemistry. Independently of the chemical family, the molecular abundances are consistent with 14N/15N~300, a value representative of the elemental atomic abundances of the parental gas. The inefficiency of the 15N-fractionation effects in the B1b region can be linked to the relatively high gas temperature ~17K which is representative of the innermost part of the cloud. Since this region shows signs of depletion onto dust grains, we can not exclude the possibility that the molecules were previously enriched in 15N, earlier in the B1b history, and that such an enrichment could have been incorporated into the ice mantles. It is thus necessary to repeat this kind of study in colder sources to test such a possibility.Comment: accepted in A&

An upper limit for the water outgassing rate of the main-belt comet 176P/LINEAR observed with Herschel/HIFI

176P/LINEAR is a member of the new cometary class known as main-belt comets (MBCs). It displayed cometary activity shortly during its 2005 perihelion passage that may be driven by the sublimation of sub-surface ices. We have therefore searched for emission of the H2O 110-101 ground state rotational line at 557 GHz toward 176P/LINEAR with the Heterodyne Instrument for the Far Infrared (HIFI) on board the Herschel Space Observatory on UT 8.78 August 2011, about 40 days after its most recent perihelion passage, when the object was at a heliocentric distance of 2.58 AU. No H2O line emission was detected in our observations, from which we derive sensitive 3-sigma upper limits for the water production rate and column density of < 4e25 molec/s and of < 3e10 cm^{-2}, respectively. From the peak brightness measured during the object's active period in 2005, this upper limit is lower than predicted by the relation between production rates and visual magnitudes observed for a sample of comets by Jorda et al. (2008) at this heliocentric distance. Thus, 176P/LINEAR was likely less active at the time of our observation than during its previous perihelion passage. The retrieved upper limit is lower than most values derived for the H2O production rate from the spectroscopic search for CN emission in MBCs.Comment: 5 pages, 2 figures. Minor changes to match published versio

Interferometric mapping of the 3.3-mm continuum emission of comet 17P/Holmes after its 2007 outburst

Comet 17P/Holmes underwent a dramatic outburst in October 2007, caused by the sudden fragmentation of its nucleus and the production of a large quantity of grains scattering sunlight. We report on 90 GHz continuum observations carried out with the IRAM Plateau de Bure interferometer on 27.1 and 28.2 October 2007 UT, i.e., 4-5 days after the outburst. These observations probed the thermal radiation of large dust particles, and therefore provide the best constraints on the mass in the ejecta debris. The thermal emission of the debris was modelled and coupled to a time-dependent description of their expansion after the outburst. The analysis was performed in the Fourier plane. Visibilities were computed for the two observing dates and compared to the data to measure their velocity and mass. Optical data and 250-GHz continuum measurements published in the literature were used to further constrain the dust kinematics and size distribution. Two distinct dust components in terms of kinematic properties are identified in the data. The large-velocity component, with typical velocities V0 of 50-100 m/s for 1 mm particles, displays a steep size distribution with a size index estimated to q = -3.7 (\pm0.1), assuming a minimum grain size of 0.1 \mum. It corresponds to the fast expanding shell observed in optical images. The slowly-moving "core" component (V0 = 7-9 m/s) detected near the nucleus has a size index |q| < 3.4 and contains a higher proportion of large particles than the shell. The dust mass in the core is in the range 0.1-1 that of the shell. Using optical constants pertaining to porous grains (50% porosity) made of astronomical silicates mixed with water ice (48% in mass), the total dust mass Mdust injected by the outburst is estimated to 4-14 x 10**11 kg, corresponding to 3-9% the nucleus mass.Comment: 15 pages with 11 figures and 7 tables. Accepted for publication in Astronomy & Astrophysic

Anticancer and antibacterial potential of robust Ruthenium(II) arene complexes regulated by choice of α-diimine and halide ligands

Several complexes of general formula [Ru(halide)(η6-p-cymene)(α-diimine)]+, in the form of nitrate, triflate and hexafluorophosphate salts, including a newly synthesized iodide compound, were investigated as potential anticancer drugs and bactericides. NMR and UV–Vis studies evidenced remarkable stability of the complexes in water and cell culture medium. In general, the complexes displayed strong cytotoxicity against A2780 and A549 cancer cell lines with IC50 values in the low micromolar range, and one complex (RUCYN) emerged as the most promising one, with a significant selectivity compared to the non-cancerous HEK293 cell line. A variable affinity of the complexes for BSA and DNA binding was ascertained by spectrophotometry/fluorimetry, circular dichroism, electrophoresis and viscometry. The performance of RUCYN appears associated to enhanced cell internalization, favored by two cyclohexyl substituents, rather than to specific interaction with the evaluated biomolecules. The chloride/iodide replacement, in one case, led to increased cellular uptake and cytotoxicity at the expense of selectivity, and tuned DNA binding towards intercalation. Complexes with iodide or a valproate bioactive fragment exhibited the best antimicrobial profiles

Detection of CO and HCN in Pluto's atmosphere with ALMA

Observations of the Pluto-Charon system, acquired with the ALMA interferometer on June 12-13, 2015, have yielded a detection of the CO(3-2) and HCN(4-3) rotational transitions from Pluto, providing a strong confirmation of the presence of CO, and the first observation of HCN, in Pluto's atmosphere. The CO and HCN lines probe Pluto's atmosphere up to ~450 km and ~900 km altitude, respectively. The CO detection yields (i) a much improved determination of the CO mole fraction, as 515+/-40 ppm for a 12 ubar surface pressure (ii) clear evidence for a well-marked temperature decrease (i.e., mesosphere) above the 30-50 km stratopause and a best-determined temperature of 70+/-2 K at 300 km, in agreement with recent inferences from New Horizons / Alice solar occultation data. The HCN line shape implies a high abundance of this species in the upper atmosphere, with a mole fraction >1.5x10-5 above 450 km and a value of 4x10-5 near 800 km. The large HCN abundance and the cold upper atmosphere imply supersaturation of HCN to a degree (7-8 orders of magnitude) hitherto unseen in planetary atmospheres, probably due to the slow kinetics of condensation at the low pressure and temperature conditions of Pluto's upper atmosphere. HCN is also present in the bottom ~100 km of the atmosphere, with a 10-8 - 10-7 mole fraction; this implies either HCN saturation or undersaturation there, depending on the precise stratopause temperature. The HCN column is (1.6+/-0.4)x10^14 cm-2, suggesting a surface-referred net production rate of ~2x10^7 cm-2s-1. Although HCN rotational line cooling affects Pluto's atmosphere heat budget, the amounts determined in this study are insufficient to explain the well-marked mesosphere and upper atmosphere's ~70 K temperature. We finally report an upper limit on the HC3N column density (< 2x10^13 cm-2) and on the HC15N / HC14N ratio (< 1/125).Comment: Revised version. Icarus, in press, Oct. 11, 2016. 57 pages, including 13 figures and 4 table

Search for CO gas in Pluto, Centaurs and Kuiper Belt objects at radio wavelengths

We have searched for several rotational lines of CO in the Pluto-Charon system, Centaurs (Chiron, Pholus, Nessus, Asbolus, Chariklo and 1998 SG35) and Kuiper Belt objects (1994 TB, 1996 TL66, 1996 TO66, 1996 TP66 and 1998 WH4). The observations were performed with the 30 m telescope of the Institut de Radioastronomie Millimétrique for Pluto/Charon, and with the James Clerk Maxwell Telescope and Caltech Submillimeter Observatory for Centaurs and Kuiper Belt objects. A tentative 4.5-σ J(2-1) CO line is present in the Pluto/Charon spectrum, which requires further confirmation. Assuming that Charon does not contribute to the CO emission, an upper limit of 1.2% and 7% is obtained for the CO/N_2 mixing ratio in Pluto's atmosphere, using the atmospheric thermal structure derived from the Stansberry et al. (1994, Icarus 111, 503) and Strobel et al. (1996, Icarus 120, 266) models, respectively. These upper limits are more constraining (by more than a factor of 6) than the upper limits reported by Young et al. (2001, Icarus, in press) from near-IR spectroscopy. None of the Centaurs or Kuiper Belt objects (KBO) were detected in CO. The CO production rate upper limit obtained for Chiron (3-5 x 10^(27) mol s^(-1)) over 1998-2000 years is a factor of 10 lower than the CO production rate derived from the marginal CO detection obtained in June 1995 by Womack & Stern ([CITE], Astron. Vestnik 33, 216), using same modelling of CO emission. Upper limits obtained for other Centaurs are typically ~10^(28) mol s^(-1), and between 1 and 5 x 10^(28) mol s^(-1) for the best observed KBOs. The comparison between these upper limits and the CO outgassing rates of comet C/1995 O1 (Hale-Bopp) measured at large distances from the Sun shows that Centaurs and KBOs underwent significant CO-devolatilization since their formation

Large excess of heavy nitrogen in both hydrogen cyanide and cyanogen from comet 17P/Holmes

From millimeter and optical observations of the Jupiter-family comet 17P/Holmes performed soon after its huge outburst of October 24, 2007, we derive 14 N/15N = 139 +/- 26 in HCN, and 14N/15N = 165 +/- 40 in CN, establishing that HCN has the same non-terrestrial isotopic composition as CN. The same conclusion is obtained for the long-period comet C/1995 O1 (Hale-Bopp) after a reanalysis of previously published measurements. These results are compatible with HCN being the prime parent of CN in cometary atmospheres. The 15N excess relative to the Earth atmospheric value indicates that N-bearing volatiles in the solar nebula underwent important N isotopic fractionation at some stage of Solar System formation. HCN molecules never isotopically equilibrated with the main nitrogen reservoir in the solar nebula before being incorporated in Oort-cloud and Kuiper-belt comets. The 12C/13C ratios in HCN and CN are measured to be consistent with the terrestrial value.Comment: Accepted for publication in the Astrophysical Journal (Letters) 4 page

Nitrogen isotopic ratios in Barnard 1: a consistent study of the N_2H^+, NH_3, CN, HCN, and HNC isotopologues

Context. The ^(15)N isotopologue abundance ratio measured today in different bodies of the solar system is thought to be connected to ^(15)N-fractionation effects that would have occurred in the protosolar nebula. Aims. The present study aims at putting constraints on the degree of 15N-fractionation that occurs during the prestellar phase, through observations of D, ^(13)C, and ^(15)N-substituted isotopologues towards B1b. Molecules both from the nitrogen hydride family, i.e. N2H+, and NH3, and from the nitrile family, i.e. HCN, HNC, and CN, are considered in the analysis. Methods. As a first step, we modelled the continuum emission in order to derive the physical structure of the cloud, i.e. gas temperature and H_2 density. These parameters were subsequently used as input in a non-local radiative transfer model to infer the radial abundance profiles of the various molecules. Results. Our modelling shows that all the molecules are affected by depletion onto dust grains in the region that encompasses the B1-bS and B1-bN cores. While high levels of deuterium fractionation are derived, we conclude that no fractionation occurs in the case of the nitrogen chemistry. Independently of the chemical family, the molecular abundances are consistent with ^(14)N/^(15)N ~ 300, a value representative of the elemental atomic abundances of the parental gas. Conclusions. The inefficiency of the ^(15)N-fractionation effects in the B1b region can be linked to the relatively high gas temperature ~17 K, which is representative of the innermost part of the cloud. Since this region shows signs of depletion onto dust grains, we cannot exclude the possibility that the molecules were previously enriched in ^(15)N, earlier in the B1b history and that such an enrichment could have been incorporated into the ice mantles. It is thus necessary to repeat this kind of study in colder sources to test such a possibility