The chemical diversity of comets

A fundamental question in cometary science is whether the different dynamical classes of comets have different chemical compositions, which would reflect different initial conditions. From the ground or Earth orbit, radio and infrared spectroscopic observations of a now significant sample of comets indeed reveal deep differences in the relative abundances of cometary ices. However, no obvious correlation with dynamical classes is found. Further results come, or are expected, from space exploration. Such investigations, by nature limited to a small number of objects, are unfortunately focussed on short-period comets (mainly Jupiter-family). But these in situ studies provide "ground truth" for remote sensing. We discuss the chemical differences in comets from our database of spectroscopic radio observations, which has been recently enriched by several Jupiter-family and Halley-type comets.Comment: In press in Earth, Moon and Planets (proceedings of the workshop "Future Ground-based Solar System Research: Synergies with Space Probes and Space Telescopes", Portoferraio, Isola d'Elba, Livorno (Italy), 8-12 September 2008). 6 pages with 2 figure

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

Antifreeze in the hot core of Orion - First detection of ethylene glycol in Orion-KL

Comparison of their chemical compositions shows, to first order, a good agreement between the cometary and interstellar abundances. However, a complex O-bearing organic molecule, ethylene glycol (CH$_{2}$OH)$_{2}$, seems to depart from this correlation because it was not easily detected in the interstellar medium although it proved to be rather abundant with respect to other O-bearing species in comet Hale-Bopp. Ethylene glycol thus appears, together with the related molecules glycolaldehyde CH$_{2}$OHCHO and ethanol CH$_{3}$CH$_{2}$OH, as a key species in the comparison of interstellar and cometary ices as well as in any discussion on the formation of cometary matter. We focus here on the analysis of ethylene glycol in the nearest and best studied hot core-like region, Orion-KL. We use ALMA interferometric data because high spatial resolution observations allow us to reduce the line confusion problem with respect to single-dish observations since different molecules are expected to exhibit different spatial distributions. Furthermore, a large spectral bandwidth is needed because many individual transitions are required to securely detect large organic molecules. Confusion and continuum subtraction are major issues and have been handled with care. We have detected the aGg' conformer of ethylene glycol in Orion-KL. The emission is compact and peaks towards the Hot Core close to the main continuum peak, about 2" to the south-west; this distribution is notably different from other O-bearing species. Assuming optically thin lines and local thermodynamic equilibrium, we derive a rotational temperature of 145 K and a column density of 4.6 10$^{15}$ cm$^{-2}$. The limit on the column density of the gGg' conformer is five times lower.Comment: 19 pages, 10 figures, A&A accepte

Mechanistic aspects of thioflavin-T self-aggregation and DNA binding: evidence for dimer attack on DNA grooves

Thioflavin-T (TFT) is a fluorescent marker widely employed in biomedical research but the mechanism of its binding to polynucleotides has been poorly understood. This paper presents a study of the mechanisms of TFT self-aggregation and binding to DNA. Relaxation kinetics of TFT solutions show that the cyanine undergoes dimerization followed by dimer isomerisation. The interaction of TFT with DNA has been investigated using static methods, such as spectrophotometric and spectrofluorometric titrations under different conditions (salt content, temperature), fluorescence quenching, viscometric experiments and the T-jump relaxation method. The combined use of these techniques enabled us to show that the TFT monomer undergoes intercalation between the DNA base pairs and external binding according to a branched mechanism. Moreover, it has also been observed that, under dye excess conditions, the TFT dimer binds to the DNA grooves. The molecular structures of intercalated TFT and the groove-bound TFT dimer are obtained by performing QM/MM MD simulations

Complex organic molecules in comets C/2012 F6 (Lemmon) and C/2013 R1 (Lovejoy): detection of ethylene glycol and formamide

A spectral survey in the 1 mm wavelength range was undertaken in the long-period comets C/2012 F6 (Lemmon) and C/2013 R1 (Lovejoy) using the 30 m telescope of the Institut de radioastronomie millim\'etrique (IRAM) in April and November-December 2013. We report the detection of ethylene glycol (CH$_2$OH)$_2$ (aGg' conformer) and formamide (NH$_2$CHO) in the two comets. The abundances relative to water of ethylene glycol and formamide are 0.2-0.3% and 0.02% in the two comets, similar to the values measured in comet C/1995 O1 (Hale-Bopp). We also report the detection of HCOOH and CH$_3$CHO in comet C/2013 R1 (Lovejoy), and a search for other complex species (methyl formate, glycolaldehyde).Comment: Accepted for publication as a Letter in Astronomy and Astrophysic

Intercalation of Zn(II) and Cu(II) complexes of the cyclic polyamine Neotrien into DNA: equilibria and kinetics

The equilibria and kinetics of the interaction of the Zn(II) and Cu(II) complexes of the macrocyclic polyamine 2,5,8,11-tetraaza[12]-[12](2,9)[1,10]-phenanthrolinophane (Neotrien) with calf thymus DNA have been investigated at pH = 7.0 and T = 25 degreesC by spectrophotometry, spectrofluorimetry and stopped-flow method. At low dye/polymer ratios both complexes bind to DNA according to the excluded site model. At high dye/polymer ratios the binding displays cooperative features. The logarithm of the binding constant depends linearly on - log[NaCl]. The kinetic results suggest the D + S reversible arrow D, S reversible arrow DS mechanism where the metal complexes (D) react with the DNA sites (S) leading to fast formation of an externally bound form (D, S) which, in turn, is converted into internally bound complex (DS) by intercalation. The binding constants, evaluated as ratios of rate constants, agree with those obtained from equilibrium binding experiments, thus confirming the validity of the proposed model. Fluorescence titrations, where the metal-Neotrien complexes were added to DNA previously saturated with ethidium bromide (EB), show that both complexes displace EB from the DNA cavities. The reverse process, i.e. the addition of excess ethidium to the DNA/metal Neotrien systems, leads to fluorescence recovery for DNA/ZnNeotrien but not for DNA/CuNeotrien. This observation suggests that the binding of CuNeotrien induces deep alterations in the DNA structure. Experiments with Poly(dA-dT) . Poly(dA-dT) and Poly(dG-dC) . Poly(dG-dC) reveal that CuNeotrien mainly affects the structure of the latter polynucleotide. (C) 2004 Elsevier Inc. All rights reserved

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

Radio observations of comet 9P/Tempel 1 with the Australia Telescope facilities during the Deep Impact encounter

We present radio observations of comet 9P/Tempel 1 associated with the Deep Impact spacecraft collision of 2005 July 4. Weak 18-cm OH emission was detected with the Parkes 64-m telescope, in data averaged over July 4 to 6, at a level of 12 +/- 3 mJy km/s, corresponding to OH production rate 2.8 x 10^{28} molecules/second (Despois et al. inversion model, or 1.0 x 10^{28} /s for the Schleicher & A'Hearn model). We did not detect the HCN 1-0 line with the Mopra 22-m telescope over the period July 2 to 6. The 3 sigma limit of 0.06 K km/s for HCN on July 4 after the impact gives the limit to the HCN production rate of < 1.8 x 10^{25} /s. We did not detect the HCN 1-0 line, 6.7 GHz CH_3OH line or 3.4-mm continuum with the Australia Telescope Compact Array (ATCA) on July 4, giving further limits on any small-scale structure due to an outburst. The 3 sigma limit on HCN emission of 2.5 K km/s from the ATCA around impact corresponds to limit < 4 x 10^{29} HCN molecules released by the impact.Comment: 7 pages, 1 figure, accepted by MNRA

Role of the P2Y(13) Receptor in the Differentiation of Bone Marrow Stromal Cells into Osteoblasts and Adipocytes

Accumulating evidence indicates that extracellular nucleotides, signaling through purinergic receptors, play a significant role in bone remodeling. Mesenchymal stem cells (MSCs) express functional P2Y receptors whose expression level is regulated during osteoblast or adipocyte differentiation. P2Y13-deficient mice were previously shown to exhibit a decreased bone turnover associated with a reduction in the number of both osteoblasts and osteoclasts on the bone surfaces. We therefore examined whether P2Y13R activation was involved in the osteogenic differentiation of MSC. Our study demonstrated that ADP stimulation of P2Y13R+/+ (but not P2Y13R-/-) adherent bone marrow stromal cells (BMSCs) increased significantly the formation of alkaline phosphatase-colony-forming units (CFU-ALP) as well as the expression of osteoblastic markers (osterix, alkaline phosphatase, and collagen I) involved in the maturation of preosteoblasts into osteoblasts. The number of CFU-ALP obtained from P2Y13R-/- BMSC and the level of osteoblastic gene expression after osteogenic stimulation were strongly reduced compared to those obtained in wild-type cell cultures. In contrast, when P2Y13R-/- BMSCs were incubated in an adipogenic medium, the number of adipocytes generated and the level of adipogenic gene expression (PPARγ2 and Adipsin) were higher than those obtained in P2Y13R+/+ MSC. Interestingly, we observed a significant increase of the number of bone marrow adipocytes in tibia of P2Y13R-/- mice. In conclusion, our findings indicate that the P2Y13R plays an important role in the balance of osteoblast and adipocyte terminal differentiation of bone marrow progenitors. Therefore, the P2Y13 receptor can be considered as a new pharmacological target for the treatment of bone diseases like osteoporosis