Interferometric imaging of carbon monoxide in comet C/1995 O1 (Hale-Bopp): evidence for a strong rotating jet

Observations of the CO J(1-0) 115 GHz and J(2-1) 230 GHz lines in comet C/1995 O1 (Hale-Bopp) were performed with the IRAM Plateau de Bure interferometer on 11 March, 1997. The observations were conducted in both single-dish (ON-OFF) and interferometric modes with 0.13 km s-1 spectral resolution. Images of CO emission with 1.7 to 3" angular resolution were obtained. The ON-OFF and interferometric spectra show a velocity shift with sinusoidal time variations related to the Hale-Bopp nucleus rotation of 11.35 h. The peak position of the CO images moves perpendicularly to the spin axis direction in the plane of the sky. This suggests the presence of a CO jet, which is active night and day at about the same extent, and is spiralling with nucleus rotation. The high quality of the data allows us to constrain the characteristics of this CO jet. We have developed a 3-D model to interpret the temporal evolution of CO spectra and maps. The CO coma is represented as the combination of an isotropic distribution and a spiralling gas jet, both of nucleus origin. Spectra and visibilities (the direct output of interferometric data) analysis shows that the CO jet comprises ~40% the total CO production and is located at a latitude ~20 degrees North on the nucleus surface. Our inability to reproduce all observational characteristics shows that the real structure of the CO coma is more complex than assumed, especially in the first thousand kilometres from the nucleus. The presence of another moving CO structure, faint but compact and possibly created by an outburst, is identified.Comment: 20 pages, 26 figures. Accepted for publication in Astronomy & Astrophysic

Effects of micelle nature and concentration on the acid dissociation constants of the metal extractor PADA

The pyridine-2-azo-p-dimethylaniline (PADA) ligand presents two acid dissociation constants, being pKa1 related to the pyridinium and pKa2 related to the anilinium residue. These have been measured by spectrophotometric titrations in aqueous solutions containing either the anionic (SDS), or the non–ionic (Triton X-100) or the cationic (DTAC) surfactants. The pKai shifts of the charged systems from that of the PADA/Triton X-100 reference (∆pKai0) are compared. For PADA/DTAC ∆pKa10 = 0.05 and ∆pKa20 = 0.6. For PADA/SDS ∆pKa10 = 2.1 and ∆pKa20 = 2.1 both yielding the value of -126 mV for the surface potential (ψ) of SDS. The ψ value, lying between the calculated Stern potential and the zeta potential, indicates that the dye is located on the SDS micelles between the fixed and the shear layer. In contrast, the behaviour of PADA/DTAC is explained assuming that the positively charged deprotonation sites of PADA are forced to protrude towards the bulk solvent by the positive charges of DTAC micelles. The shifts of the apparent pKai from the aqueous values (∆pKaiw) have also been analysed. Concerning PADA/Triton X-100, the shifts ∆pKa1w = -0.1 and ∆pKa2w = -0.9 are rationalized in terms of dielectric constant reduction at the reaction sites. Concerning PADA/DTAC, ∆pKa1w= -0.05 and ∆pKa2w= -0.3 whereas, for PADA/SDS, ∆pKa1w = 2.0 and ∆pKa2w = 1.2. The pKa2w values decrease on raising the surfactant concentrations for all the investigated systems. This behaviour is explained assuming that the increase of the overall micellar surface and, by consequence, of the reaction sites number, results in a site dilution effect which disfavours proton association. The addition of NaCl induces changes of pKa1 and pKa2 which are explained in terms of (large) reduction of ψ for PADA/SDS and of (small) reduction of the dielectric constant for the other systems

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&

Spectroscopic analysis of the binding of paraquat and diquat herbicides to biosubstrates

The study of the interaction of persistent organic pollutants with biosubstrates helps to unravel the pathways for toxicity, however, few mechanistic data are present in the literature for these systems. We analyzed the binding of paraquat (PQ) and diquat (DQ) herbicides to natural calf thymus DNA and a DNA G-quadruplex by spectrophotometric titrations, ethidium bromide exchange tests, viscometry, and melting experiments. The interaction with bovine serum albumin (BSA) protein was studied spectrofluorimetrically at different temperatures. The retention of the targets on positive, negative, and neutral micellar aggregates and liposomes was analyzed by ultrafiltration experiments. Despite some favorable features, PQ and DQ only externally bind natural DNA and do not interact with DNA oligonucleotides. Both herbicides bind bovine serum albumin (BSA). PQ binds BSA mainly according to an electrostatics-driven process. However, ultrafiltration data also show that some hydrophobic contribution participates in the features of these systems. The practical problems related to unfavorable spectroscopic signals and inner filter effects are also discussed. Overall, both herbicides show a low affinity for nucleic acids and weak penetration into liposomes; in addition, the equilibrium constants values found for BSA system suggest optimal conditions for transport in the body

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

On the Different Mode of Action of Au(I)/Ag(I)-NHC Bis-Anthracenyl Complexes Towards Selected Target Biomolecules

Gold and silver N-heterocyclic carbenes (NHCs) are emerging for therapeutic applications. Multiple techniques are here used to unveil the mechanistic details of the binding to different biosubstrates of bis(1-(anthracen-9-ylmethyl)-3-ethylimidazol-2-ylidene) silver chloride [Ag(EIA)2]Cl and bis(1-(anthracen-9-ylmethyl)-3-ethylimidazol-2-ylidene) gold chloride [Au(EIA)2]Cl. As the biosubstrates, we tested natural double-stranded DNA, synthetic RNA polynucleotides (single-poly(A), double-poly(A)poly(U) and triple-stranded poly(A)2poly(U)), DNA G-quadruplex structures (G4s), and bovine serum albumin (BSA) protein. Absorbance and fluorescence titrations, mass spectrometry together with melting and viscometry tests show significant differences in the binding features between silver and gold compounds. [Au(EIA)2]Cl covalently binds BSA. It is here evidenced that the selectivity is high: low affinity and external binding for all polynucleotides and G4s are found. Conversely, in the case of [Ag(EIA)2]Cl, the binding to BSA is weak and relies on electrostatic interactions. [Ag(EIA)2]Cl strongly/selectively interacts only with double strands by a mechanism where intercalation plays the major role, but groove binding is also operative. The absence of an interaction with triplexes indicates the major role played by the geometrical constraints to drive the binding mode

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

Adding Diversity to a Diruthenium Biscyclopentadienyl Scaffold via Alkyne Incorporation: Synthesis and Biological Studies

We report the synthesis and the assessment of the anticancer potential of two series of diruthenium biscyclopentadienyl carbonyl complexes. Novel dimetallacyclopentenone compounds (2-4) were obtained (45-92% yields) from the thermal reaction(PhCCPh exchange) of [Ru2Cp2(CO)(& mu;-CO){& mu;-& eta;(1):& eta;(3)-C(Ph)C(Ph)C(O)}], 1, with alkynes HCCR [R = C5H4FeCp (Fc),3-C6H4(Asp), 2-naphthyl; Cp = & eta;(5)-C5H5, Asp = OC(O)-2-C6H4C(O)Me]. Protonation of 1-3 by HBF4 afforded the corresponding & mu;-alkenyl derivatives 5-7, in 40-86% yields. All productswere characterized by IR and NMR spectroscopy; moreover, cyclic voltammetry(1, 2, 5, 7) andsingle-crystal X-ray diffraction (5, 7)analyses were performed on representative compounds. Complexes 5-7 revealed a cytotoxic activity comparableto that of cisplatin in A549 (lung adenocarcinoma), SW480 (colon adenocarcinoma),and ovarian (A2780) cancer cell lines, and 2, 5, 6, and 7 overcame cisplatin resistancein A2780cis cells. Complexes 2, 5, and 7 (but not the aspirin derivative 6) inducedan increase in intracellular ROS levels. Otherwise, 6 strongly stabilizes and elongates natural DNA (from calf thymus,CT-DNA), suggesting a possible intercalation binding mode, whereas 5 is less effective in binding CT-DNA, and 7 isineffective. This trend is reversed concerning RNA, and in particular, 7 is able to bind poly(rA)poly(rU) showing selectivity forthis nucleic acid. Complexes 5-7 caninteract with the albumin protein with a thermodynamic signature dominatedby hydrophobic interactions. Overall, we show that organometallicspecies based on the Ru2Cp2(CO)( x ) scaffold (x = 2, 3) are activeagainst cancer cells, with different incorporated fragments influencingthe interactions with nucleic acids and the production of ROS

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

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