73 resultados para ion-neutral reactions, astrochemistry, interstellar medium

em Indian Institute of Science - Bangalore - Índia


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We consider the hydrodynamic evolution of gas in the interstellar medium of the host galaxy of a quasar due to Compton heating by the QSO radiation. We show that a Lagrangean formulation of the problem is necessary. It is found that the "hydrodynamic time scale" becomes important compared to the Compton heating time scale. We also relax the "single fluid" approximation by considering the existence of clouds and taking into account the mass loss from stars. The results predict star burst activity, and thus we explain the blue colors of the active galaxies.

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The two-component self-assembly of a 90 degrees PdII acceptor and a triimidazole donor led to the formation of a water-soluble semi-cylindrical cage with a hydrophobic cavity, which was separately crystallized with hydrophilic- and hydrophobic guests. The parent cage was found to catalyze the Knoevenagel condensation reaction of a series of aromatic mono-aldehydes with active methylene compounds, such as Meldrum's acid or 1,3-dimethylbarbituric acid. The confined hydrophobic nanospace within this cage was also used in the catalytic DielsAlder reactions of 9-hydroxymethylanthracene with N-phenylmaleimide or N-cyclohexylmaleimide.

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The host-guest chemistry of most inorganic layered solids is limited to ion-exchange reactions. The guest species are either cations or anions to compensate for the charge deficit, either positive or negative, of the inorganic layers. Here, we outline a strategy to include neutral molecules like ortho- and para-chloranil, that are known to be good acceptors in donor-acceptor or charge-transfer complexes, within the galleries of a layered solid. We have succeeded in including neutral ortho- and para-chloranil molecules within the galleries of an Mg-Al layered double hydroxide (LDH) by using charge-transfer interactions with preintercalated p-aminobenzoate ions as the driving force. The p-aminobenzoate ions are introduced in the Mg-Al LDH via ion exchange. The intercalated LDH can adsorb ortho- and para-chloranil from chloroform solutions by forming charge-transfer complexes with the p-aminobenzoate anions present in the galleries. We use X-ray diffraction, spectroscopy, and molecular dynamics simulations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide.

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The results of an experimental investigation of 1 keV electron irradiation of ices (deposited at 30 K) of (i) pure methanol and (ii) of a 1:1 mixture of NH3:CH3OH are reported. Molecular products formed within the ice were detected and monitored using FTIR spectroscopy. The products observed were methyl formate (H3COHCO), methane (CH4), hydroxymethyl (CH2OH), formamide (HCONH2), formic acid (HCOOH), formaldehyde (H2CO), formyl radical (HCO), cyanate ion (OCN-), isocyanic acid (HNCO), carbon monoxide (CO) and carbon dioxide (CO2). The consequences of these results for prebiotic chemistry in the interstellar medium and star forming regions are discussed. Crown Copyright (C) 2012 Published by Elsevier B. V. All rights reserved.

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We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+. under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

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A survey of recent developments in preparative solid state chemistry shows that, with a knowledge of structural chemistry and reactivity patterns of solids, it is possible to synthesize a variety of new solids possessing novel structures. A distinction is made between synthesis ofnew solids and synthesis of solids bynew methods. Three new routes to solid state synthesis are recognized: the precursor method, and topochemical methods involving redox and ion-exchange reactions. The low-temperature topochemical methods enable synthesis of metastable phases that are inaccessible by the high temperature route. Several illustrative examples of solid state synthesis from the recent literature are presented.

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Transmembrane channel-forming polypeptides can function as uncouplers of mitochondrial oxidative phosphorylation. The observed effects are dependent on the phosphate ion (Pi) concentration in the medium. At low Pi (2.5 mM) the order of uncoupling efficiencies is gramicidin A much greater than alamethicin greater than tetraacetyl melittin greater than melittin. The remarkably high activity of gramicidin A suggests insertion of preformed channel dimers into the membrane. It is also suggested that lipid phase association of peptides is necessary in the other cases. At Pi = 100 mM inhibitory effects are observed for alamethicin and tetraacetyl melittin. Less pronounced inhibition is seen for melittin, while no such effect is noted for gramicidin A. The site of inhibition is shown to be complex IV, and the differences in the behavior of the peptides are rationalized in terms of channel structures.

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Transmembrane channel-forming polypeptides can function as uncouplers of mitochondrial oxidative phosphorylation. The observed effects are dependent on the phosphate ion (Pi) concentration in the medium. At low Pi (2.5 mM) the order of uncoupling efficiencies is gramicidin A much greater than alamethicin greater than tetraacetyl melittin greater than melittin. The remarkably high activity of gramicidin A suggests insertion of preformed channel dimers into the membrane. It is also suggested that lipid phase association of peptides is necessary in the other cases. At Pi = 100 mM inhibitory effects are observed for alamethicin and tetraacetyl melittin. Less pronounced inhibition is seen for melittin, while no such effect is noted for gramicidin A. The site of inhibition is shown to be complex IV, and the differences in the behavior of the peptides are rationalized in terms of channel structures.

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We report new radio continuum and 21 cm HI observations using the Giant Metrewave Radio Telescope (GMRT) of the group Holmberg 124 ( Ho 124) comprising four late-type galaxies, namely NGC 2820, Mrk 108, NGC 2814 and NGC 2805. The three galaxies, NGC 2820, Mrk 108 and NGC 2814 which are closely located in the sky plane have clearly undergone tidal interactions as seen from the various morphological tidal signatures and debris. Moreover we note various features in the group members which we believe might be due to ram pressure. In this paper, we describe four interesting results emerging from our observations: a) detection of the tidal radio continuum bridge at 330 MHz connecting the galaxies NGC 2820+ Mrk 108 with NGC 2814. The radio bridge was discovered at 1465 MHz by van der Hulst & Hummel ( 1985, A& A, 150, 17). We find that the bridge has a fairly steep spectrum with a spectral index alpha(S proportional to nu(alpha)) of - 1.8(-0.2)(+0.3) which is much steeper than the - 0.8 quoted by van der Hulst & Hummel ( 1985); b) detection of other tidal features like the tilted HI and radio continuum disk of NGC 2814, a HI streamer and a radio continuum tail arising from the south of NGC 2814. We also report the detection of a possible tidal dwarf galaxy in HI; c) sharp truncation in the HI distribution in the south of NGC 2820 and in the HI and radio continuum distribution in the north of NGC 2814. The optical disks in both the cases look undisturbed. As pointed out by Davis et al. ( 1997, AJ, 114, 613), ram pressure affects different components of the interstellar medium to varying degrees. Simple estimates of pressure in different components of the interstellar medium ( radio continuum, Ha and HI) in NGC 2820 indicate that ram pressure will significantly influence HI; d) detection of a large one-sided HI loop to the north of NGC 2820. No radio continuum emission or Ha emission is associated with the HI loop. We discuss various scenarios for the origin of this loop including a central starburst, ram pressure stripping and tidal interaction. We do not support the central starburst scenario since the loop is not detected in ionized gas. Using the upper limit on X-ray luminosity of Ho 124 (Mulchaey et al. 2003, ApJS, 145, 39), we estimate an upper limit on the intragroup medium (IGrM) density of 8.8 x 10(-4) cm(-3). For half this electron density, we estimate the ram pressure force of the IGrM to be comparable to the gravitational pull of the disk of NGC 2820. Since tidal interaction has obviously influenced the group, we suggest that the loop could have formed by ram pressure stripping if tidal effects had reduced the surface density of HI in NGC 2820. From the complex observational picture of Ho 124 and the numerical estimates, we suggest that the evolution of the Ho 124 group may be governed by both tidal forces due to the interaction and the ram pressure due to motion of the member galaxies in the IGrM and that the IGrM densities should not be too low (i.e. >= 4 x 10(-4)). However this needs to be verified by further observations.

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Pyridinium poly(hydrogen fluoride) reacts with the oxide of vanadium(V) and chlorides of chromium(III), iron (III) and Co(II) at room temperature forming the pyridinium salts of hexafluoro vanadate(V), hexafluorochromate(III), hexafluoroferrate(III) and hexafluorocobaltate(II) in near quantitative yields (80%). These pyridinium salts are the precursors for the preparation of the alkali metal hexafluorometallates by metathetic reactions in acetonitrile medium with the corresponding metal chlorides. The prepared salts have been identified by their infrared spectral data and elemental analysis.

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We propose a physical mechanism to explain the origin of the intense burst of massive-star formation seen in colliding/merging, gas-rich, field spiral galaxies. We explicitly take account of the different parameters for the two main mass components, H-2 and H I, of the interstellar medium within a galaxy and follow their consequent different evolution during a collision between two galaxies. We also note that, in a typical spiral galaxy-like our galaxy, the Giant Molecular Clouds (GMCs) are in a near-virial equilibrium and form the current sites of massive-star formation, but have a low star formation rate. We show that this star formation rate is increased following a collision between galaxies. During a typical collision between two field spiral galaxies, the H I clouds from the two galaxies undergo collisions at a relative velocity of approximately 300 km s-1. However, the GMCs, with their smaller volume filling factor, do not collide. The collisions among the H I clouds from the two galaxies lead to the formation of a hot, ionized, high-pressure remnant gas. The over-pressure due to this hot gas causes a radiative shock compression of the outer layers of a preexisting GMC in the overlapping wedge region. This makes these layers gravitationally unstable, thus triggering a burst of massive-star formation in the initially barely stable GMCs.The resulting value of the typical IR luminosity from the young, massive stars from a pair of colliding galaxies is estimated to be approximately 2 x 10(11) L., in agreement with the observed values. In our model, the massive-star formation occurs in situ in the overlapping regions of a pair of colliding galaxies. We can thus explain the origin of enhanced star formation over an extended, central area approximately several kiloparsecs in size, as seen in typical colliding galaxies, and also the origin of starbursts in extranuclear regions of disk overlap as seen in Arp 299 (NGC 3690/IC 694) and in Arp 244 (NGC 4038/39). Whether the IR emission from the central region or that from the surrounding extranuclear galactic disk dominates depends on the geometry and the epoch of the collision and on the initial radial gas distribution in the two galaxies. In general, the central starburst would be stronger than that in the disks, due to the higher preexisting gas densities in the central region. The burst of star formation is expected to last over a galactic gas disk crossing time approximately 4 x 10(7) yr. We can also explain the simultaneous existence of nearly normal CO galaxy luminosities and shocked H-2 gas, as seen in colliding field galaxies.This is a minimal model, in that the only necessary condition for it to work is that there should be a sufficient overlap between the spatial gas distributions of the colliding galaxy pair.

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The role of growth conditions and adhesion of Thiobacillus ferrooxidans on the leaching of chalcopyrite was investigated. Thiobacillus ferrooxidans grown on sulfur, thiosulfate and ferrous ion substrates was used in this comparative study. Growth on sulfur, a solid substrate, requires bacterial adhesion unlike that required in the presence of soluble thiosulfate and ferrous ion in a mineral-salts medium. Solid substrate-grown cells showed higher rates of leaching than those grown in liquid media. An initial lag period noticed during leaching by solution-grown cells was absent when solid substrate-grown cells were used. Such a behavior is attributed to the presence of an inducible proteinaceous cell-surface appendage on the sulfur-grown cells. This appendage aids in bacterial adhesion onto the mineral surfaces. Such an appendage is absent in solution-grown cells, as substantiated by electrophoretic measurements. The importance of bacterial adhesion and the direct mechanism in leaching by Thiobacillus ferrooxidans are demonstrated.

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The isothermal section of the phase diagram for the system NiO-MgO-SiO2 at 1373 K is established, The tie lines between (NiXMg1-X)O solid solution with rock salt structure and orthosilicate solid solution (NiYMg1-Y)Si0.5O2 and between orthosilicate and metasilicate (NiZMg1-Z)SiO3 crystalline solutions are determined using electron probe microanalysis (EPMA) and lattice parameter measurement on equilibrated samples, Although the monoxides and orthosilicates of Ni and Mg form a continuous range of solid solutions, the metasilicate phase exists only for 0 < Z < 0.096, The activity of NiO in the rock salt solid solution is determined as a function of composition and temperature in the range of 1023 to 1377 K using a solid state galvanic cell, The Gibbs energy of mixing of the monoxide solid solution can be expressed by a pseudo-subregular solution model: Delta G(ex) = X(1 - X)[(-2430 + 0.925T)X + (-5390 + 1.758T)(1 - X)] J/mol, The thermodynamic data for the rock salt phase are combined with information on interphase partitioning of Ni and Mg to generate the mixing properties for the orthosilicate and the metasilicate solid solutions, The regular solution model describes the orthosilicate and the metasilicate solid solutions at 1373 K within experimental uncertainties, The regular solution parameter Delta G(ex)/Y(1 - Y) is -820 (+/-70) J/mol for the orthosilicate solid solution, The corresponding value for the metasilicate solid solution is -220 (+/-150) J/mol, The derived activities for the orthosilicate solid solution are discussed in relation to the intracrystalline ion exchange equilibrium between M1 and M2 sites. The tie line information, in conjunction with the activity data for orthosilicate and metasilicate solid solutions, is used to calculate the Gibbs energy changes for the intercrystalline ion exchange reactions, Combining this with the known data for NiSi0.5O2, Gibbs energies of formation of MgSi0.5O2, MgSiO3, and metastable NiSiO3 are calculated, The Gibbs energy of formation of NiSiO3, from its component oxides, is equal to 7.67 (+/-0.6) kJ/mol at 1373 K.

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We present observations of low-frequency recombination lines of carbon toward Cas A near 34.5 MHz (n similar to 575) using the Gauribidanur radio telescope and near 560 MHz (n similar to 225) and 770 MHz (n similar to 205) using the NRAO 140 foot (43 m) telescope in Greenbank. We also present high angular resolution (1') observations of the C270 alpha line near 332 MHz using the Very Large Array in B-configuration. A high signal-to-noise ratio spectrum is obtained at 34.5 MHz, which clearly shows a Voigt profile with distinct Lorentzian wings, resulting from significant pressure and radiation broadening at such high quantum numbers. The emission lines detected near 332, 550, and 770 MHz, on the other hand, are narrow and essentially Doppler-broadened. The measured Lorentzian width at 34.5 MHz constrains the allowed combinations of radiation temperature, electron density, and electron temperature in the line-forming region. Radiation broadening at 34.5 MHz places a lower limit of 115 pc on the separation between Cas A and the line-forming clouds. Modeling the variation in the integrated line-to-continuum ratio with frequency indicates that the region is likely to be associated with the cold atomic hydrogen component of the interstellar medium, and the physical properties of this region are likely to be T-e = 75 K, n(e) = 0.02 cm(-3), T-R100 = 3200 K, and n(H) T-e = 10,000 cm(-3) K. Comparison of the distribution of the C270 alpha recombination line emission across Cas A with that of (CO)-C-12 and H I also supports the above conclusion.

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The utility of tetrathiomolybdate in a variety of organic transformations is presented in this account. The sulfur transfer ability of tetrathiomolybdate is exploited in the synthesis of organic disulfides under mild reaction conditions. The induced internal redox reactions associated with tetrathiomolybdate have been thoroughly exploited in developing various methodologies, which include the reduction of organic azides, synthesis of diselenides, cyclic imines, thioamides, and thiolactams. In addition, novel deprotection strategies using tetrathiomolybdate have been developed to cleave the propargyl and propargyloxy carbonyl (POC) protecting groups. Tetrathiomolybdate mediated tandem sulfur transfer-reduction-Michael reactions have been applied to the synthesis of sulfur containing bicyclic systems. Furthermore, the reactions in the solid state and the reactions in water medium assisted by tetrathiomolybdate have greatly simplified the synthesis of organic disulfides.