484 research outputs found

    Probing the Interstellar Medium of External Galaxies Using Quasar Absorption Lines: the 3C 232/NGC 3067 System

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    Quasar absorption lines offer unique opportunities to probe the interstellar medium of external galaxies. Researchers present new optical and UV absorption line spectroscopy of the quasar 3C232 (z=0.55) revealing new detail in the foreground absorption system due to the bright, spiral galaxy NGC 3067 (cz=1420 km/s). Specifically, the spectra show evidence for two and possibly three separate absorption components in CaII and Na I spanning approx. 150 km/s. The original HI detection of Haschick and Burke (1975) corresponds to the strongest of these metal systems which exhibits doublet ratios consistent with saturation in both CaII and Na I. Due to the recent detection in HI emission of a tidal tail or finger of HI extending from the western edge of NGC 3067 through the position of 3C 232 (Carilli, van Gorkom and Stocke, 1989), the morphology of the HI absorber is now known and is not either a warped disk nor a spherical halo as had been proposed. New deep continuum and H alpha imaging provides a sensitive upper limit on the the ionizing continuum impinging upon this cloud (and thus a limit on the intensity of the extragalactic ionizing radiation field). Together with the observed UV spectrum of 3C 232, the optical emission line ratios and the deep H alpha imaging set a minimum distance between the quasar and the HI cloud disregarding redshift information. This limit strains the non-cosmological redshift interpretation for 3C 232 -- and this quasar is one of the original 5 3C quasars found to be too close to NGC galaxies as if by chance (Burbidge, Burbidge, Solomon and Strittmatter, 1972)

    A polymorph of tetra­ethyl­ammonium chloride

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    The structure of the title compound, C8H20N+·Cl−, is compared with a polymorph that was described earlier in the same space group. Differences in the conformations of the ethyl groups of the cation exist between the polymorphs. This study is given here in order to provide additional unit-cell data for use in qualitative identification of crystalline samples obtained in syntheses in which Et4N+·Cl− is either used or generated

    Ligand radicals as modular organic electron spin qubits

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    The intrinsic redox activity of the dithiolene ligand is presented here as the novel spin host in the design of prototype molecular electron spin qubit where the traditional roles of the metal and ligand components in coordination complexes are inverted. A series of paramagnetic bis(dithiolene) complexes with group 10 metals – nickel, palladium, platinum – provides a backdrop to investigate the spin dynamics of the organic ligand radical using pulsed EPR spectroscopy. The temperature dependence of the phase memory time (TM) is shown to be dependent on the identity of the diamagnetic metal ion with the short times recorded for platinum a consequence of a diminishing spin‐lattice (T1) relaxation time driven by spin‐orbit coupling. The utility of the radical ligand spin center is confirmed when it delivers one of the longest phase memory times ever recorded for a molecular two‐qubit prototype

    Expanding the scope of ligand substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) to afford new heteroleptic dithiolene complexes

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    The scope of direct substitution of the dithiolene ligand from [M(S2C2Ph2)2] [M = Ni2+ (1), Pd2+ (2), Pt2+ (3)] to produce heteroleptic species [M(S2C2Ph2)2Ln] (n = 1, 2) has been broadened to include isonitriles and dithiooxamides in addition to phosphines and diimines. Collective observations regarding ligands that cleanly produce [M(S2C2Ph2)Ln], do not react at all, or lead to ill-defined decomposition identify soft σ donors as the ligand type capable of dithiolene substitution. Substitution of MeNC from [Ni(S2C2Ph2)(CNMe)2] by L provides access to a variety of heteroleptic dithiolene complexes not accessible from 1. Substitution of a dithiolene ligand from 1 involves net redox disproportionation of the ligands from radical monoanions, –S•SC2Ph2, to enedithiolate and dithione, the latter of which is an enhanced leaving group that is subject to further irreversible reactions

    Infrared Emission from the Nearby Cool Core Cluster Abell 2597

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    We observed the brightest central galaxy (BCG) in the nearby (z=0.0821) cool core galaxy cluster Abell 2597 with the IRAC and MIPS instruments on board the Spitzer Space Telescope. The BCG was clearly detected in all Spitzer bandpasses, including the 70 and 160 micron wavebands. We report aperture photometry of the BCG. The spectral energy distribution exhibits a clear excess in the FIR over a Rayleigh-Jeans stellar tail, indicating a star formation rate of ~4-5 solar masses per year, consistent with the estimates from the UV and its H-alpha luminosity. This large FIR luminosity is consistent with that of a starburst or a Luminous Infrared Galaxy (LIRG), but together with a very massive and old population of stars that dominate the energy output of the galaxy. If the dust is at one temperature, the ratio of 70 to 160 micron fluxes indicate that the dust emitting mid-IR in this source is somewhat hotter than the dust emitting mid-IR in two BCGs at higher-redshift (z~0.2-0.3) and higher FIR luminosities observed earlier by Spitzer, in clusters Abell 1835 and Zwicky 3146.Comment: Accepted at Ap

    trans-Bis(N,N-diethyl­ethylenediamine)­nickel(II) dibromide

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    The structure of the title compound, [Ni(C6H16N2)2]Br2 or [Ni(Et2en)2]Br2 (Et2en is asymmetric N,N-diethyl­ethylene­diamine), containing an NiII atom (site symmetry ) in square-planar NiN4 coordination, is described and contrasted with related structures containing NiII in octa­hedral coordination with axial X − ligands (X − = variable anions). The dialkyl­ated N atom has an appreciably longer bond length to the NiII atom [1.9666 (13) Å] than does the unsubstituted N atom [1.9202 (14) Å]. The Ni—N bond lengths in [Ni(Et2en)2]Br2 are significantly shorter than corresponding values in tetra­gonally distorted [Ni(Et2en)2 X 2] compounds (X = −O2CCF3, OH2, or −NCS), which have a triplet ground state. The electronic configuration in these axially ligated [Ni(Et2en)2 X 2] compounds populates the metal-based d x 2 -y 2 orbital, which is Ni—N anti­bonding in character. Each Et2en ligand in each [Ni(Et2en)2]2+ cation forms a pair of N—H⋯Br hydrogen bonds to the Br− anions, one above and below the NiN4 square plane. Thus, a ribbon of alternating Br− pairs and [Ni(Et2en)2]2+ cations that are canted at 65° relative to one another is formed by hydrogen bonds

    Group 10 metal dithiolene bis(isonitrile) complexes: synthesis, structures, properties and reactivity

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    The reaction of [(Ph2C2S2)2M] (M = Ni2+, Pd2+, Pt2+) with 2 equiv of RN≡C (R = Me (a), Bn (b), Cy (c), tBu (d), 1-Ad (e), Ph (f)) yields [(Ph2C2S2)M(C≡NR)2] (M = Ni2+, 4a–f; M = Pd2+, 5a–f; M = Pt2+, 6a–f), which are air-stable and amenable to chromatographic purification. All members have been characterized crystallographically. Structurally, progressively greater planarity tends to be manifested as M varies from Ni to Pt, and a modest decrease in the C≡N bond length of coordinated C≡NR appears in moving from Ni toward Pt. Vibrational spectroscopy (CH2Cl2 solution) reveals νC≡N frequencies for [(Ph2C2S2)M(C≡NR)2] that are substantially higher than those for free C≡NR and increase as M ranges from Ni to Pt. This trend is interpreted as arising from an increasingly positive charge at M that stabilizes the linear, charge-separated resonance form of the ligand over the bent form with lowered C–N bond order. UV–vis spectra reveal lowest energy transitions that are assigned as HOMO (dithiolene π) → LUMO (M–L σ*) excitations. One-electron oxidations of [(Ph2C2S2)M(C≡NR)2] are observed at ∼+0.5 V due to Ph2C2S22– → Ph2C2S–S• + e–. Chemical oxidation of [(Ph2C2S2)Pt(C≡NtBu)2] with [(Br-p-C6H4)3N][SbCl6] yields [(Ph2C2S–S•)Pt(C≡NtBu)2]+, identified spectroscopically, but in the crystalline state [[(Ph2C2S–S•)Pt(C≡NtBu)2]2]2+ prevails, which forms via axial Pt···S interactions and pyramidalization at the metal. Complete substitution of MeNC from [(Ph2C2S2)Ni(C≡NMe)2] by 2,6-Me2py under forcing conditions yields [(2,6-Me2py)Ni(μ2-η1,η1-S′,η1-S″-S2C2Ph2)]2 (8), which features a folded Ni2S2 core. In most cases, isocyanide substitution from [(Ph2C2S2)M(C≡NMe)2] with monodentate ligands (L = phosphine, CN–, carbene) leads to [(Ph2C2S2)M(L)(C≡NMe)]n (n = 0, 1−), wherein νC≡N varies according to the relative σ-donating power of L (9–21). The use of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) provides [(Ph2C2S2)M(IPr)(C≡NMe)] for M = Ni (18), Pd (19), but for Pt, attack by IPr at the isocyanide carbon occurs to yield the unusual η1,κC-ketenimine complex [(Ph2C2S2)Pt(C(NMe)(IPr))(C≡NMe)] (20)

    Redox-active metallodithiolene groups separated by insulating tetraphosphinobenzene spacers

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    Compounds of the type [(S2C2R2)M(μ-tpbz)M(S2C2R2)] (R = CN, Me, Ph, p-anisyl; M = Ni, Pd, Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) have been prepared by transmetalation with [(S2C2R2)SnR′2] reagents, by direct displacement of dithiolene ligand from [M(S2C2R2)2] with 0.5 equiv of tpbz, or by salt metathesis using Na2[S2C2(CN)2] in conjunction with X2M(μ-tpbz)MX2 (X = halide). X-ray crystallography reveals a range of topologies (undulating, chair, bowed) for the (S2C2)M(P2C6P2)M(S2C2) core. The [(S2C2R2)M(μ-tpbz)M(S2C2R2)] (R = Me, Ph, p-anisyl) compounds support reversible or quasireversible oxidations corresponding to concurrent oxidation of the dithiolene terminal ligands from ene-1,2-dithiolates to radical monoanions, forming [(−S•SC2R2)M(μ-tpbz)M(−S•SC2R2)]2+. The R = Ph and p-anisyl compounds support a second, reversible oxidation of the dithiolene ligands to their α-dithione form. In contrast, [(S2C2(CN)2)Ni(tpbz)Ni(S2C2(CN)2)] sustains only reversible, metal-centered reductions. Spectroscopic examination of [(−S•SC2(p-anisyl)2)Ni(μ-tpbz)Ni(−S•SC2(p-anisyl)2)]2+ by EPR reveals a near degenerate singlet–triplet ground state, with spectral simulation revealing a remarkably small dipolar coupling constant of 18 × 10–4 cm–1 that is representative of an interspin distance of 11.3 Å. This weak interaction is mediated by the rigid tpbz ligand, whose capacity to electronically insulate is an essential quality in the development of molecular-based spintronic devices

    CAPG is required for Ebola virus infection by controlling virus egress from infected cells

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    The replication of Ebola virus (EBOV) is dependent upon actin functionality, especially at cell entry through macropinocytosis and at release of virus from cells. Previously, major actin-regulatory factors involved in actin nucleation, such as Rac1 and Arp2/3, were shown important in both steps. However, downstream of nucleation, many other cell factors are needed to control actin dynamics. How these regulate EBOV infection remains largely unclear. Here, we identified the actin-regulating protein, CAPG, as important for EBOV replication. Notably, knockdown of CAPG specifically inhibited viral infectivity and yield of infectious particles. Cell-based mechanistic analysis revealed a requirement of CAPG for virus production from infected cells. Proximity ligation and split-green fluorescent protein reconstitution assays revealed strong association of CAPG with VP40 that was mediated through the S1 domain of CAPG. Overall, CAPG is a novel host factor regulating EBOV infection through connecting actin filament stabilization to viral egress from cells
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