Calix[4]pyrrolato Aluminate Catalyzes the Dehydrocoupling of Phenylphosphine Borane to High Molar Weight Polymers

High molar weight polyphosphinoboranes represent materials with auspicious properties, but their preparation requires transition metal-based catalysts. Here, calix[4]pyrrolato aluminate is shown to induce the dehydropolymerization of phosphine boranes to high molar mass polyphosphinoboranes (up to Mn=43 000 Da). Combined GPC and 31P DOSY NMR spectroscopic analyses, quantum chemical computations, and stoichiometric reactions disclose a P−H bond activation by the cooperative action of the square-planar aluminate and the electron-rich ligand framework. This first transition metal-free catalyst for P−B dehydrocoupling overcomes the problem of residual d-block metal impurities in the resulting polymers that might interfere with the reproducibility of the properties for this emerging class of inorganic materials

Vaccinia Virus Arrests and Shifts the Cell Cycle

Modulation of the host cell cycle is a common strategy used by viruses to create a proreplicative environment. To facilitate viral genome replication, vaccinia virus (VACV) has been reported to alter cell cycle regulation and trigger the host cell DNA damage response. However, the cellular factors and viral effectors that mediate these changes remain unknown. Here, we set out to investigate the effect of VACV infection on cell proliferation and host cell cycle progression. Using a subset of VACV mutants, we characterise the stage of infection required for inhibition of cell proliferation and define the viral effectors required to dysregulate the host cell cycle. Consistent with previous studies, we show that VACV inhibits and subsequently shifts the host cell cycle. We demonstrate that these two phenomena are independent of one another, with viral early genes being responsible for cell cycle inhibition, and post-replicative viral gene(s) responsible for the cell cycle shift. Extending previous findings, we show that the viral kinase F10 is required to activate the DNA damage checkpoint and that the viral B1 kinase and/or B12 pseudokinase mediate degradation of checkpoint effectors p53 and p21 during infection. We conclude that VACV modulates host cell proliferation and host cell cycle progression through temporal expression of multiple VACV effector proteins. (209/200.

The Vaccinia Virus (VACV) B1 and Cellular VRK2 Kinases Promote VACV Replication Factory Formation through Phosphorylation-Dependent Inhibition of VACV B12

Comparative examination of viral and host protein homologs reveals novel mechanisms governing downstream signaling effectors of both cellular and vi- ral origin. The vaccinia virus B1 protein kinase is involved in promoting multiple facets of the virus life cycle and is a homolog of three conserved cellular enzymes called vaccinia virus-related kinases (VRKs). Recent evidence indicates that B1 and VRK2 mediate a com- mon pathway that is largely uncharacterized but appears independent of previous VRK substrates. Interestingly, separate studies described a novel role for B1 in inhibiting vac- cinia virus protein B12, which otherwise impedes an early event in the viral lifecycle. Herein, we characterize the B1/VRK2 signaling axis to better understand their shared functions. First, we demonstrate that vaccinia virus uniquely requires VRK2 for viral repli- cation in the absence of B1, unlike other DNA viruses. Employing loss-of-function analy- sis, we demonstrate that vaccinia virus’s dependence on VRK2 is only observed in the presence of B12, suggesting that B1 and VRK2 share a pathway controlling B12. More- over, we substantiate a B1/VRK2/B12 signaling axis by examining coprecipitation of B12 by B1 and VRK2. Employing execution point analysis, we reveal that virus replication proceeds normally through early protein translation and uncoating but stalls at replica- tion factory formation in the presence of B12 activity. Finally, structure/function analyses of B1 and VRK2 demonstrate that enzymatic activity is essential for B1 or VRK2 to inhibit B12. Together, these data provide novel insights into B1/VRK signaling coregulation and support a model in which these enzymes modulate B12 in a phosphorylation-depen- dent manner

Diverse silver(I) coordination chemistry with cyclic selenourea ligands

The coordination chemistry of two selenourea ligands (SeIMes and SeIPr) towards silver(I) triflate and silver(I) nitrate was investigated. Two aggregation modes were observed in the solid state, strongly influenced by the size of the aromatic substituents on the ligand. With mesityl groups, selenium-bridged bimetallic motifs [AgX(SeIMes)]2 were obtained, while for the bulkier diisopropylphenyl groups ion-separated species of formulae [Ag(SeIPr)2]+[X]− were obtained. Recrystallization of [Ag(NO3)(SeIMes)]2 from hot methanol resulted in the formation of a unique coordination polymer featuring three silver environments. Characterization of the complexes by NMR spectroscopy and mass spectrometry suggested all complexes adopt the ionic aggregation mode in methanol solution.Natural Sciences and Engineering Research Council of Canada (Discovery Development Grant (DDG-2017-00041))https://pubs.rsc.org/en/content/articlelanding/2018/DT/C7DT04243D#!divAbstrac

A panchromatic study of BLAST counterparts: total star-formation rate, morphology, AGN fraction and stellar mass

We carry out a multi-wavelength study of individual galaxies detected by the Balloon-borne Large Aperture Submillimeter Telescope (BLAST) and identified at other wavelengths, using data spanning the radio to the ultraviolet (UV). We develop a Monte Carlo method to account for flux boosting, source blending, and correlations among bands, which we use to derive deboosted far-infrared (FIR) luminosities for our sample. We estimate total star-formation rates for BLAST counterparts with z < 0.9 by combining their FIR and UV luminosities. Star formation is heavily obscured at L_FIR > 10^11 L_sun, z > 0.5, but the contribution from unobscured starlight cannot be neglected at L_FIR < 10^11 L_sun, z < 0.25. We assess that about 20% of the galaxies in our sample show indication of a type-1 active galactic nucleus (AGN), but their submillimeter emission is mainly due to star formation in the host galaxy. We compute stellar masses for a subset of 92 BLAST counterparts; these are relatively massive objects, with a median mass of ~10^11 M_sun, which seem to link the 24um and SCUBA populations, in terms of both stellar mass and star-formation activity. The bulk of the BLAST counterparts at z<1 appear to be run-of-the-mill star-forming galaxies, typically spiral in shape, with intermediate stellar masses and practically constant specific star-formation rates. On the other hand, the high-z tail of the BLAST counterparts significantly overlaps with the SCUBA population, in terms of both star-formation rates and stellar masses, with observed trends of specific star-formation rate that support strong evolution and downsizing.Comment: Accepted for publication in the Astrophysical Journal. 44 pages, 11 figures. The SED template for the derivation of L_FIR has changed (added new figure) and the discussion on the stellar masses has been improved. The complete set of full-color postage-stamps can be found at http://blastexperiment.info/results_images/moncelsi

A Bright Submillimeter Source in the Bullet Cluster (1E0657--56) Field Detected with BLAST

We present the 250, 350, and 500 micron detection of bright submillimeter emission in the direction of the Bullet Cluster measured by the Balloon-borne Large Aperture Submillimeter Telescope (BLAST). The 500 micron centroid is coincident with an AzTEC 1.1 mm point-source detection at a position close to the peak lensing magnification produced by the cluster. However, the 250 micron and 350 micron centroids are elongated and shifted toward the south with a differential shift between bands that cannot be explained by pointing uncertainties. We therefore conclude that the BLAST detection is likely contaminated by emission from foreground galaxies associated with the Bullet Cluster. The submillimeter redshift estimate based on 250-1100 micron photometry at the position of the AzTEC source is z_phot = 2.9 (+0.6 -0.3), consistent with the infrared color redshift estimation of the most likely IRAC counterpart. These flux densities indicate an apparent far-infrared luminosity of L_FIR = 2E13 Lsun. When the amplification due to the gravitational lensing of the cluster is removed, the intrinsic far-infrared luminosity of the source is found to be L_FIR <= 10^12 Lsun, consistent with typical luminous infrared galaxies.Comment: Accepted for publication in the Astrophysical Journal. Maps are available at http://blastexperiment.info

BLAST: The Mass Function, Lifetimes, and Properties of Intermediate Mass Cores from a 50 Square Degree Submillimeter Galactic Survey in Vela (l = ~265)

We present first results from an unbiased 50 deg^2 submillimeter Galactic survey at 250, 350, and 500 micron from the 2006 flight of the Balloon-borne Large Aperture Submillimeter Telescope (BLAST). The map has resolution ranging from 36 arcsec to 60 arcsec in the three submillimeter bands spanning the thermal emission peak of cold starless cores. We determine the temperature, luminosity, and mass of more than one thousand compact sources in a range of evolutionary stages and an unbiased statistical characterization of the population. From comparison with C^(18)O data, we find the dust opacity per gas mass, kappa r = 0.16 cm^2 g^(-1) at 250 micron, for cold clumps. We find that 2% of the mass of the molecular gas over this diverse region is in cores colder than 14 K, and that the mass function for these cold cores is consistent with a power law with index alpha = -3.22 +/- 0.14 over the mass range 14 M_sun < M < 80 M_sun. Additionally, we infer a mass-dependent cold core lifetime of t_c(M) = 4E6 (M/20 M_sun)^(-0.9) years - longer than what has been found in previous surveys of either low or high mass cores, and significantly longer than free fall or likely turbulent decay times. This implies some form of non-thermal support for cold cores during this early stage of star formation.Comment: Accepted for publication in the Astrophysical Journal. Maps available at http://blastexperiment.info

Over half of the far-infrared background light comes from galaxies at z >= 1.2

Submillimetre surveys during the past decade have discovered a population of luminous, high-redshift, dusty starburst galaxies. In the redshift range 1 <= z <= 4, these massive submillimetre galaxies go through a phase characterized by optically obscured star formation at rates several hundred times that in the local Universe. Half of the starlight from this highly energetic process is absorbed and thermally re-radiated by clouds of dust at temperatures near 30 K with spectral energy distributions peaking at 100 microns in the rest frame. At 1 <= z <= 4, the peak is redshifted to wavelengths between 200 and 500 microns. The cumulative effect of these galaxies is to yield extragalactic optical and far-infrared backgrounds with approximately equal energy densities. Since the initial detection of the far-infrared background (FIRB), higher-resolution experiments have sought to decompose this integrated radiation into the contributions from individual galaxies. Here we report the results of an extragalactic survey at 250, 350 and 500 microns. Combining our results at 500 microns with those at 24 microns, we determine that all of the FIRB comes from individual galaxies, with galaxies at z >= 1.2 accounting for 70 per cent of it. As expected, at the longest wavelengths the signal is dominated by ultraluminous galaxies at z > 1.Comment: Accepted to Nature. Maps available at http://blastexperiment.info

The BLAST Survey of the Vela Molecular Cloud: Physical Properties of the Dense Cores in Vela-D

The Balloon-borne Large-Aperture Submillimeter Telescope (BLAST) carried out a 250, 350 and 500 micron survey of the galactic plane encompassing the Vela Molecular Ridge, with the primary goal of identifying the coldest dense cores possibly associated with the earliest stages of star formation. Here we present the results from observations of the Vela-D region, covering about 4 square degrees, in which we find 141 BLAST cores. We exploit existing data taken with the Spitzer MIPS, IRAC and SEST-SIMBA instruments to constrain their (single-temperature) spectral energy distributions, assuming a dust emissivity index beta = 2.0. This combination of data allows us to determine the temperature, luminosity and mass of each BLAST core, and also enables us to separate starless from proto-stellar sources. We also analyze the effects that the uncertainties on the derived physical parameters of the individual sources have on the overall physical properties of starless and proto-stellar cores, and we find that there appear to be a smooth transition from the pre- to the proto-stellar phase. In particular, for proto-stellar cores we find a correlation between the MIPS24 flux, associated with the central protostar, and the temperature of the dust envelope. We also find that the core mass function of the Vela-D cores has a slope consistent with other similar (sub)millimeter surveys.Comment: Accepted for publication in the Astrophysical Journal. Data and maps are available at http://blastexperiment.info