Methanation of CO over Ni catalyst: A theoretical study

Theoretical methods (generalized valence‐bond calculations) were used to examine the bond energies and geometries of numerous species chemisorbed onto Ni clusters representing Ni surface. These results were used to obtain thermochemical information and to examine various mechanisms for the methanation of CO over Ni: CO+3H^(→)_(2(Ni)) CH_4+H_2O. It is found that chemisorbed formyl radicals (Ni–CHO) lead to a favorably appearing chain reaction that is consistent with current experimental results. In addition, we find a chemisorbed C_2 species that may be the catalytically active C_(ad) formed from dissociation of CO

Probing 3D Density and Velocity Fields of ISM in Centers of Galaxies with Future X-Ray Observations

Observations of bright and variable "reflected" X-ray emission from molecular clouds located within inner hundred parsec of our Galaxy have demonstrated that the central supermassive black hole, Sgr A*, experienced short and powerful flares in the past few hundred years. These flares offer a truly unique opportunity to determine 3D location of the illuminated clouds (with ~10 pc accuracy) and to reveal their internal structure (down to 0.1 pc scales). Short duration of the flare(s), combined with X-rays high penetration power and insensitivity of the reflection signal to thermo- and chemo-dynamical state of the gas, ensures that the provided diagnostics of the density and velocity fields is unbiased and almost free of the projection and opacity effects. Sharp and sensitive snapshots of molecular gas accessible with aid of future X-ray observatories featuring large collecting area and high angular (arcsec-level) and spectral (eV-level) resolution cryogenic bolometers will present invaluable information on properties of the supersonic turbulence inside the illuminated clouds, map their shear velocity field and allow cross-matching between X-ray data and velocity-resolved emission of various molecular species provided by ALMA and other ground-based facilities. This will highlight large and small-scale dynamics of the dense gas and help uncovering specifics of the ISM lifecycle and high-mass star formation under very extreme conditions of galactic centers. While the former is of particular importance for the SMBH feeding and triggering AGN feedback, the latter might be an excellent test case for star formation taking place in high-redshift galaxies.Comment: White paper submitted to the Astro2020 Decadal Surve

Expression of a catalytically inactive mutant form of glutathione peroxidase 4 (Gpx4) confers a dominant-negative effect in male fertility.

The selenoenzyme Gpx4 is essential for early embryogenesis and cell viability for its unique function to prevent phospholipid oxidation. Recently, the cytosolic form of Gpx4 was identified as an upstream regulator of a novel form of non-apoptotic cell death, called ferroptosis, whereas the mitochondrial isoform of Gpx4 (mGpx4) was previously shown to be crucial for male fertility. Here, we generated and analyzed mice with targeted mutation of the active site selenocysteine (Sec) of Gpx4 (Gpx4_U46S). Mice homozygous for Gpx4_U46S died at the same embryonic stage (E7.5) as Gpx4-/- embryos as expected. Surprisingly, male mice heterozygous for Gpx4_U46S presented subfertility. Subfertility was manifested in a reduced number of litters from heterozygous breedings and an impairment of spermatozoa to fertilize oocytes in vitro. Morphologically, sperm isolated from heterozygous Gpx4_U46S mice revealed many structural abnormalities particularly in the spermatozoan midpiece due to improper oxidation and polymerization of sperm capsular proteins and malformation of the mitochondrial capsule surrounding and stabilizing sperm mitochondria. These findings are reminiscent of sperm isolated from selenium-deprived rodents or from mice specifically lacking mGpx4. Due to a strongly facilitated incorporation of Ser in the polypeptide chain as compared to Sec at the UGA codon, expression of the catalytically inactive Gpx4_U46S was found to be strongly increased. Since the stability of the mitochondrial capsule of mature spermatozoa depends on the moonlighting function of Gpx4 both as an enzyme oxidizing capsular protein thiols and being a structural protein, tightly controlled expression of functional Gpx4 emerges being key for full male fertility

The influence of the turbulent perturbation scale on prestellar core fragmentation and disk formation

The collapse of weakly turbulent prestellar cores is a critical stage in the process of star formation. Being highly non-linear and stochastic, the outcome of collapse can only be explored theoretically by performing large ensembles of numerical simulations. Standard practice is to quantify the initial turbulent velocity field in a core in terms of the amount of turbulent energy (or some equivalent) and the exponent in the power spectrum (n \equiv -d log Pk /d log k). In this paper, we present a numerical study of the influence of the details of the turbulent velocity field on the collapse of an isolated, weakly turbulent, low-mass prestellar core. We show that, as long as n > 3 (as is usually assumed), a more critical parameter than n is the maximum wavelength in the turbulent velocity field, {\lambda}_MAX. This is because {\lambda}_MAX carries most of the turbulent energy, and thereby influences both the amount and the spatial coherence of the angular momentum in the core. We show that the formation of dense filaments during collapse depends critically on {\lambda}_MAX, and we explain this finding using a force balance analysis. We also show that the core only has a high probability of fragmenting if {\lambda}_MAX > 0.5 R_CORE (where R_CORE is the core radius); that the dominant mode of fragmentation involves the formation and break-up of filaments; and that, although small protostellar disks (with radius R_DISK <= 20 AU) form routinely, more extended disks are rare. In turbulent, low-mass cores of the type we simulate here, the formation of large, fragmenting protostellar disks is suppressed by early fragmentation in the filaments.Comment: 11 pages, 7 figures; accepted for publication by MNRA

The SILCC (SImulating the LifeCycle of molecular Clouds) project: I. Chemical evolution of the supernova-driven ISM

The SILCC project (SImulating the Life-Cycle of molecular Clouds) aims at a more self-consistent understanding of the interstellar medium (ISM) on small scales and its link to galaxy evolution. We simulate the evolution of the multi-phase ISM in a 500 pc x 500 pc x 10 kpc region of a galactic disc, with a gas surface density of $\Sigma_{_{\rm GAS}} = 10 \;{\rm M}_\odot/{\rm pc}^2$. The Flash 4.1 simulations include an external potential, self-gravity, magnetic fields, heating and radiative cooling, time-dependent chemistry of H$_2$ and CO considering (self-) shielding, and supernova (SN) feedback. We explore SN explosions at different (fixed) rates in high-density regions (peak), in random locations (random), in a combination of both (mixed), or clustered in space and time (clustered). Only random or clustered models with self-gravity (which evolve similarly) are in agreement with observations. Molecular hydrogen forms in dense filaments and clumps and contributes 20% - 40% to the total mass, whereas most of the mass (55% - 75%) is in atomic hydrogen. The ionised gas contributes <10%. For high SN rates (0.5 dex above Kennicutt-Schmidt) as well as for peak and mixed driving the formation of H$_2$ is strongly suppressed. Also without self-gravity the H$_2$ fraction is significantly lower ($\sim$ 5%). Most of the volume is filled with hot gas ($\sim$90% within $\pm$2 kpc). Only for random or clustered driving, a vertically expanding warm component of atomic hydrogen indicates a fountain flow. Magnetic fields have little impact on the final disc structure. However, they affect dense gas ($n\gtrsim 10\;{\rm cm}^{-3}$) and delay H$_2$ formation. We highlight that individual chemical species, in particular atomic hydrogen, populate different ISM phases and cannot be accurately accounted for by simple temperature-/density-based phase cut-offs.Comment: 30 pages, 23 figures, submitted to MNRAS. Comments welcome! For movies of the simulations and download of selected Flash data see the SILCC website: http://www.astro.uni-koeln.de/silc

The SILCC project: III. Regulation of star formation and outflows by stellar winds and supernovae

We study the impact of stellar winds and supernovae on the multi-phase interstellar medium using three-dimensional hydrodynamical simulations carried out with FLASH. The selected galactic disc region has a size of (500 pc)$^2$ x $\pm$ 5 kpc and a gas surface density of 10 M$_{\odot}$/pc$^2$. The simulations include an external stellar potential and gas self-gravity, radiative cooling and diffuse heating, sink particles representing star clusters, stellar winds from these clusters which combine the winds from indi- vidual massive stars by following their evolution tracks, and subsequent supernova explosions. Dust and gas (self-)shielding is followed to compute the chemical state of the gas with a chemical network. We find that stellar winds can regulate star (cluster) formation. Since the winds suppress the accretion of fresh gas soon after the cluster has formed, they lead to clusters which have lower average masses (10$^2$ - 10$^{4.3}$ M$_{\odot}$) and form on shorter timescales (10$^{-3}$ - 10 Myr). In particular we find an anti-correlation of cluster mass and accretion time scale. Without winds the star clusters easily grow to larger masses for ~5 Myr until the first supernova explodes. Overall the most massive stars provide the most wind energy input, while objects beginning their evolution as B-type stars contribute most of the supernova energy input. A significant outflow from the disk (mass loading $\gtrsim$ 1 at 1 kpc) can be launched by thermal gas pressure if more than 50% of the volume near the disc mid-plane can be heated to T > 3x10$^5$ K. Stellar winds alone cannot create a hot volume-filling phase. The models which are in best agreement with observed star formation rates drive either no outflows or weak outflows.Comment: 23 pages; submitted to MNRA

Radiation Driven Implosion and Triggered Star Formation

We present simulations of initially stable isothermal clouds exposed to ionizing radiation from a discrete external source, and identify the conditions that lead to radiatively driven implosion and star formation. We use the Smoothed Particle Hydrodynamics code SEREN (Hubber et al. 2010) and the HEALPix-based photoionization algorithm described in Bisbas et al. (2009). We find that the incident ionizing flux is the critical parameter determining the evolution: high fluxes simply disperse the cloud, whereas low fluxes trigger star formation. We find a clear connection between the intensity of the incident flux and the parameters of star formation.Comment: 4 pages, 2 figures, conference proceedings, IAU Symposium 270 (eds. Alves, Elmegreen, Girart, Trimble

Massive stars in massive clusters - IV. Disruption of clouds by momentum-driven winds

We examine the effect of momentum-driven OB-star stellar winds on a parameter space of simulated turbulent giant molecular clouds using smoothed particle hydrodynamic simulations. By comparison with identical simulations in which ionizing radiation was included instead of winds, we show that momentum-driven winds are considerably less effective in disrupting their host clouds than are H ii regions. The wind bubbles produced are smaller and generally smoother than the corresponding ionization-driven bubbles. Winds are roughly as effective in destroying the very dense gas in which the O stars are embedded, and thus shutting down the main regions of star-forming activity in the model clouds. However, their influence falls off rapidly with distance from the sources, so they are not as good at sweeping up dense gas and triggering star formation further out in the clouds. As a result, their effect on the star formation rate and efficiency is generally more negative than that of ionization, if they exert any effect at all.Peer reviewe

Graphene-based LbL deposited films: further study of electrical and gas sensing properties

Graphene-surfactant composite materials obtained by the ultrasonic exfoliation of graphite powder in the presence of ionic surfactants (either CTAB or SDS) were utilised to construct thin films using layer-by-layer (LbL) electrostatic deposition technique. A series of graphene-based thin films were made by alternating layers of either graphene-SDS with polycations (PEI or PAH) or graphene-CTAB with polyanions (PSS). Also, graphene-phthalocyanine composite films were produced by alternating layers of graphene-CTAB with tetrasulfonated nickel phthalocyanine. Graphene-surfactant LbL films exhibited good electric conductivity (about 0.1 S/cm) of semiconductor type with a band gap of about 20 meV. Judging from UV-vis spectra measurements, graphene-phthalocyanine LbL films appeared to form joint π-electron system. Gas sensing testing of such composite films combining high conductivity of graphene with the gas sensing abilities of phthalocyanines showed substantial changes (up to 10%) in electrical conductivity upon exposure to electro-active gases such as HCl and NH3