7,184 research outputs found

    Reversible Protonated Resting State of the Nitrogenase Active Site

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    Protonated states of the nitrogenase active site are mechanistically significant since substrate reduction is invariably accompanied by proton uptake. We report the low pH characterization by X-ray crystallography and EPR spectroscopy of the nitrogenase molybdenum iron (MoFe) proteins from two phylogenetically distinct nitrogenases (Azotobacter vinelandii, Av, and Clostridium pasteurianum, Cp) at pHs between 4.5 and 8. X-ray data at pHs of 4.5–6 reveal the repositioning of side chains along one side of the FeMo-cofactor, and the corresponding EPR data shows a new S = 3/2 spin system with spectral features similar to a state previously observed during catalytic turnover. The structural changes suggest that FeMo-cofactor belt sulfurs S3A or S5A are potential protonation sites. Notably, the observed structural and electronic low pH changes are correlated and reversible. The detailed structural rearrangements differ between the two MoFe proteins, which may reflect differences in potential protonation sites at the active site among nitrogenase species. These observations emphasize the benefits of investigating multiple nitrogenase species. Our experimental data suggest that reversible protonation of the resting state is likely occurring, and we term this state “E_0H+”, following the Lowe–Thorneley naming scheme

    Binding of ligands to the active site of carboxypeptidase A.

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    Super-Eddington Atmospheres that Don't Blow Away

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    We show that magnetized, radiation dominated atmospheres can support steady state patterns of density inhomogeneity that enable them to radiate at far above the Eddington limit, without suffering mass loss. The inhomogeneities consist of periodic shock fronts bounding narrow, high-density regions, interspersed with much broader regions of low density. The radiation flux avoids the regions of high density, which are therefore weighed down by gravity, while gas in the low-density regions is slammed upward into the shock fronts by radiation force. As the wave pattern moves through the atmosphere, each parcel of matter alternately experiences upward and downward forces, which balance on average. Magnetic tension shares the competing forces between regions of different densities, preventing the atmosphere from blowing apart. We calculate the density structure and phase speed of the wave pattern, and relate these to the wavelength, the density contrast, and the factor by which the net radiation flux exceeds the Eddington limit. In principle, this factor can be as large as the ratio of magnetic pressure to mean gas pressure, or the ratio of radiation pressure to gas pressure, whichever is smaller. Although the magnetic pressure must be large compared to the mean gas pressure in order to support a large density contrast, it need not be large compared to the radiation pressure. These highly inhomogeneous flows could represent the nonlinear development of the "photon bubble" instability discovered by Gammie. We briefly discuss the applicability of these solutions to astrophysical systems.Comment: 11 pages, 1 figure, accepted for publication in The Astrophysical Journa

    A survey of a small group of workers exposed to toluene di-isocyanate

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    All 20 workers exposed to toluene di-isocyanate (TDI) in a chemical processing and packing factory were tested for TDI-induced asthma. The assessment included a respiratory symptom questionnaire, spirometry, skin prick tests for common allergens and assessment of total and TDI-specific immunoglobulin E (IgE) levels by radio-allergo-sorbent tests. Six workers had symptoms suggestive of TDI-related asthtna. Three of these 6 workers had a significant cross-shift decline in forced expiratory volume in 1 second (FEV1) (10% or greater). Two of the 6 had high levels of TDI-specific IgE. Of the 14 workers without work-related symptoms, 1 had a significant cross-shift decline in FEV1. There was no significant association between the levels of exposure to TDI and symptoms, lung function paratneters or immunological findings. This study demonstrates the difficulties in correlating immunological status with clinical and lung function findings in workers exposed to TDI. Recommendations include a stepwise approach to diagnosing TDI-induced asthma in exposed workers

    Jet-Induced Emission-Line Nebulosity and Star Formation in the High-Redshift Radio Galaxy 4C41.17

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    The high redshift radio galaxy 4C41.17 consists of a powerful radio source in which previous work has shown that there is strong evidence for jet-induced star formation along the radio axis. We argue that nuclear photoionization is not responsible for the excitation of the emission line clouds and we construct a jet-cloud interaction model to explain the major features revealed by the data. The interaction of a high-powered jet with a dense cloud in the halo of 4C41.17 produces shock-excited emission-line nebulosity through ~1000 km/s shocks and induces star formation. The CIII to CIV line ratio and the CIV luminosity emanating from the shock, imply that the pre-shock density in the line-emitting cloud is high enough (~1-10 cm^-3) that shock initiated star formation could proceed on a timescale of order a few x 10^6 yrs, well within the estimated dynamical age of the radio source. Broad (FWHM ~ 100 - 1400 km/s) emission lines are attributed to the disturbance of the gas cloud by a partial bow--shock and narrow emission lines (FWHM ~ 500 - 650 km/s) (in particular CIV) arise in precursor emission in relatively low metallicity gas. The implied baryonic mass ~ 8 \times 10^{10} solar masses of the cloud is high and implies that Milky Way size condensations existed in the environments of forming radio galaxies at a redshift of 3.8. Our interpretation of the data provides a physical basis for the alignment of the radio, emission-line and UV continuum images in some of the highest redshift radio galaxies and the analysis presented here may form a basis for the calculation of densities and cloud masses in other high redshift radio galaxies.Comment: 18 pages, 5 figures; uses astrobib.sty and aaspp4.sty. Better versions of figures available via anonymous from ftp://mso.anu.edu.au:pub/pub/geoff/4C41.1

    Quasars at z=6: the survival of the fittest

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    The Sloan Digital Sky survey detected luminous quasars at very high redshift, z>6. Follow-up observations indicated that at least some of these quasars are powered by supermassive black holes (SMBHs) with masses in excess of billion solar masses. SMBHs, therefore, seem to have already existed when the Universe was less than 1 Gyr old, and the bulk of galaxy formation still has to take place. We investigate in this paper to which extent accretion and dynamical processes influence the early growth of SMBHs. We assess the impact of (i) black hole mergers, (ii) the influence of the merging efficiency and (iii) the negative contribution due to dynamical effects which can kick black holes out of their host halos (gravitational recoil). We find that if accretion is always limited by the Eddington rate via a thin disc, the maximum radiative efficiency allowed to reproduce the LF at z=6 is of order 12%, when the adverse effect of the gravitational recoil is taken into consideration. Dynamical effects cannot be neglected in studies of high-redshift SMBHs. If black holes can accrete at super-critical rate during an early phase, reproducing the observed SMBH mass values is not an issue, even in the case that the recoil velocity is in the upper limits range, as the mass ratios of merging binaries are skewed towards low values, where the gravitational recoil effect is very mild. We propose that SMBH growth at early times is very selective, and efficient only for black holes hosted in high density peak halos.Comment: Accepted for publication in the ApJ. 9 pages, 6 b/w figure

    Sunyaev - Zel'dovich fluctuations from spatial correlations between clusters of galaxies

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    We present angular power spectra of the cosmic microwave background radiation anisotropy due to fluctuations of the Sunyaev-Zel'dovich (SZ) effect through clusters of galaxies. A contribution from the correlation among clusters is especially focused on, which has been neglected in the previous analyses. Employing the evolving linear bias factor based on the Press-Schechter formalism, we find that the clustering contribution amounts to 20-30% of the Poissonian one at degree angular scales. If we exclude clusters in the local universe, it even exceeds the Poissonian noise, and makes dominant contribution to the angular power spectrum. As a concrete example, we demonstrate the subtraction of the ROSAT X-ray flux-limited cluster samples. It indicates that we should include the clustering effect in the analysis of the SZ fluctuations. We further find that the degree scale spectra essentially depend upon the normalization of the density fluctuations, i.e., \sigma_8, and the gas mass fraction of the cluster, rather than the density parameter of the universe and details of cluster evolution models. Our results show that the SZ fluctuations at the degree scale will provide a possible measure of \sigma_8, while the arc-minute spectra a probe of the cluster evolution. In addition, the clustering spectrum will give us valuable information on the bias at high redshift, if we can detect it by removing X-ray luminous clusters.Comment: 11 pages, 4 figures, submitted to Astrophysical Journa

    Dark Matter: Introduction

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    This short review was prepared as an introduction to the Royal Society's 'Dark Matter' conference. It addresses the embarrassing fact that 95% of the universe is unaccounted for. Favoured dark matter candidates are axions or weakly-interacting particles that have survived from the very early universe, but more exotic options cannot be excluded. Experimental searches are being made for the 'dark' particles but we have indirect clues to their nature too. Comparisons of data (from, eg, gravitational lensing) with numerical simulations of galaxy formation can constrain (eg) the particle velocities and collision cross sections. The mean cosmic density of dark matter (plus baryons) is now pinned down to be only about 30% of the critical density However, other recent evidence -- microwave background anisotropies, complemented by data on distant supernovae -- reveals that our universe actually is 'flat', and that its dominant ingredient (about 70% of the total mass-energy) is something quite unexpected -- 'dark energy' pervading all space, with negative pressure. We now confront two mysteries: (i) Why does the universe have three quite distinct basic ingredients -- baryons, dark matter and dark energy -- in the proportions (roughly) 5%, 25% and 70%? (ii) What are the (almost certainly profound) implications of the 'dark energy' for fundamental physics?Comment: 10 pages, 1 figure. Late
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