Non-heme iron hydroperoxo species in superoxide reductase as a catalyst for oxidation reactions

International audienceThe non-hemehigh-spin ferric iron hydroperoxo species formed in superoxide reductase catalyzesoxidative aldehyde deformylation through its nucleophile character.This species also acts as an electrophile to catalyze oxygen atom transfer in sulfoxidation reactions, highlighting the oxidation potential of non-heme iron hydroperoxo species. The mechanisms of oxygen activation and oxidation reactions catalyzed by metalloenzymes have been thoroughly investigated during the last past decades. 1-5 For cytochrome P450 5, 6 and several non-heme iron monooxygenases, 4, 7, 8 it is now well admitted that high-valent iron-oxo species formed at their active site is the effective oxidant for organic substrate oxidation and oxygen transfer. Nevertheless, the fact that alternative species, e.g. ferric iron (hydro)peroxide intermediate, 1 or other metal-oxidant adducts, 9

De-pollution efficacy of photocatalytic roofing granules

Photocatalytic building surfaces can harness sunlight to reduce urban air pollution. The NOx abatement capacity of TiO2-coated granules used in roofing products was evaluated for commercial product development. A laboratory test chamber and ancillary setup were built following conditions prescribed by ISO Standard 22197-1. It was validated by exposing reference P25-coated aluminum plates to a 3 L min−1 air flow enriched in 1 ppm NO under UVA irradiation (360 nm, 11.5 W m−2). We characterized prototype granule-surfaced asphalt shingles and loose granules prepared with different TiO2 loadings and post-treatment formulations. Tests performed at surface temperatures of 25 and 60 °C showed that NOx abatement was more effective at the higher temperature. Preliminary tests explored the use of 1 ppm NO2 and of 1 ppm and 0.3 ppm NO/NO2 mixtures. Specimens were aged in a laboratory accelerated weathering apparatus, and by exposure to the outdoor environment over periods that included dry and rainy seasons. Laboratory aging led to higher NO removal and NO2 formation rates, and the same catalyst activation was observed after field exposure with frequent precipitation. However, exposure during the dry season reduced the performance. This inactivation was mitigated by cleaning the surface of field-exposed specimens. Doubling the TiO2 loading led to a 50–150% increase in NO removal and NOx deposition rates. Application of different post-treatment coatings decreased NO removal rates (21–35%) and NOx deposition rates (26–74%) with respect to untreated granules. The mass balance of nitrogenated species was assessed by extracting granules after UV exposure in a 1 ppm NO-enriched atmosphere

A simple and efficient DNA isolation method for Ornithogalum L. species (Hyacinthaceae, Asparagales)

We report an efficient, simple and cost-effective protocol for the isolation of genomic DNA from Ornithogalum species. Our modification of the standard CTAB protocol includes two polyphenol adsorbents (insoluble PVPP and activated charcoal), high NaCl concentrations (4 M) for removing polysaccharides, and addition of phenol to remove proteins and other contaminants. DNA yield obtained with our protocol was 223 and 312 μg DNA g-1 of dry leaf tissue. The absorbance ratio 260/280 nm was 1.879 (O. refractum) and 1.753 (O. sibthorpii), and the absorbance ratio 260/230 nm was 1.779 (O. refractum) and 1.545 (O. sibthorpii), revealing lack of contamination. PCR amplifications of one nuclear marker (26S rDNA) indicated that this DNA isolation protocol may be used for Ornithogalum plants containing many interfering compounds for further analyses in population genetics and phylogeographic studies

Optical Photon Simulation with Mitsuba3

Optical photon propagation is an embarrassingly parallel operation, well suited to acceleration on GPU devices. Rendering of images employs similar techniques -- for this reason, a pipeline to offload optical photon propagation from Geant4 to the industry-standard open-source renderer Mitsuba3 has been devised. With the creation of a dedicated plugin for single point multi-source emission, we find a photon propagation rate of $2\times10^{5}$ photons per second per CPU thread using LLVM and $1.2\times10^{6}$ photons per second per GPU using CUDA. This represents a speed-up of 70 on CPU and 400 on GPU over Geant4 and is competitive with other similar applications. The potential for further applications is discussed.Comment: 7 pages, 8 figure

Anharmonic vs. relaxational sound damping in glasses: I. Brillouin scattering from densified silica

This series discusses the origin of sound damping and dispersion in glasses. In particular, we address the relative importance of anharmonicity versus thermally activated relaxation. In this first article, Brillouin-scattering measurements of permanently densified silica glass are presented. It is found that in this case the results are compatible with a model in which damping and dispersion are only produced by the anharmonic coupling of the sound waves with thermally excited modes. The thermal relaxation time and the unrelaxed velocity are estimated.Comment: 9 pages with 7 figures, added reference

Slider-Block Friction Model for Landslides: Application to Vaiont and La Clapiere Landslides

Accelerating displacements preceding some catastrophic landslides have been found empirically to follow a time-to-failure power law, corresponding to a finite-time singularity of the velocity $v \sim 1/(t_c-t)$ [{\it Voight}, 1988]. Here, we provide a physical basis for this phenomenological law based on a slider-block model using a state and velocity dependent friction law established in the laboratory and used to model earthquake friction. This physical model accounts for and generalizes Voight's observation: depending on the ratio $B/A$ of two parameters of the rate and state friction law and on the initial frictional state of the sliding surfaces characterized by a reduced parameter $x_i$, four possible regimes are found. Two regimes can account for an acceleration of the displacement. We use the slider-block friction model to analyze quantitatively the displacement and velocity data preceding two landslides, Vaiont and La Clapi\`ere. The Vaiont landslide was the catastrophic culmination of an accelerated slope velocity. La Clapi\`ere landslide was characterized by a peak of slope acceleration that followed decades of ongoing accelerating displacements, succeeded by a restabilizing phase. Our inversion of the slider-block model on these data sets shows good fits and suggest to classify the Vaiont (respectively La Clapi\`ere) landslide as belonging to the velocity weakening unstable (respectively strengthening stable) sliding regime.Comment: shortened by focusing of the frictional model, Latex document with AGU style file of 14 pages + 11 figures (1 jpeg photo of figure 6 given separately) + 1 tabl

The crossover from propagating to strongly scattered acoustic modes of glasses observed in densified silica

Spectroscopic results on low frequency excitations of densified silica are presented and related to characteristic thermal properties of glasses. The end of the longitudinal acoustic branch is marked by a rapid increase of the Brillouin linewidth with the scattering vector. This rapid growth saturates at a crossover frequency Omega_co which nearly coincides with the center of the boson peak. The latter is clearly due to additional optic-like excitations related to nearly rigid SiO_4 librations as indicated by hyper-Raman scattering. Whether the onset of strong scattering is best described by hybridization of acoustic modes with these librations, by their elastic scattering (Rayleigh scattering) on the local excitations, or by soft potentials remains to be settled.Comment: 14 pages, 6 figures, to be published in a special issue of J. Phys. Condens. Matte

Numerical study of anharmonic vibrational decay in amorphous and paracrystalline silicon

The anharmonic decay rates of atomic vibrations in amorphous silicon (a-Si) and paracrystalline silicon (p-Si), containing small crystalline grains embedded in a disordered matrix, are calculated using realistic structural models. The models are 1000-atom four-coordinated networks relaxed to a local minimum of the Stillinger-Weber interatomic potential. The vibrational decay rates are calculated numerically by perturbation theory, taking into account cubic anharmonicity as the perturbation. The vibrational lifetimes for a-Si are found to be on picosecond time scales, in agreement with the previous perturbative and classical molecular dynamics calculations on a 216-atom model. The calculated decay rates for p-Si are similar to those of a-Si. No modes in p-Si reside entirely on the crystalline cluster, decoupled from the amorphous matrix. The localized modes with the largest (up to 59%) weight on the cluster decay primarily to two diffusons. The numerical results are discussed in relation to a recent suggestion by van der Voort et al. [Phys. Rev. B {\bf 62}, 8072 (2000)] that long vibrational relaxation inferred experimentally may be due to possible crystalline nanostructures in some types of a-Si.Comment: 9 two-column pages, 13 figure