Copper Containing Silicates as Catalysts for Liquid Phase Cyclohexane Oxidation

Copper containing silicates have been prepared by an acid-catalyzed sol-gel process. The materials were characterized by X-ray diffraction and fluorescence, EPR spectroscopy, elemental analysis, N2-physisorption, thermogravimetry, differential scanning calorimetry, temperature-programmed reduction, FTIR and UV/VIS spectroscopy. The silicates were shown to be efficient catalysts for the oxidation of cyclohexane with tert-butyl hydroperoxide as oxidant. Cyclohexanol and cyclohexanone were obtained as the main products. The metal was shown to be weakly bound to the silicate matrix and metal leaching was observed. Leaching was quantified by X-ray fluorescence and leaching tests showed that the catalytic activity is due to supported copper species. Leached copper showed no activity in the homogeneous phase.Silicatos contendo cobre foram preparados pelo processo sol-gel catalisado por ácido. Os materiais foram caracterizados por difração e fluorescência de raios X, espectroscopia EPR, análise elementar, fisissorção de N2, termogravimetria, calorimetria diferencial de varredura, redução à temperatura programada, espectroscopia FTIR e UV/VIS. Os silicatos mostram-se catalisadores eficientes para a oxidação do cicloexano com hidroperóxido de tert-butila como oxidante e obtiveram-se cicloexanona e cicloexanol como produtos principais da reação. O metal mostrou-se fracamente ligado à matriz de sílica e foi observada lixiviação do metal para a fase líquida. A lixiviação foi quantificada por fluorescência de raios X. Testes de lixiviação mostraram que a atividade catalítica é devida às espécies de cobre suportadas. O cobre lixiviado não mostrou nenhuma atividade catalítica em fase homogênea.170176Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Smooth stable and unstable manifolds for stochastic partial differential equations

Invariant manifolds are fundamental tools for describing and understanding nonlinear dynamics. In this paper, we present a theory of stable and unstable manifolds for infinite dimensional random dynamical systems generated by a class of stochastic partial differential equations. We first show the existence of Lipschitz continuous stable and unstable manifolds by the Lyapunov-Perron's method. Then, we prove the smoothness of these invariant manifolds

Insertion Element IS6110 based characterisation of Nepalese tuberculosis strains into different genetic lineages

Nepal is geographically located between India and China, a region containing significant Tuberculosis (TB) and Multi-Drug Resistance (MDR-TB) burdens. However, limited information is available on the phylogenetic diversity of Mycobacterium tuberculosis (Mtb) in Nepal. To gain further insight into the diversity of Mtb in Nepal, consecutive clinical samples from 176 newly diagnosed pulmonary tuberculosis patients were collected from two hospitals in Nepal. Insertion Site IS6110 Fluorescent Amplified Fragment Length Polymorphism (FAFLP) PCR and rpoB sequence analysis were carried out on genomic DNA extracts of cultured strains to assign them to accepted genetic lineages and identify MDR-TB. In this study, the IS6110 based characterisation showed a prevalence of 36.36% Central Asian Strain (CAS), 18.75% Beijing, 7.95 % Haarlem, 3.97% X, 2.2% each of Latin American Mediterranean (LAM), T-Uganda and T, 1.7% S and 24.4% were unassigned. Further, 3.9% of total M. tuberculosis isolates were of rifampicin resistant genotypes thus indicating that the prevalence of MDR could be higher than the country wide prevalence of MDR among new TB cases (2.2%) as reported by the national drug resistance survey carried out in 2011/2012

Differential Geometry applied to Acoustics : Non Linear Propagation in Reissner Beams

Although acoustics is one of the disciplines of mechanics, its "geometrization" is still limited to a few areas. As shown in the work on nonlinear propagation in Reissner beams, it seems that an interpretation of the theories of acoustics through the concepts of differential geometry can help to address the non-linear phenomena in their intrinsic qualities. This results in a field of research aimed at establishing and solving dynamic models purged of any artificial nonlinearity by taking advantage of symmetry properties underlying the use of Lie groups. The geometric constructions needed for reduction are presented in the context of the "covariant" approach.Comment: Submitted to GSI2013 - Geometric Science of Informatio

Radiative corrections to the Chern-Simons term at finite temperature in the noncommutative Chern-Simons-Higgs model

By analyzing the odd parity part of the gauge field two and three point vertex functions, the one-loop radiative correction to the Chern-Simons coefficient is computed in noncommutative Chern-Simons-Higgs model at zero and at high temperature. At high temperature, we show that the static limit of this correction is proportional to $T$ but the first noncommutative correction increases as $T\log T$. Our results are analytic functions of the noncommutative parameter.Comment: Revised version with a new section on the gauge field three point vertex function adde

Random attractors for degenerate stochastic partial differential equations

We prove the existence of random attractors for a large class of degenerate stochastic partial differential equations (SPDE) perturbed by joint additive Wiener noise and real, linear multiplicative Brownian noise, assuming only the standard assumptions of the variational approach to SPDE with compact embeddings in the associated Gelfand triple. This allows spatially much rougher noise than in known results. The approach is based on a construction of strictly stationary solutions to related strongly monotone SPDE. Applications include stochastic generalized porous media equations, stochastic generalized degenerate p-Laplace equations and stochastic reaction diffusion equations. For perturbed, degenerate p-Laplace equations we prove that the deterministic, infinite dimensional attractor collapses to a single random point if enough noise is added.Comment: 34 pages; The final publication is available at http://link.springer.com/article/10.1007%2Fs10884-013-9294-

Analytic Results for Higgs Production in Bottom Fusion

We evaluate analytically the cross section for Higgs production plus one jet through bottom quark fusion. By considering the small pT limit we derive expressions for the resummation coefficients governing the structure of large logarithms, and compare these expressions with those available in the literature.Comment: 14 pages, 7 figure

Biomass burning influence on high-latitude tropospheric ozone and reactive nitrogen in summer 2008: a multi-model analysis based on POLMIP simulations

We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high latitudes (> 50° N) in July 2008, using 10 global chemical transport model simulations from the POLMIP multi-model comparison exercise. In model air masses dominated by fire emissions, ΔO3/ΔCO values ranged between 0.039 and 0.196 ppbv ppbv−1 (mean: 0.113 ppbv ppbv−1) in freshly fire-influenced air, and between 0.140 and 0.261 ppbv ppbv−1 (mean: 0.193 ppbv) in more aged fire-influenced air. These values are in broad agreement with the range of observational estimates from the literature. Model ΔPAN/ΔCO enhancement ratios show distinct groupings according to the meteorological data used to drive the models. ECMWF-forced models produce larger ΔPAN/ΔCO values (4.47 to 7.00 pptv ppbv−1) than GEOS5-forced models (1.87 to 3.28 pptv ppbv−1), which we show is likely linked to differences in efficiency of vertical transport during poleward export from mid-latitude source regions. Simulations of a large plume of biomass burning and anthropogenic emissions exported from towards the Arctic using a Lagrangian chemical transport model show that 4-day net ozone change in the plume is sensitive to differences in plume chemical composition and plume vertical position among the POLMIP models. In particular, Arctic ozone evolution in the plume is highly sensitive to initial concentrations of PAN, as well as oxygenated VOCs (acetone, acetaldehyde), due to their role in producing the peroxyacetyl radical PAN precursor. Vertical displacement is also important due to its effects on the stability of PAN, and subsequent effect on NOx abundance. In plumes where net ozone production is limited, we find that the lifetime of ozone in the plume is sensitive to hydrogen peroxide loading, due to the production of HOx from peroxide photolysis, and the key role of HO2 + O3 in controlling ozone loss. Overall, our results suggest that emissions from biomass burning lead to large-scale photochemical enhancement in high-latitude tropospheric ozone during summer

In utero exposure to cigarette smoke dysregulates human fetal ovarian developmental signalling

STUDY QUESTION How does maternal cigarette smoking disturb development of the human fetal ovary?<p></p> SUMMARY ANSWER Maternal smoking increases fetal estrogen titres and dysregulates several developmental processes in the fetal ovary.<p></p> WHAT IS KNOWN ALREADY Exposure to maternal cigarette smoking during gestation reduces human fetal ovarian cell numbers, germ cell proliferation and subsequent adult fecundity.<p></p> STUDY DESIGN, SIZE, DURATION The effects of maternal cigarette smoking on the second trimester human fetal ovary, fetal endocrine signalling and fetal chemical burden were studied. A total of 105 fetuses were studied, 56 from mothers who smoked during pregnancy and 49 from those who did not.<p></p> PARTICIPANTS/MATERIALS, SETTING METHODS Ovary, liver and plasma samples were collected from electively terminated, normally progressing, second trimester human fetuses. Circulating fetal hormones, levels of 73 fetal ovarian transcripts, protein localization, density of oocytes/primordial follicles and levels of 16 polycyclic aromatic hydrocarbons (PAHs) in the fetal liver were determined.<p></p> MAIN RESULTS AND THE ROLE OF CHANCE Circulating fetal estrogen levels were very high and were increased by maternal smoking (ANOVA, P = 0.055–0.004 versus control). Smoke exposure also dysregulated (two-way ANOVA, smoking versus gestation weeks interaction, P = 0.046–0.023) four fetal ovarian genes (cytochrome P450 scc [CYP11A1], NOBOX oogenesis homeobox [NOBOX], activator of apoptosis harakiri [HRK], nuclear receptor subfamily 2, group E, member 1 [NR2E1]), shifted the ovarian Inhibin βA/inhibin α ratio (NHBA/INHA) transcript ratio in favour of activin (ANOVA, P = 0.049 versus control) and reduced the proportion of dominant-negative estrogen receptor 2 (ERβ: ESR2) isoforms in half the exposed fetuses. PAHs, ligands for the aryl hydrocarbon receptor (AHR), were increased nearly 6-fold by maternal smoking (ANOVA, P = 0.011 versus control). A fifth transcript, COUP transcription factor 1 (nuclear receptor subfamily 2, group F, member 1: NR2F1, which contains multiple AHR-binding sites), was both significantly increased (ANOVA, P = 0.026 versus control) and dysregulated by (two-way ANOVA, smoking versus gestation weeks interaction, P = 0.021) maternal smoking. NR2F1 is associated with repression of FSHR expression and smoke-exposed ovaries failed to show the normal increase in FSHR expression during the second trimester. There was a significantly higher number of DEAD (Asp-Glu-Ala-Asp) box polypeptide 4 (DDX4) VASA-positive (ANOVA, P = 0.016 versus control), but not POU domain, class 1, transcription factor 1 (POU5F1) OCT3/4-positive, oocytes in smoke-exposed fetuses and this matched with a significantly higher number of primordial follicles (ANOVA, P = 0.024 versus control).<p></p> LIMITATIONS, REASONS FOR CAUTION The effects of maternal smoking on establishment of the maximum fetal primordial follicle pool cannot be reliably studied in our population since the process is not completed until 28 weeks of gestation and normal fetuses older than 21 weeks of gestation are not available for study. Our data suggest that some fetal ovaries are affected by smoke exposure while others are not, indicating that additional studies, with larger numbers, may show more significant effects.<p></p> WIDER IMPLICATIONS OF THE FINDINGS Fetal exposure to chemicals in cigarette smoke is known to lead to reduced fecundity in women. Our study suggests, for the first time, that this occurs via mechanisms involving activation of AHR, disruption of inhibin/activin and estrogen signalling, increased exposure to estrogen and dysregulation of multiple molecular pathways in the exposed human fetal ovary. Our data also suggest that alterations in the ESR2 positive and dominant negative isoforms may be associated with reduced sensitivity of some fetuses to increased estrogens and maternal smoking