Mechanism of Oxidation of Brilliant Cresyl Blue with Acidic Chlorite and Hypochlorous Acid. A Kinetic Approach

The kinetics and mechanism of oxidation of brilliant cresyl blue (7-amino-3-diethylamino-8-methyl-phenoxazine chloride) (BB+) by chlorite in the presence of acid is reported. Under [H+]0>[ClO2–]0>[BB+]0 conditions, the oxidation reaction followed pseudo first-order kinetics with respect to BB+. During the reaction, chlorite ion disproportionates, resulting in accumulation of chlorine dioxide. The overall reaction is third-order with first-order dependence on both H+ and ClO2– ions. The rate coefficient for the overall reaction is (0.158 ± 0.003) l2 mol–2 s–1. The stoichiometry of the reaction is 2BB+ + 7ClO2 – + 2H+  2P + → 2CH3COOH + 4ClO2 + 3Cl– where P=7-amino-3-ethylamino-8-methyl-phenoxazine-10-N-oxide, and it varied with the initial concentrations of chlorite and acid. Near neutral pH, the hypochlorite-initiated oxidation of BB+ proceeded through two second-order pathways, one driven by OCl– ion and the other by HOCl. The latter reaction is much faster, with k=(1.26±0.04)×103 l mol–1 s–1. At low pH, the reaction was much faster and had first-order dependence on the concentrations of BB+, H+ and HOCl. Ru(III) catalysed the BB+-chlorite reaction with efficiency and the kinetics of the catalysed reaction are reported. Ru(III) had a catalytic constant, kCAT=1.2 × 106 l3 mol–3 s–1. The activation parameters for both uncatalysed and catalysed reactions were also reported. The kinetic profiles of the title reaction were computed using the proposed 11-step mechanism and Simkine software. The simulated curves agreed well with the experimental curves.Keywords: Kinetics, reaction mechanisms, dyes, water chemistry, computer chemistry

A theoretical study of non-adiabatic surface effects for a model in the NTF cryogenic wind tunnel

A theoretical analysis was made of the severity and effect of nonadiabatic surface conditions for a model in the NTF cryogenic wind tunnel. The nonadiabatic condition arises from heaters that are used to maintain a constant thermal environment for instrumentation internal to the model. The analysis was made for several axi-symmetric representations of a fuselage cavity, using a finite element heat conduction code. Potential flow and boundary layer codes were used to calculate the convection condition for the exterior surface of the model. The results of the steady state analysis show that it is possible to maintain the surface temperature very near the adiabatic value, with the judicious use of insulating material. Even for the most severe nonadiabatic condition studied, the effects on skin friction drag and displacement thickness were only marginally significant. The thermal analysis also provided an estimate of the power required to maintain a specified cavity temperature

Heavy metal removal from aqueous solutions by sorption using natural clays from Burkina Faso

The acid-base properties of two raw and purified mixed clays from Burkina Faso were studied, as well as their potential to remove copper(II), lead(II) and chromium(III), and thereby their ability to be used to purify water from heavy metals. The purification procedure of the clays involved removal of carbonates, iron oxides and organic matter. A determination of the elemental composition of the mixed clays revealed the presence of aluminum, iron and silicon as main constituents. The high alkaline pH in one of the samples is attributable to the presence of carbonate in the raw clay. The point of zero charge (pHpzc) values of the clays, as determined by potentiometric titrations, were 6.79 and 9.52 for the raw clays, while after purification they were 6.87 and 6.76, respectively. Metal adsorption to the clay surfaces started at pH values below pHpzc, strongly indicating formation of inner-sphere complexes. With contact time of 48 h, complete removal of copper(II) was achieved at pH 8 for all samples. More than 90% of the lead(II) removal was attributed to adsorption while for chromium(III), it was 85%. Adsorption to organic matter and iron oxides, and precipitation of metal hydroxides gave significant contributions to the removal of metal ions in aqueous systems.Key words: Mixed clays, potentiometric titration, heavy metals, pHpzc

Stimulus - response curves of a neuronal model for noisy subthreshold oscillations and related spike generation

We investigate the stimulus-dependent tuning properties of a noisy ionic conductance model for intrinsic subthreshold oscillations in membrane potential and associated spike generation. On depolarization by an applied current, the model exhibits subthreshold oscillatory activity with occasional spike generation when oscillations reach the spike threshold. We consider how the amount of applied current, the noise intensity, variation of maximum conductance values and scaling to different temperature ranges alter the responses of the model with respect to voltage traces, interspike intervals and their statistics and the mean spike frequency curves. We demonstrate that subthreshold oscillatory neurons in the presence of noise can sensitively and also selectively be tuned by stimulus-dependent variation of model parameters.Comment: 19 pages, 7 figure

Spectrum and Variability of Mrk501 as observed by the CAT Imaging Telescope

The CAT Imaging Telescope has observed the BL Lac object Markarian 501 between March and August 1997. We report here on the variability over this time including several large flares. We present also preliminary spectra for all these data, for the low emission state, and for the largest flare.Comment: 4 pages, 4 figures, Late

Observation of the Crab Nebula Gamma-Ray Emission Above 220 Gev by the Cat Cherenkov Imaging Telescope

The CAT imaging telescope, recently built on the site of the former solar plant Themis (French Pyrenees), observed gamma-rays from the Crab nebula from October 1996 to March 1997. This steady source, often considered as the standard candle of very-high-energy gamma-ray astronomy, is used as a test-beam to probe the performances of the new telescope, particularly its energy threshold (220 GeV at 20 degrees zenith angle) and the stability of its response. Due to the fine-grain camera, an accurate analysis of the longitudinal profiles of shower images is performed, yielding the source position in two dimensions for each individual shower.Comment: 5 pages, 3 figures, Tex, contribution to 25th ICRC Durba

Detection of Vhe Gamma-Rays from MRK 501 with the Cat Imaging Telescope

The CAT imaging telescope on the site on the former solar plant Themis has been observing gamma-rays from Mrk501 above 220 GeV in March and April 1997. This source is shown to be highly variable and the light curve is presented. The detected gamma-ray rate for the most intense flare is in excess of 10 per minute.Comment: 5 pages, 4 figures, Tex, contribution to 25th ICRC Durba

BRCA2 variants and cardiovascular disease in a multi-ethnic study.

BACKGROUND: Germline mutations of BRCA1/2 are associated with hereditary breast and ovarian cancer. Recent data suggests excess mortality in mutation carriers beyond that conferred by neoplasia, and recent in vivo and in vitro studies suggest a modulatory role for BRCA proteins in endothelial and cardiomyocyte function. We therefore tested the association of BRCA2 variants with clinical cardiovascular disease (CVD). METHODS: Using data from 1,170 individuals included in two multi-ethnic population-based studies (SHARE and SHARE-AP), the association between BRCA2 variants and CVD was evaluated. 15 SNPs in BRCA2 with minor allele frequencies (MAF) > 0.01 had been previously genotyped using the cardiovascular gene-centric 50 k SNP array. 115 individuals (9.8%) reported a CVD event, defined as myocardial infarction (MI), angina, silent MI, stroke, and angioplasty or coronary artery bypass surgery. Analyses were adjusted for age and sex. The SNPs rs11571836 and rs1799943 were subsequently genotyped using the MassARRAY platform in 1,045 cases of incident MI and 1,135 controls from the South Asian subset of an international case-control study of acute MI (INTERHEART), and rs11571836 was imputed in 4,686 cases and 4500 controls from the Pakistan Risk of Myocardial Infarction Study (PROMIS). RESULTS: Two BRCA2 SNPs, rs11571836 and rs1799943, both located in untranslated regions, were associated with lower risk of CVD (OR 0.47 p = 0.01 and OR 0.56 p = 0.03 respectively) in the SHARE studies. Analysis by specific ethnicities demonstrated an association with CVD for both SNPs in Aboriginal People, and for rs11571836 only in South Asians. No association was observed in the European and Chinese subgroups. A non-significant trend towards an association between rs11571836 and lower risk of MI was observed in South Asians from INTERHEART [OR = 0.87 (95% CI: 0.75-1.01) p = 0.068], but was not evident in PROMIS [OR = 0.96 (95% CI: 0.90-1.03) p = 0.230]. Meta-analysis of both case-control studies resulted in a combined OR of 0.94 (95% CI: 0.89-1.004, p = 0.06). CONCLUSIONS: Although there was an association between two SNPs in BRCA2 and CVD in a multi-ethnic population, these results were not replicated in two South Asian case-control studies of incident MI. Future studies exploring the association between BRCA variants and cardiovascular disorders are needed to clarify the role, if any, for BRCA variants in CVD pathogenesis.RIGHTS : This article is licensed under the BioMed Central licence at http://www.biomedcentral.com/about/license which is similar to the 'Creative Commons Attribution Licence'. In brief you may : copy, distribute, and display the work; make derivative works; or make commercial use of the work - under the following conditions: the original author must be given credit; for any reuse or distribution, it must be made clear to others what the license terms of this work are