140 research outputs found

    Oxygen reduction in acid media: influence of the activity of CoNPc(1,2) bilayer deposits in relation to their attachment to the carbon black support and role of surface groups as a function of heat treatment

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    O2 reduction was investigated using rotating disk electrode and voltammetry techniques on NPcCo(1,2) impregnations deposited onto two kinds of carbon black support. They were selected on the basis of their similar pH and dibuthylphthalate (DBP) adsorption values. Samples were also characterized by IR and X-ray photoelectron spectroscopy techniques. An optimized thermal treatment yielded an improvement in the O2 reducibility and identical activities (with N = 3.8) on both supports. These spectroscopic methods revealed a bilayer structure and suggested the presence of two sorts of site (active and inactive) which differed in their attachment of the substrate via surface groups which were characterized

    Oxygen reduction in acid media: effect of iron substitution by cobalt on heat-treated naphthalocyanine impregnations supported on preselected carbon blacks

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    FeNPc(1.2) impregnations were investigated at various loadings using a rotating-disk electrode, voltammetry and X-ray photoelectron spectroscopy (XPS) techniques. Optimal activity takes place at monolayer coverage, and major demetallation occurs after prolonged exposure to acid solution. The substitution of Fe by Co enables the electrochemical performances to reach those presented by 10% Pt on Vulcan and stops the demetallation process. The application of fast atomic bombardment secondary ion mass spectrometry (FABS) together with XPS sheds light on the detrimental role of some electrophilic groups attached to the carbon black-catalyst interface

    Oxygen reduction in acid media on supported iron naphthalocyanine: Effect of isomer configuration and pyrolysis

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    O2 reduction in H2SO4 medium has been investigated on FeNPc impregnations on Norit BrX by the rotating disk electrode technique. Important differences in activity and stability were found between the 1,2- and 2,3-FeNPc isomers (pyrolysed or not). XPS analyses show, for the most inactive sample, strong demetallation and nitrogen losses. This phenomenon can be attributed to the differences in flexibility between the FeNPc isomers, which influences their stabilization on the substrate

    Oxygen reduction in acid media: influence of the heat treatment on the FeNPc(1–20 isomer mixture impregnated on carbon blacks and active charcoals

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    Oxygen reduction with the aid of a number of FeNPc(1–2) impregnated carbon supports in sulphuric acid solutions has been investigated.\ud \ud Loading of the carbon samples amounted to about 10 wt.%. After a 10 day stay in the aerated solutions the samples were investigated with rotating disk electrode and X-ray photoelectron spectroscopy techniques. The most active and stable samples correspond to mono- or submonolayers of FeNPc deposited on high dibutylphthalate adsorption carbon blacks. Comparison with data obtained previously on Norit BrX impregnations emphasizes the rôle of the electron density on the inner nitrogen atoms rather than that on the iron centres

    Oxygen reduction in an acid medium : electrocatalysis by CoNPc(1,2) impregnated on a carbon black support; effect of loading and heat treatment

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    O2 reduction in an acid medium has been investigated on a transition metal macrocycle, CoNPc(1,2), impregnated on a carbon black support with a high dibutylphthalate adsorption value, using a rotating disk electrode and voltammetry techniques described previously, combined with X-ray photoelectron spectroscopy measurements. Optimal activity was found for a bilayer coverage (n = 2) at 17%-18% w/w loading. Heat treatment seems to be beneficial for n 3: it increases the overall number N of exchanged electrons and improves the electrode wetting. For the most active samples, mixed Co(II)/Co(III) valencies were displayed

    Optimization and validation of multi-coloured capillary electrophoresis for genotyping of Plasmodium falciparum merozoite surface proteins (msp1 and 2)

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    BACKGROUND: Genotyping of Plasmodium falciparum based on PCR amplification of the polymorphic genes encoding the merozoite surface proteins 1 and 2 (msp1 and msp2) is well established in the field of malaria research to determine the number and types of concurrent clones in an infection. Genotyping is regarded essential in anti-malarial drug trials to define treatment outcome, by distinguishing recrudescent parasites from new infections. Because of the limitations in specificity and resolution of gel electrophoresis used for fragment analysis in most genotyping assays it became necessary to improve the methodology. An alternative technique for fragment analysis is capillary electrophoresis (CE) performed using automated DNA sequencers. Here, one of the most widely-used protocols for genotyping of P. falciparum msp1 and msp2 has been adapted to the CE technique. The protocol and optimization process as well as the potentials and limitations of the technique in molecular epidemiology studies and anti-malarial drug trials are reported. METHODS: The original genotyping assay was adapted by fluorescent labeling of the msp1 and msp2 allelic type specific primers in the nested PCR and analysis of the final PCR products in a DNA sequencer. A substantial optimization of the fluorescent assay was performed. The CE method was validated using known mixtures of laboratory lines and field samples from Ghana and Tanzania, and compared to the original PCR assay with gel electrophoresis. RESULTS: The CE-based method showed high precision and reproducibility in determining fragment size (< 1 bp). More genotypes were detected in mixtures of laboratory lines and blood samples from malaria infected children, compared to gel electrophoresis. The capacity to distinguish recrudescent parasites from new infections in an anti-malarial drug trial was similar by both methods, resulting in the same outcome classification, however with more precise determination by CE. CONCLUSION: The improved resolution and reproducibility of CE in fragment sizing allows for comparison of alleles between separate runs and determination of allele frequencies in a population. The more detailed characterization of individual msp1 and msp2 genotypes may contribute to improved assessments in anti-malarial drug trials and to a further understanding of the molecular epidemiology of these polymorphic P. falciparum antigens
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