929 resultados para Nucleophilic additions


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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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The characteristics, performance, and application of an electrode, namely, Pt vertical bar Hg vertical bar Hg-2(IBP)(2)vertical bar Graphite, where IBP stands for ibuprofenate ion, are described. This electrode responds to IBP with sensitivity of (58.6 +/- 0.9) mV decade 1 over the range 5.0 x 10(-5)-1.0 x 10(-1) mol L-1 at pH 6.0-9.0 and a detection limit of 3.8 x 10(-5) mol L-1. The electrode is easily constructed at a relatively low cost with fast response time (within 1530 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for ibuprofen in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used for the direct assay of ibuprofen in commercial tablets by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedure. (c) 2006 Elsevier B.V. All rights reserved.

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The effect of the addition of Cr and Nb on the microstructure and the electrochemical corrosion of the weldable, high-strength and stress corrosion cracking (SCC) resistant Al-5%Zn-1.67%Mg-0.23%Cu alloy (H) has been studied. Combined additions of the alloying elements, J (with Nb), L (with Cr) and O (with Cr and Nb) and different heat treatments, ST (cold-rolled), A (annealed), F (quenched), B (quenched and aged) and C (quenched in two steps and aged), to obtain different microstructures and hardness have been performed. To correlate the electrochemical corrosion with the microstructure of the specimens, corrosion potential (E(cor)) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O-2 or H2O2, the present alloys were polarized up to the pitting attack. It was shown that the E(cor) measurements were very sensitive to the alloy composition and heat treatment, increasing in the order H < J < L < O < Al (for a given heat treatment) and F < A approximate to ST < B < C (for a given alloy). The MgZn2 precipitates of the annealed (A) and cold-rolled (ST) specimens were dissolved in chloride solutions containing oxidizing agents and pitting attack was shown to develop in the cavities where the precipitates were present. In the specimens B and C, the compositions of the precipitate free zones was found to be equal to that of the matrix solid solution and preferential intergranular attack was not evident, this being in agreement with their SCC resistance. The addition of Cr and Nb increased the pitting corrosion resistance. The effects of Cr and Nb were additive, that of Cr being predominant, either, in the E(cor) shift or in the increase in the pitting corrosion resistance.

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The characteristics, performance, and application of an electrode, namely. Pt\Hg\Hg-2(Bzt)(2)\graphite, where Bzt stands for benzoate ion. are described. This electrode responds to Bzt with sensitivity of 57.7 +/- 1.0 mV/decade over the range 5 x 10(-4)-1 x 10(-1) mol l(-1) at pH 6.0-8.0 with a detection limit of 1.6 x 10(-4) mol l(-1). The electrode shows easy construction, fast response rime (between 10-30 s), low-cost, acid excellent response stability (lifetime > 6 months, in continuous use), the proposed sensor displayed good selectivity for benzoate in the presence of several carboxylate and inorganic anions. It was used to determine benzoate in various beverages by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by the official AOAC spectrophotometric method and by a HPLC procedure as well. (C) 2001 Elsevier B.V. B.V. All rights reserved.

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Flotation is a process of cell separation based on the affinity of cells to air bubbles. In the present work, flotability and hydrophobicity were determined using cells from different yeasts (Hansenulla polymorpha, Saccharomyces cerevisiae, Candida albicans), which were propagated in different media and at different temperatures. Alterations to the supernatant of the cells were also carried out before the flotation assays. The results described here indicate that supernatants of the yeast cells can play a more important role on flotation than cell-wall hydrophobicity. For example, wall-hydrophobicity of strain FLT-01 of S. cerevisiae was high but flotation did not occur when their washed cells were resuspended in water. Additions of neopeptone to cultures of S. cerevisiae and H. polymorpha repressed flotation and increased the volume of foam. An additional task of the present work was to show that the relationship between cell-wall hydrophobicity and flotation performance was dependent on the method used for the measurement of hydrophobicity. Based on the assay procedure, two types of hydrophobicity were distinguished: (a) the apparent hydrophobicity for cells suspended in the medium and expressed by the degree of cell affinity to the organic solvent in the two-phase system supernatant/hexane; (b) the standard hydrophobicity, which was determined for cells suspended in a standard solution (acetate buffer, in the present work) within the acetate buffer/hexane system. Flotation of cells of S. cerevisiae and C albicans were best related to the degree of apparent hydrophobicity (varying with the supernatant composition at the cell/medium interface) rather than to the degree of standard hydrophobicity (varying with the alterations in the wall components, since the liquid phase was constant in the assay). However, depending on the yeast unpredictable results can be obtained. For example, cells of H. polymorpha exhibited good flotation associated to a high degree of standard hydrophobicity while having a lower degree of apparent hydrophobicity. Concerning growth temperature, flotation of cells of C albicans was strongly repressed when the temperature was raised from 30 to 38 degreesC while a similar effect was not observed in cultures of S. cerevisiae and H. polymorpha. It is difficult to understand and predict flotation of yeast cells but simple modifications made to the supernatant of cultures can activate or repress flotation. (C) 2003 Elsevier B.V. B.V. All rights reserved.

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The characteristics, performance, and application of an electrode, namely, Pt\Hg\Hg-2(PABzt)(2)\ graphite, where PABzt stands for p-aminobenzoate ion, are described. This electrode responds to PABzt with sensivity of (58.1 +/- 1.0) mV per decade over the range 1.0 x 10(-4) to 1.0 x 10(-1) mol l(-1) at pH 6.5-8.0 and a detection limit of 3.2 x 10(-5) mol l(-1). The electrode shows easy construction, fast response time (within 10-30 s), low-cost, and excellent response stability (lifetime greater than 6 months, in continuous use). The proposed sensor displayed good selectivity for p-aminobenzoate in the presence of several substances, especially, concerning carboxylate and inorganic anions. It was used to determine p-aminobenzoate in pharmaceutical formulations by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by an HPLC procedure. (C) 2004 Elsevier B.V. All rights reserved.

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The physicochemical electronic characteristics of SnO2 render it useful in many technical applications, including ceramic varistors, stable electrodes used in electric glass-melting furnaces and electrometallurgy of aluminum, transparent windows and chemical sensors. The use of ZnO as a sintering aid was explored in this study to obtain SnO2 as a dense ceramic. Compacts were obtained by mechanical mixing of oxides, isostatic pressing at 210 MPa and sintering in situ inside a dilatometer at heating rates of 10degreesC/min. The grain size and microstructure were investigated by scanning and transmission electron microscopy (SEM/TEM). The phases and chemical composition were analyzed by energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The results indicated that ZnO acts as a densification aid for SnO2, improving its grain growth with additions of up to 2 mol%. ZnO forms a solid solution with SnO2 UP to 1 mol%, above which SnZnO3 precipitates in the grain boundary, potentially inhibiting shrinkage and grain growth. (C) 2004 Kluwer Academic Publishers

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The electrochemical reduction of benzenesulfinic, p-toluenesulfinic, and p-nitrobenzenesulfinic acids was studied in dimethylsulfoxide solutions. From cyclic voltammetry experiments, a chemical reaction following the first electron transfer was detected during the reduction process. A cyclic voltammetry technique using ultramicroelectrodes has provided kinetic parameters for the electron-transfer steps, from which it was possible to observe the influence of the ring substituent on the electrochemical reduction. The mechanism of the electroreduction of aromatic sulfinic acids in dimethylsulfoxide depends upon the nucleophilic attack of the radical anion produced on the starting compound during the reduction processes.

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A constructive heuristic algorithm to solve the transmission system expansion planning problem is proposed with the aim of circumventing some critical problems of classical heuristic algorithms that employ relaxed mathematical models to calculate a sensitivity index that guides the circuit additions. The proposed heuristic algorithm is in a branch-and-bound algorithm structure, which can be used with any planning model, such as Transportation model, DC model, AC model or Hybrid models. Tests of the proposed algorithm are presented on real Brazilian systems.

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The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

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We have used surface tension measurements, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and cryo-transmission electron microscopy (cryo-TEM) to investigate the dynamic and structural behavior of octadecyltrimethylammonium bromide (C(18)TAB) micelles in water and NaBr solution. The surface tension data for fixed C(18)TAB concentrations of 25 mM and varied NaBr additions (0-50 mM) shows that the critical micelle concentration (cmc) increases after an initial decrease at 0.5 mM NaBr. This unusual effect has been explained using results from DSC and DLS. At low salt concentrations (below ca. 25 mM) the relaxation time distribution is bimodal with a dominant fast mode due to spherical micelles. Above ca. 35 mM NaBr disklike structures are favored and the relaxation time distribution is more closely unimodal. The postulated sphere-to-disk transition is supported by cryo-TEM micrographs. A pronounced increase in the micellar effective hydrodynamic radius (R-H) is observed as the NaBr concentration is increased above about 35 mM; below 35 mM the R-H of the spherical micelles changes Little with ionic strength.

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Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

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The characteristics, performance, and application of an electrode, namely Pt| Hg|Hg-2(DCF)(2)|graphite, where DCF stands for diclofenac ion, are described. This electrode responds to diclofenac with sensitivity of (58.1 +/- 0.8) mV/decade over the range 5.0 x 10(-5) to 1.0 x 10(-2) Mol l(-1) at pH 6.5-9.0 and a detection limit of 3.2 x 10(-5) mol l(-1). The electrode is easily constructed at a relatively low cost with fast response time (within 10-30 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for diclofenac in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used to determine diclofenac in pharmaceutical preparations by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedures. (c) 2005 Elsevier B.V. All rights reserved.