144 resultados para electrodes modified
em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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This work describes the construction and application of two amperometric sensors for sensitive UV-filter determination. The sensors were prepared using stainless steel electrodes in which polyaniline (PANI) was electrochemically polymerized in the presence of nickel (NiPcTS) or iron (FePcTS) tetrasulfonated phthalocyanines. The sensor surface characterizations were carried out using atomic force microscopy (AFM). The PANI/NiPcTS sensor was selective for the chemical UV-filter p-aminobenzoic acid (PABA) and the PANI/FePcTS sensor was selective for octyldimethyl-PABA (ODP), both in a mixture of tetrahydrofuran (THF) and 0.1 mol L(-1) H(2)SO(4) at a volume ratio of 30 : 70, and with an applied potential of 0.0 mV vs. Ag vertical bar AgCl. A detailed investigation of the selectivity was carried out for both sensors, in order to determine their responses for ten different UV filters. Finally, each sensor was successfully applied to PABA or ODP quantification in sunscreen formulations and water from swimming pools.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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In this study we describe the electrochemical behavior of 5,10,15,20-tetrakis(2'-aminophenylporphyrin)manganese(III) chloride supported on a glassy carbon electrode, as well as the electrochemical preparation and characterization of thin films based on pyrrole-3-carboxylic acid. The electrocatalytic action of the electrode modified with the Mn(III) porphyrin toward an azo dye was tested, and the characteristic strong interaction between the incorporated metalloporphyrin and RR120 dye was verified. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.
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Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.
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The electrocatalytic oxidation of 1-propanol was investigated on platinum electrodes modified by submonolayers of Pb and Sn in acid media. An increase of oxidation rates observed for both Pb and Sn, and the influence of theta values was investigated. The values of the apparent activation energy evaluated from the Arrhenius plots concerning the electrochemical oxidation of 1-propanol on modified platinzed platinum electrodes, reveal a significant decrease in the presence of upd Sn and Ph adatoms. A decrease from 56 to 26 U mol(-1) in the presence of Sn. and from 78 to 25 U mol(-1) for Ph adatoms are some illustrative values which reflect the promoting effect of the upd adatoms.
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Interest in the electronic properties of carbon nanotubes has increased in recent years. These materials can be used in the development of electrochemical sensors for the measurement and monitoring of analytes of environmental interest, such as pharmaceuticals, dyes, and pesticides. This work describes the use of homemade screen-printed electrodes modified with multi-walled carbon nanotubes (MWCNT) for the electrochemical detection of the fungicide thiram. The electrochemical characteristics of the proposed system were evaluated using cyclic voltammetry, with investigation of the electrochemical behavior of the sensor in the presence of the analyte, and estimation of electrochemical parameters including the diffusion coefficient, electron transfer coefficient (α), and number of electrons transferred in the catalytic electro-oxidation. The sensor response was optimized using amperometry. The best sensor performance was obtained in 0.1 mol L-1 phosphate buffer solution at pH 8.0, where a detection limit of 7.9 x 10-6 mol L-1 was achieved. Finally, in order to improve the sensitivity of the sensor, square wave voltammetry (SWV) was used for thiram quantification, instead of amperometry. Using SWV, a response range for thiram from 9.9 x 10-6 to 9.1 x 10-5 mol L-1 was obtained, with a sensitivity of 30948 µA mol L-1, and limits of detection and quantification of 1.6 x 10-6 and 5.4 x 10-6 mol L-1, respectively. The applicability of this efficient new alternative methodology for thiram detection was demonstrated using analyses of enriched soil samples.
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The fabrication of supramolecular structures from the tetraruthenated porphyrin-containing phosphines, {TPyP[RuCl3(dppb)](4)}, RuTPyP, is demonstrated with Langmuir and Langmuir-Blodgett films. The surface pressure-molecular area isotherms (pi-A) point to an edge-on arrangement for the RuTPyP molecules in the condensed state. Weak aggregation in the Langmuir films was indicated by non-zero surface potentials at large areas per molecule and a slight red shift in the ultraviolet-visible absorption spectrum in comparison to the spectrum in solution. Further aggregation occurs in the Z-type Lang muir-Blodgett films, which was confirmed with ultraviolet-visible spectroscopy of the deposited films. Fourier transform infrared and Raman spectroscopic data for powder and Langmuir-Blodgett films indicate that the RuTPyP molecules are chemically stable in Langmuir-Blodgett films regardless of the contact with water during film fabrication. The nanostructured nature of the Langmuir-Blodgett films was manifested in cyclic voltammetry due to the high sensitivity of the metallic centers in RuTPyR Electrodes modified with Langmuir-Blodgett films exhibit an anodic peak at 100 mV and a cathodic peak at 7 mV, which is assigned to RuIII/RuII redox processes. Furthermore, Langmuir-Blodgett films from RuTPyP showed electrocatalytic activity for oxidation of benzyl alcohol, illustrated by a large shift of 100 mV in the anodic peak at 400 mV, while electropolymerized and cast films of the same compound displayed smaller and no activities, respectively.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Fractional factorial design and factorial with center point design were applied to the development of an amperometric biosensor for the detection of the hepatitis C virus. Biomolecules were immobilized by adsorption on graphite electrodes modified with siloxane-poly(propyleneoxide) hybrid matrix prepared using the sol-gel method. Several parameters were optimized, such as the streptavidin concentration at 0.01 mg mL(-1) and 1.0% bovine serum albumin, the incubation time of the electrodes in the complementary DNA solution for 30 minutes and a 1: 1500 dilution of the avidin-peroxidase conjugate, among others. The application of chemometric studies has been efficient, since the best conditions have been established with a restricted number of experiments, indicating the influence of different factors on the system.
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Langmuir films of a tetracarboxylic perylene derivative and polypyrrole display condensed surface pressure isotherms that are shifted when Cu2+ ions are added to the ultrapure water subphase. These films were transferred onto interdigitated gold electrodes leading to Y-type Langmuir-Blodgett (LB) films. The electrodes modified with 5-layer LB films were immersed into a flask with ultrapure water and water containing Cu2+ ions at concentrations ranging from mM to muM. Impedance measurements indicated a distinct electrical response for the two types of films. Although the materials chosen have no specificity for ionic metals, they can be combined for detecting trace levels of Cu2+, which may be exploited in water quality monitoring. (C) 2004 Elsevier B.V. All rights reserved.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Pós-graduação em Química - IQ
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)